WO2019039497A1 - Heating tool - Google Patents

Heating tool Download PDF

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Publication number
WO2019039497A1
WO2019039497A1 PCT/JP2018/030926 JP2018030926W WO2019039497A1 WO 2019039497 A1 WO2019039497 A1 WO 2019039497A1 JP 2018030926 W JP2018030926 W JP 2018030926W WO 2019039497 A1 WO2019039497 A1 WO 2019039497A1
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WO
WIPO (PCT)
Prior art keywords
sheet
layer
heat generating
cooling agent
heating
Prior art date
Application number
PCT/JP2018/030926
Other languages
French (fr)
Japanese (ja)
Inventor
穂貴 高桑
和俊 大塚
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201880054217.7A priority Critical patent/CN111031973A/en
Publication of WO2019039497A1 publication Critical patent/WO2019039497A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A61F7/03—Compresses or poultices for effecting heating or cooling thermophore, i.e. self-heating, e.g. using a chemical reaction

Definitions

  • the present invention relates to a heating tool.
  • a steam heater which comprises an oxidizable metal such as iron powder, an electrolyte such as sodium chloride and water, and utilizes the heat of oxidation generated by the oxidation reaction of the oxidizable metal.
  • a steam heating tool utilizes that it can supply a chemical
  • a steam heating implement for the purpose of alleviating this is disclosed. That is, from the viewpoint of alleviating a hot feeling by simultaneously imparting a warm feeling and a cool feeling, a heat generating tool in which a cooling agent such as menthol is contained in the heat generating portion is disclosed.
  • Patent Document 2 in the heating tool containing a chemical solution such as menthol, from the viewpoint of suppressing the delamination between the layer coated with the chemical solution and the layer coated with the heating element, By forming the area, a technique is disclosed that suppresses the delamination by utilizing the surface tension of the uncoated area and the heat generating layer.
  • the present invention A breathable first sheet, The second sheet, A heat generating layer disposed between the first sheet and the second sheet; A drug layer disposed between the heat generating layer and the second sheet; Equipped with The air permeability from the heat generating layer to the first sheet is configured to be higher than the air permeability from the heat generating layer to the second sheet,
  • the drug layer provides a heating tool comprising a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less.
  • FIG. 1 It is a sectional view showing a heating implement concerning an embodiment of the present invention. It is sectional drawing which shows the heat generating body concerning embodiment of this invention. It is a perspective view showing a heating element. It is a sectional view showing a part of exothermic part. It is a figure showing an example of a state where a user wears a heating implement.
  • Patent Document 2 focuses on delamination, and does not focus on such a user's request and does not sufficiently meet the request.
  • the air permeability is a value measured according to JIS P8117, and is defined as a time in which 100 ml of air passes an area of 6.45 cm 2 under a constant pressure.
  • the air permeability can be measured with an Oken type air permeability meter or a measuring instrument according thereto. That is, high air permeability means that the passage of air takes time, that is, air permeability is low. Conversely, low air permeability means high air permeability.
  • the basis weight means the mass with respect to the area in planar view of a heat-generating layer.
  • FIG. 1 is a cross-sectional view showing a heating implement according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing a heating element according to an embodiment of the present invention.
  • the heating implement 1 is disposed between the first sheet 11 having air permeability, the second sheet 12, and the first sheet 11 and the second sheet 12, and is disposed in parallel 2 Provided with two heating elements 18. That is, the heating implement 1 has an outer bag made of the first sheet 11 and the second sheet 12. Further, as shown in FIG.
  • the inner bag 17 which accommodates the heat-emitting part 20 in an inside.
  • the inner bag 17 is configured by joining the sheet 171 and the peripheral portion of the sheet 172.
  • the heating implement 1 includes the first sheet 11 having air permeability, the second sheet 12, the heat generating layer 13 disposed between the first sheet 1 and the second sheet 12, the heat generating layer 13 and the second layer. And a drug layer 16 disposed between the sheets 12.
  • the heating implement 1 is configured such 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 thermal steam generated in the heat generating layer 13 is less likely to be released to the outside from the second sheet 12 side, and preferentially released from the first sheet 11 side.
  • the thermal steam and the cooling agent can be effectively supplied to the skin of the user.
  • the first adhesive layer 14 and the second adhesive layer 15 are formed on the outer surface of the first sheet 11, and the release paper 21 is provided thereon.
  • the release paper 21 can be peeled off at the time of use of the heating tool 1, and the heating tool 1 can be fixed to the skin of the user by the first adhesive layer 14 and the second adhesive layer 15; It is suppressed that the tool 1 detaches from the user, and the user can be stably supplied with the thermal steam.
  • the heat generating portion 20 has a structure in which the base layer 10, the drug layer 16, the heat generating layer 13, and the water retaining layer 19 are laminated in this order.
  • the heat generating layer 13 generates steam when it generates 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, etc. ing.
  • the oxidizable metal is a metal that emits the heat of oxidation reaction, and examples thereof include powders and fibers such as iron, aluminum, zinc, manganese, magnesium, calcium, and mixed metals in which two or more of these are mixed.
  • the oxidizable metal preferably has an average particle diameter of 10 ⁇ m or more, more preferably 15 ⁇ m or more, and still more preferably 20 ⁇ m or more from the viewpoint of efficient oxidation reaction, when it is powdered. .
  • the average particle diameter of the oxidizable metal is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less, and still more preferably 150 ⁇ m or less.
  • the particle size of the oxidizable metal refers to the maximum length in the form of powder, and can be measured by classification with a sieve, dynamic light scattering method, laser diffraction method, etc., among which laser diffraction method It is preferable to measure.
  • the content of the oxidizable metal in the heat generating layer 13 is preferably 100 g / m in terms of basis weight from the viewpoint that the heat generating layer 13 can be raised to a desired temperature in the heating implement 1 provided with the drug layer 16. It is 2 or more, More preferably, it is 200 g / m ⁇ 2 > or more, More preferably, it is 300 g / m ⁇ 2 > or more, More preferably, it is 500 g / m ⁇ 2 > or more.
  • the content of the oxidizable metal in the heat generating layer 13 is preferably not more than 3,000 g / m 2, more preferably not more than 2,000 g / m 2, more preferably 1 , 500 g / m 2 or less.
  • the content of the oxidizable metal in the heat generating layer 13 can be determined by an ash content test according to JIS P8128 or a thermogravimeter.
  • when an external magnetic field is applied it can be quantified by a vibrating sample type magnetization measurement test or the like by utilizing the property of generating magnetization. Among them, it is preferable to use a thermogravimeter.
  • the carbon component has a water holding ability, an oxygen supplying ability, and a catalytic ability, and may use, for example, one or more materials selected from the group consisting of activated carbon, carbon black, acetylene black, and graphite. it can. Among them, activated carbon is preferably used because oxygen is easily adsorbed when wet. In addition, one or two or more types of fine powder or small particles selected from the group consisting of coconut shell charcoal, wood flour charcoal, and peat charcoal are more preferably used. Wood charcoal is more preferable from the viewpoint of facilitating the surface temperature of the heating element 18 to rise to a desired temperature.
  • the carbon component preferably has an average particle diameter of 10 ⁇ m or more, more preferably 12 ⁇ m or more, and still more preferably 15 ⁇ m or more, from the viewpoint of being uniformly mixed with the oxidizable metal. From the same viewpoint, the average particle diameter of the carbon component is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and still more preferably 100 ⁇ m or less.
  • the average particle size of the carbon component refers to the maximum length in the form of powder, and can be measured by a dynamic light scattering method, a laser diffraction method, etc., among which it is preferable to measure by a laser diffraction method. .
  • the carbon component is preferably in the form of powder, but may be in the form other than powder, for example, in the form of fiber.
  • the content of the carbon component in the heat generating layer 13 is preferably 1 part by mass or more with respect to 100 parts by mass of the content of the oxidizable metal from the viewpoint of sufficient supply of water to the heat generating layer 13. More preferably, it is 3 mass parts or more, More preferably, it is 6 mass parts or more.
  • the content of the carbon component in the heat generating layer 13 is preferably 40 parts by mass or less with respect to 100 parts by mass of the oxidizable metal from the viewpoint that oxygen supply to the heat generating layer 13 is sufficiently obtained. More preferably, it is 15 parts by mass or less, and more preferably 12 parts by mass or less.
  • the content of the carbon component in the heat generating layer 13 is preferably 10 g / m 2 or more, more preferably 20 g / m 2 or more, and still more preferably 25 g / m 2 or more in terms of basis weight. is there.
  • the content of the carbon component is preferably 400 g / m 2 or less, more preferably 250 g / m 2 or less, and still more preferably 120 g / m 2 or less, in terms of basis weight.
  • the content of water in the heat generating layer 13 is preferably 20 parts by mass or more, more preferably 30 parts by mass with respect to 100 parts by mass of the oxidizable metal, from the viewpoint of favorably advancing the oxidation reaction of the oxidizable metal. It is at least a part by mass, more preferably at least 40 parts by mass.
  • the content of water in the heat generating layer 13 is preferably 100 parts by mass or less, and more preferably 90 parts by mass or less, with respect to 100 parts by mass of the oxidizable metal, from the viewpoint of setting the highest temperature to a predetermined temperature or higher. More preferably, it is 80 parts by mass or less.
  • a part of water in the heat generating layer 13 becomes water vapor due to the temperature rise accompanying heat generation due to the oxidation reaction of the oxidizable metal.
  • a water absorbing agent can be contained in the heat generating layer 13 in order to retain moisture and efficiently advance the oxidation reaction of the oxidizable metal.
  • a polymer having water absorbency or a powder having water absorbency can be used as the water absorbing agent.
  • the polymer having water absorbability examples include hydrophilic polymers having a cross-linked structure capable of absorbing and holding a liquid 20 times or more of its own weight, and as powder having water absorbency, vermiculite, sawdust, silica gel, and pulp powder And at least one powder selected from the group consisting of
  • the content of the water absorbing agent is preferably 2 parts by mass or more, preferably 20 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass of water in the heat generating layer 13. It is more preferable that
  • the heat generating layer 13 can further contain a reaction accelerator.
  • a reaction accelerator By including a reaction accelerator, the oxidation reaction of the oxidizable metal can be easily sustained.
  • the oxide film formed on the oxidizable metal accompanying the oxidation reaction can be destroyed to promote the oxidation reaction.
  • the reaction accelerator includes, for example, one or more materials selected from the group consisting of alkali metal and sulfate or chloride of alkaline earth metal. Among them, various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride, and ferric chloride, and sodium sulfate from the viewpoint of excellent conductivity, chemical stability, and production cost. It is preferable to use one or more materials selected from the group.
  • a thickener When a thickener is included in the heat generating composition, it is possible to suppress a decrease in heat generating characteristics during storage of the heat generating body 18.
  • a substance which absorbs moisture to increase the consistency or which imparts thixotropy can be used, and alginates such as sodium alginate, gum arabic, gum tragacanth, locust Polysaccharide thickeners such as bean gum, guar gum, gum arabic gum, carrageenan, agar, and xanthan gum; starch thickeners such as dextrin, pregelatinized starch, and starch for processing; carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, Cellulose derivative thickeners such as hydroxymethyl cellulose and hydroxypropyl cellulose; metal soap thickeners such as stearates; mineral thickeners such as bentonite, etc. One or two or more selected from these can be used. .
  • the heat generating composition contains a phosphate
  • it has the effect of increasing the flowability of the heat generating composition, so that it becomes easy to manufacture when the heat generating layer 13 is manufactured by applying it to a substrate such as paper.
  • a phosphate 1 type or 2 types or more selected from a primary phosphate potassium salt, a secondary phosphate potassium salt, a tertiary phosphate potassium salt, a primary phosphate sodium salt, and a secondary phosphate sodium salt Can be used.
  • the heat generating layer 13 may be a powder or a molded product of powder, or may be a sheet, and in the present embodiment, it is a sheet of a rectangular shape (square, rectangle) in plan view.
  • the heat generating layer 13 is in the form of a sheet in this embodiment, the heat generating layer 13 may be in the form of powder or in the form of a sheet. However, it is preferable to be in the form of a sheet from the viewpoint of being excellent in the feeling in use.
  • the heat generating layer 13 for example, one obtained by wet forming a heat generating composition, one formed by pressing the heat generating composition, one formed by sandwiching the heat generating composition with the substrate layer 10 described later, heat generation What disperse
  • the basis weight of the base material layer 10 is preferably 10 g / m 2 or more and 200 g / m 2 or less, and more preferably 35 g / m 2 or more and 150 g / m 2 or less.
  • a sheet in which a hydrophilic layer 10 a and a liquid impermeable layer 10 b are laminated and laminated is used.
  • the hydrophilic layer 10a is a layer containing hydrophilic fibers. It is preferable that it is 20 to 99.9 mass%, and, as for the ratio of the hydrophilic fiber contained in the whole in the base material layer 10, it is more preferable that it is 50 to 99.5 mass%.
  • the hydrophilic fiber for example, it is preferable to use a cellulose fiber.
  • cellulose fiber chemical fiber (synthetic fiber) and natural fiber can be used.
  • rayon and acetate can be used as the chemical fiber of cellulose.
  • natural cellulose fibers include various plant fibers such as wood pulp, non-wood pulp, cotton, hemp, wheat straw, hemp, jute, kapok, coconut, and rag.
  • wood pulp is preferably used from the viewpoint that thick fibers can be easily obtained.
  • Examples of the resin constituting the liquid impermeable layer 10 b include resins such as polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrenes, nylons, polyvinylidene chlorides, and polyethylene-vinyl acetate copolymers.
  • resins such as polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrenes, nylons, polyvinylidene chlorides, and polyethylene-vinyl acetate copolymers.
  • a known laminating process can be used as a laminating method of the hydrophilic layer 10a and the liquid impermeable layer 10b.
  • 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 10 a is preferably on the side closer to the heat generating layer 13.
  • the drug layer 16 is composed of a cooling agent and a drug composition containing a solvent having a molecular weight of 1,000 or less. That is, it is different from the prior art in which the drug composition is impregnated into the heat generating portion. In addition, the drug layer 16 supplies the cooling agent to the user together with the thermal steam when the thermal implement 1 is used. The heating implement 1 can improve the volatilization of the cooling agent by including the drug layer 16.
  • the drug layer 16 is formed by any method, as shown in FIG. 2, when the heat generating portion 20 has the base layer 10, the drug layer 16 includes a cooling agent and a solvent having a molecular weight of 1,000 or less.
  • the drug composition is preferably formed on the substrate layer 10 by coating.
  • the surface of the base material layer 10 is covered with the drug layer 16.
  • covering it is not restricted to the case where it is continuous, and one part may be discontinuous.
  • a part of the cooling agent may penetrate into the inside of the base material layer 10 or the heat generating layer 13 adjacent to the drug layer 16. In this case, for example, the concentration of the cooling agent on the surface of the heat generating layer 13 in contact with the drug layer 16 is the highest.
  • the drug 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 instrumental analysis method.
  • the heat generation part 20 including the drug layer 16 can be analyzed in the cross-sectional direction using a three-dimensional measurement X-ray computed tomography (CT) apparatus, and can be confirmed by performing elemental analysis.
  • CT three-dimensional measurement X-ray computed tomography
  • the drug layer 16 is present on the side of the heat generating portion 20 on the side where the amount of the cooling agent is large, by infrared absorption spectroscopy.
  • menthol 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1,2-propanediol, and N-ethyl-3-p-menthancarboxamide
  • menthol 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1,2-propanediol, and N-ethyl-3-p-menthancarboxamide
  • One or two or more compounds selected from the group consisting of it becomes easy to maintain a cold sensation, and it is possible to improve the sensation of a cold sensation by combining an aroma. It is preferable that it is menthol from a viewpoint of raising the comfortable irritation
  • the cooling agent is dissolved in a solvent having a molecular weight of 1,000 or less described later.
  • cooling agent is something which acts on the skin, mucous membrane, etc. of the user to give the user a cold feeling, that is, a cold feeling.
  • the solvent having a molecular weight of 1,000 or less is preferably a polyhydric alcohol, and more preferably one or more selected from polyethylene glycol (PEG), glycerin and propylene glycol.
  • polyethylene glycol is preferable from the viewpoint of maintaining good volatilization of the cooling agent and obtaining good heat buildup, and from the viewpoint of improving the feeling of effect on the application site and obtaining a high immediate effect.
  • the molecular weight of the solvent is 1,000 or less, the viewpoint of obtaining good heat buildup, the viewpoint of being able to reduce the content of the cooling agent as much as possible, and effectively obtaining the comfortable stimulation by the cooling agent, From the viewpoint of maintaining the good volatility of the photosensitive agent, it is preferably 600 or less, and more preferably 450 or less.
  • the lower limit value is not particularly limited, but is preferably 50 or more, and more preferably 100 or more.
  • molecular weight as used in this specification means a weight average molecular weight, when distribution arises in molecular weight like polyethylene glycol.
  • PEG is contained in the heating element 18, the solvent in the heating element 18 is extracted by a solvent extraction method performed when determining the content of the solvent in the heating element 18 described later, and the extract is analyzed by GPC Identify the weight average molecular weight.
  • the content of the solvent having a molecular weight of 1,000 or less from the viewpoint of effectively obtaining a comfortable stimulus by the cooling agent while providing a good feeling of warmth immediately after the start of use, with the cooling agent in the pharmaceutical composition It is preferable that it is 30 mass% or more with respect to the total amount of this solvent, and it is more preferable that it is 50 mass% or more.
  • the content of the solvent having a molecular weight of 1,000 or less is relative to the total amount of the cooling agent and the solvent in the pharmaceutical composition from the viewpoint of imparting a comfortable stimulus by the cooling agent while securing safety.
  • the content is preferably 85% by mass or less, and more preferably 70% by mass or less.
  • the content of the solvent having a molecular weight of 1,000 or less is a heat generating layer from the viewpoint of effectively obtaining a comfortable stimulus by the cooling agent while imparting a good thermal sensation immediately after the start of use. It is preferable that it is 2.0 mg / cm ⁇ 2 > or more per unit area in planar view of 13, and it is more preferable that it is 4.0 mg / cm ⁇ 2 > or more.
  • the content of the solvent having a molecular weight of 1,000 or less per unit area in plan view of the heat generating layer 13 from the viewpoint of providing a comfortable stimulus by the cooling agent while securing safety.
  • the content of the solvent having a molecular weight of 1,000 or less is obtained 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 plan view. Further, the content of the solvent having a molecular weight of 1,000 or less contained in the heating element 18 can be determined by analyzing and quantifying the extract obtained by the solvent extraction method by gas chromatography. Specifically, the heating element 18 is taken out of the heating tool 1, and the heating element 18 is immersed in a solvent (preferably ethanol), and left sealed at room temperature for 9 hours while being sealed to obtain an extract. Thereafter, the extract obtained is analyzed by gas chromatography.
  • a solvent preferably ethanol
  • the content of the cooling agent relative to the area of the heat generating layer 13 in plan view is preferably 1.0 mg / cm 2 or more, more preferably 1.5 mg / cm 2 from the viewpoint of effectively obtaining a comfortable stimulus by the cooling agent.
  • the above more preferably 1.7 mg / cm 2 or more.
  • the content of the cooling agent relative to the area of the heat generating layer 13 in plan view is preferably from the viewpoint of providing a comfortable stimulus by the cooling agent while maintaining safety, and from the viewpoint of maintaining good heat generation characteristics. 6.0 mg / cm 2 or less, more preferably 4.5 mg / cm 2 or less, more preferably 3.2 g / cm 2 or less.
  • 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 in plan view.
  • the amount of cooling agent contained in the heating element 18 is quantified by analyzing the extract obtained by the solvent extraction method by gas chromatography. Specifically, the heating element 18 is taken out of the heating tool 1, the heating element 18 is immersed in a solvent (ethanol is preferred), sealed, and left at room temperature for 9 hours. The extract obtained in this way is analyzed by gas chromatography.
  • the weight ratio of the oxidizable metal to the cooling agent contained in the heating tool 1 is preferably 5 or more and 55 or less, and more preferably 10 or more and 50 or less. More preferably, it is 10 or more and 40 or less.
  • 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 more preferably 10 or more and 40 or less from the viewpoint of obtaining effect and immediate effect more effectively. It is more preferable that it is the following.
  • the volatilization amount of the cooling agent is, for example, 1 mg / 2 hours or more and 5 mg / 2 hours or less. It is preferably 1.3 mg / 2 hours or more from the viewpoint of obtaining a feeling of effect on pain by a cooling agent and immediate effect, and is preferably 1.7 mg / 2 hours or more from the viewpoint of obtaining a gingin feeling. More preferably, it is 1.9 mg / 2 hours or more.
  • the volatilization amount of the cooling agent is preferably from the viewpoint of providing a comfortable stimulus by the cooling agent while maintaining safety and maintaining good heat generation characteristics to improve the feeling of effect and the immediate effect. It is 3.5 mg / 2 hours or less, more preferably 3.0 mg / 2 hours or less, still more preferably 2.8 mg / 2 hours.
  • the volatilization amount of the cooling agent can be measured as follows. First, a 15 cm ⁇ 25 cm polyvinyl fluoride resin gas collection bag (Tedlar (registered trademark) bag) containing a sufficient amount of air to cause an oxidation reaction between the heating element 18 containing a cooling agent or the heating implement 1. Dupont Co., Ltd. is prepared, one end of the gas collection bag is connected to the air supply source, and the discharge port of the other end is immersed in ethanol at the tip of the tube connected to the discharge port. Next, the heating element 18 or the heating tool 1 containing a cooling agent is taken out from the oxygen blocking bag, put in the gas collecting bag, and placed on a hot plate set at 35 ° C. for 2 hours.
  • Tedlar registered trademark
  • the pharmaceutical composition may contain other components as long as the effects of the present invention are not impaired.
  • the drug composition preferably contains substantially no surfactant.
  • the phrase “not substantially contained in the drug composition” means that the content of the target compound in the drug layer is preferably relative to the total amount of the cooling agent and the solvent having a molecular weight of 1,000 or less. Less than 0.1%, more preferably less than 0.01%, more preferably not contained in the drug layer.
  • the water-retaining layer 19 contains moisture, which enables it to supply thermal steam and maintain its heat generation characteristics well.
  • the content of water contained in the water retention layer 19 is preferably 10 to 45% by mass, more preferably 12 to 40% by mass, and more preferably 13 to 30% by mass of the maximum water absorption amount of the water retention layer 19. Even when the heat generating composition is filled in a large amount in one heat generating portion 20 for some reason or unevenly distributed in a specific place at a large amount at the time of manufacturing the heat generating portion 20, abnormal heat generation is prevented and good. It is further preferable in that the heat generation characteristics can be stably obtained.
  • the content of water contained in the water retention layer 19 is preferably 12% by mass or more of the maximum water absorption amount of the water retention layer 19, and more preferably 13% by mass or more. Moreover, it is preferable that it is 40 mass% or less, and, as for content of the water contained in the water holding layer 19, it is more preferable that it is 30 mass% or less.
  • the maximum water absorption can be measured as follows.
  • the water-retaining layer 19 preferably has water absorbency capable of absorbing and holding 10 to 45% by mass of water of the maximum water absorption amount, regardless of the presence or absence of the air permeability, but preferably the one having the air permeability.
  • the air permeability of the water-retaining layer 19 in the state of absorbing 10 to 45% by mass of the maximum water absorption is preferably 500 seconds / 100 ml or less, and more preferably 1 to 300 seconds / 100 ml. With such an air permeability, air permeability of the heat generating portion 20 is sufficiently ensured, so that oxygen supply is sufficiently obtained, high heat generation efficiency is obtained, and oxidation reaction of the oxidizable metal becomes good. Also, it may be possible to generate a large amount of water vapor. Further, it is more preferably 300 seconds / 100 ml or less, and from the viewpoint of preventing an excessive temperature rise, it is more preferably 1 second / 100 ml or more.
  • FIG. 4 shows an example in which the heat retention layer 13 and the water retention layer 19 are laminated, and the material including the component (a) fiber material and the component (b) water absorbent polymer is used as the water retention layer 19.
  • the water retaining layer 19 is formed of a water absorbing sheet 102.
  • the heat generating layer 13 shows the oxidizable metal (M) and the carbon component (C).
  • the water retention layer 19 may be composed of a sheet containing the component (a), for example, a single fiber sheet, or two or more layers may be laminated.
  • a fiber sheet the paper, the nonwoven fabric manufactured from the fiber material mentioned later, or what laminated paper and a nonwoven fabric etc. are mentioned.
  • the sheet containing the component (a) may be a sheet material such as paper or non-woven fabric in which a fiber material is laminated or laminated on a material having no water absorbency such as polyethylene fiber, polypropylene fiber, polyethylene sheet, polypropylene sheet, It may be a sheet material such as paper making, non-woven fabric, etc., in which another fiber material is laminated or mixed with fiber material such as pulp fiber or rayon fiber.
  • the content of water contained in the water retention layer 19 can be easily adjusted, the water content in the heat generation layer is made appropriate, and good heat buildup and warmth It is preferable from the point of maintaining well.
  • the water retention layer 19 may further contain the component (b).
  • the form of the water retaining layer 19 is (i) one sheet in which the component (a) and the component (b) are uniformly mixed, (ii) the component Among the same or different sheets including (a), those in which the component (b) is disposed, and (iii) those in which the component (b) is dispersed to form a sheet can be exemplified.
  • the water content of the heat generating layer 13 can be easily controlled, the water content of the water holding layer 19 can be easily adjusted, and the preferable amount is the form of (ii) belongs to.
  • the water retention layer 19 of the form of (ii) spreads the component (b) uniformly on the sheet
  • any of hydrophilic fibers and hydrophobic fibers can be used, but it is preferable to use hydrophilic fibers.
  • using cellulose fibers promotes the water transfer to the water retention layer 19, It is more preferable from the point of being easy to adjust the content of the water contained in the water retention layer 19, to make the water content in the heat generating layer appropriate, and to favorably maintain the rise of good heat generation and the warm feeling.
  • a cellulose fiber a chemical fiber (synthetic fiber) or a natural fiber can be used.
  • cellulose fibers for example, rayon and acetate can be used as chemical fibers.
  • natural fibers among cellulose fibers include, for example, various plant fibers, wood pulp fibers, non-wood pulp fibers, cotton fibers, hemp fibers, wheat straw fibers, hemp fibers, jute fibers, kapok fibers, palm fibers, and One or more selected from rag fiber can be used.
  • using wood pulp fibers makes it easy to adjust the content of water contained in the water retaining layer 19, makes the amount of water in the heat generating layer appropriate, and makes the rise of heat generation and the sense of warmth favorable. It is preferable from the point of sustaining.
  • the fiber length of various fiber materials is preferably 0.5 to 6 mm, and more preferably 0.8 to 4 mm.
  • the fiber length of the fiber material is preferably 0.5 mm or more, and more preferably 0.8 mm or more.
  • the fiber length of the fiber material is preferably 6 mm or less, more preferably 4 mm or less.
  • the water-retaining layer 19 may contain hydrophobic fibers, particularly heat-fusible fibers, if necessary.
  • the content of the heat-fusible fiber is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, with respect to the total amount of fibers in the water retention layer 19.
  • the content of the heat-fusible fiber is preferably 0.1% by mass or more with respect to the total amount of fibers in the water retention layer 19, and more preferably 0.5% by mass or more.
  • the content of the heat-fusible fiber is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of fibers in the water retention layer 19.
  • the content of water contained in the water retention layer 19 by using, as the component (b), a hydrophilic polymer having a crosslinked structure capable of absorbing and holding a liquid 20 times or more its own weight, as in the above component (a) Can be properly adjusted.
  • a shape of a component (b) 1 type (s) or 2 or more types selected from spherical shape, lump shape, grape-tuft shape, and fibrous form are mentioned.
  • the average particle diameter of the component (b) is preferably 1 to 1000 ⁇ m, and more preferably 10 to 500 ⁇ m.
  • the average particle diameter of the component (b) is preferably 1 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the average particle diameter of the component (b) is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m 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.
  • component (b) examples include, for example, starch, crosslinked carboxylmethylated cellulose, a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid, polyacrylic acid and its salt, and polyacrylate graft weight 1 type, or 2 or more types selected from union are mentioned.
  • polyacrylic acid and its salt and polyacrylate graft polymer such as a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid, adjustment of the content of water contained in water retention layer 19 It is preferable from the viewpoint of facilitating peeling, making the amount of water in the heat generating layer appropriate, and maintaining good heat build-up and warm feeling favorably.
  • the proportion of the component (b) in the water retaining layer 19 is preferably 10 to 70% by mass in the dry state, and further 20 to 65% by mass promotes rapid water transfer to the water retaining layer 19
  • the water content of the water retention layer 19 can be easily adjusted, and the amount of water in the heat generation layer can be appropriately adjusted, which is preferable from the viewpoint of maintaining good rising of heat generation and good feeling of warmth.
  • the proportion 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 70% by mass or less in the dry state. It is preferable that it is 65 mass% or less.
  • the water retaining layer 19 is easy to adjust the content of water contained in the water retaining layer 19 and makes the amount of water in the heat generating layer appropriate, and in order to maintain good rising heat generation and a good sense of warmth,
  • the basis weight is preferably 20 to 200 g / m 2 , more preferably 35 to 150 g / m 2 , and still more preferably 50 to 140 g / m 2 .
  • the basis weight of the component (b) contained in the water retention layer 19 makes it easy to adjust the content of water contained in the water retention layer 19, makes the water content in the heat generation layer appropriate, and makes good heat buildup and warmth It is preferably 5 to 150 g / m 2 in a dry state, more preferably 10 to 100 g / m 2 , and still more preferably 30 to 90 g / m 2 from the viewpoint of maintaining excellently.
  • the water retention layer 19 preferably has a basis weight of 20 g / m 2 or more in a dry state, more preferably 35 g / m 2 or more, and still more preferably 50 g / m 2 or more.
  • the water retention layer 19 preferably has a basis weight of 200 g / m 2 or less in a dry state, more preferably 150 g / m 2 or less, and still more preferably 140 g / m 2 or less.
  • the basis weight of the component (b) contained in the water retention layer 19 is preferably 5 g / m 2 or more, more preferably 10 g / m 2 or more, and more preferably 30 g / m 2 or more in the dry state. It is further preferred that The water retention layer 19 preferably has a basis weight of 150 g / m 2 or less in a dry state, more preferably 100 g / m 2 or less, and still more preferably 90 g / m 2 or less.
  • the water retaining layer 19 may have the heat generating layer 13 formed on one side of the water retaining layer 19 as shown in FIG. 4 or may have the heat generating layer 13 formed on both sides of the water retaining layer 19. .
  • the base layer 10 is prepared, and a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less is coated on the base layer 10 to form the drug layer 16.
  • the coating method of the drug composition is not particularly limited, and a die coater, roller coating, screen printing, roller gravure, knife coating, curtain coater, or the like may be used.
  • the viscosity of the drug composition in the vicinity of the coating temperature is preferably 5 to 100 mPa ⁇ s, and it is preferably 10 to 50 mPa ⁇ s from the viewpoint of ease of coating and the spreadability of the chemical solution. preferable.
  • the viscosity under the conditions of 50 ° C. and 50 RH be in the above-mentioned range as a pharmaceutical composition.
  • the measurement of the said viscosity is performed at 60 rpm of rotor rotational speeds using the No. 4 rotor of a Brookfield viscometer.
  • the heat generating layer 13 is a coating layer of the heat generating composition.
  • the coating method of the heat-generating powder water dispersion is not particularly limited, and examples thereof include a die coater and the like.
  • the heat-generating powder water dispersion can be obtained by 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 components mentioned above at one time, the reaction accelerator is previously dissolved in a solution in which a thickener is dissolved in water to prepare an aqueous solution. Then, a pre-mixed oxidizable metal and carbon component may be mixed with the aqueous solution.
  • the water retention layer 19 is formed on the heat generating layer 13, whereby the heat generating portion 20 is manufactured.
  • the formation method of the water holding layer 19 is not specifically limited, For example, you may distribute the layer containing the particle
  • the heat generating portion 20 in which the drug layer 16 is formed between the base layer 10 and the heat generating layer 13 can be manufactured.
  • the heat generating body 18 includes a heat generating portion 20 and an inner bag 17 accommodating the heat generating portion 20 therein.
  • the inner bag 17 is configured by joining the sheet 171 and the peripheral portion of the sheet 172.
  • An area other than the sheet 171 and the peripheral portion of the sheet 172 is a non-joining area, and the heat generating layer 13 is disposed in the non-joining area.
  • the sheet 171 is disposed closer to the skin than the heat generating layer 13 when the user wears the heating implement 1 on the skin.
  • the sheet 171 is a breathable sheet, and the air permeability thereof is preferably 40,000 seconds / 100 ml or less, more preferably 25,000 seconds / 100 ml or less.
  • the air permeability of the sheet 171 is preferably 10 seconds / 100 ml or more, and more preferably 100 seconds / 100 ml or more.
  • the sheet 171 having such an air permeability for example, it is preferable to use a porous sheet made of a synthetic resin having moisture permeability but not water permeability. Specifically, a film obtained by containing calcium carbonate or the like in polyethylene and stretched can be used.
  • the sheet 172 When the user wears the heating tool 1 on the skin, the sheet 172 is located on the side farther than the heat generation layer 13 than the skin. It is preferable that the air permeability of the sheet 172 be higher than the air permeability 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, from the viewpoint of capturing oxygen little by little and maintaining good heat generation characteristics, and more preferably 85,000 seconds. It is more preferable that the amount be less than / 100 ml.
  • 50,000 seconds / 100 ml or more is preferable, and 60,000 seconds / 100 ml or more is more preferable.
  • the sheet 172 having such air permeability for example, it is preferable to use a porous sheet made of a synthetic resin having moisture permeability but not water permeability. Specifically, a film obtained by containing calcium carbonate or the like in polyethylene and stretched can be used.
  • the breathability of the entire sheet layer configured of the second sheet 12 and the sheet 172 is configured of the first sheet 11, the sheet 171, and the base material layer 10. Is lower than the breathability of the entire sheet layer.
  • the second sheet 12 is the outermost layer
  • the air permeability of the entire sheet layer from the second sheet 12 to the heat generating layer 13 is the first sheet 11 as the outermost layer
  • the first sheet 11 to the heat generating layer 13 It is higher than the air permeability of the entire sheet layer.
  • 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.
  • planar shape of the heat generating body 18 is preferably a rectangular shape, 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 heat generating body 18 may be fixed to the second sheet 12 by an adhesive such as a hot melt adhesive. Thus, movement of the heat generating body 20 can be suppressed in the outer bag.
  • the surface maximum temperature of the heat generating body 18 is preferably 36 ° C. or more, more preferably 38 ° C. or more, and still more preferably 41 ° C., from the viewpoint of achieving both warmth and coolness comfortable for the user. It is above. Further, the surface maximum temperature of the heating element 18 is preferably 60 ° C. or less, more preferably 55 ° C. or less, and still more preferably 50 ° C. or less, from the viewpoint of giving a comfortable warmth to the user. The surface maximum temperature can be measured using a measuring device in accordance with JIS S4100.
  • the heating implement 1 has a laterally long shape having a longitudinal direction X and a width direction Y orthogonal to the longitudinal direction X in a plan view from the first sheet 11 side. As described above, by making the heating tool 1 into a horizontally long flat shape in plan view from the first sheet 11 side, the heating tool 1 can be attached so as to extend in the left-right direction of the user it can.
  • first sheet 11 and the second sheet 12 may be configured as separate sheets, and the outer peripheral edge may be pasted together to configure a bag body.
  • second sheet 12 may be configured as a series of sheets, the series of sheets may be folded, and the bag body may be configured by bonding the opposing outer peripheral edges to each other.
  • the first sheet 11 is positioned on the skin side of the user when the user wears the heating implement 1.
  • the first sheet 11 is a breathable sheet, and the air permeability thereof is 8000 seconds / 100 ml or less.
  • the air permeability of the first sheet 11 is 6,000 seconds / 100 ml or less and 1,000 seconds / 100 ml or less Is more preferred.
  • the lower limit value of the air permeability of the first sheet 11 is not particularly limited. However, in consideration of the basis weight and the like for preventing the inner bag 17 positioned inside the first sheet 11 from being seen through, in particular, it is preferably 1 second / 100 ml or more.
  • a fiber sheet including non-woven fabric can be used as the first sheet 11.
  • the second sheet 12 is configured of a sheet having the same air permeability as the first sheet 11.
  • the heating tool 1 may be configured to be extensible and contractable at least in the X-axis direction.
  • the first sheet 11 and the second sheet 12 may be the above-described breathable and stretchable sheets that expand and contract in the X-axis direction.
  • the stretch sheet include synthetic fibers selected from polyesters such as polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), polyamides, polyacrylics, etc .; cellulose, silk, cotton, wool, etc.
  • the stretch sheet is selected from air through method, spun bond method, needle punch method, melt blown method, card method, heat fusion method, water entanglement method, solvent adhesion method using two or more kinds of fibers.
  • Nonwoven fabrics produced by the method can also be used.
  • non-woven fabrics knitted fabrics can also be used.
  • the non-woven fabric having elasticity an air through non-woven fabric or a spun-bonded non-woven fabric containing elastic fibers (for example, polyurethane, polyester) as constituent fibers is preferable, and from the viewpoint of texture the non-woven fabric is surface-treated with silicone or surfactant It can also be used.
  • the first sheet 11 and the second sheet 12 may be stretchable sheets made of the same material, or may be stretchable sheets made of different materials.
  • 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 for attaching the heating implement 1 to the skin of the user.
  • the first adhesive layer 14 is a pair, and the pair of first adhesive layers 14 extend in one direction parallel to the outer surface of the first sheet 11 and are spaced apart, preferably in the X-axis direction of the first sheet 11 Are arranged at the ends of the In a plan view from the outer surface side of the first sheet 11, the pair of first adhesive layers 14 preferably do not overlap with the heat generating layer 13 from the viewpoint of heat generation characteristics.
  • the second adhesive layer 15 is disposed in the region between the pair of first adhesive layers 14 in a plan view from the first sheet 11 side, and extends in the same direction following the first adhesive layers 14. There is.
  • the second adhesive layer 15 has a rectangular shape in plan view 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 one or more selected from an acrylic resin, a vinyl acetate resin, and an olefin resin to the outer surface of the first sheet 11 It is formed.
  • the above-mentioned heating implement 1 be enclosed in an oxygen barrier bag.
  • the oxygen barrier bag is opened and the heating tool 1 is taken out. Thereafter, the release paper 21 is removed, and the heating implement 1 is attached to the back side of the user's neck by the first adhesive layer 14 and the second adhesive layer 15. As a result, the heating implement 1 is fixed to the user.
  • the oxidizable metal in the heat generating layer 13 contacts air, the oxidizable metal is oxidized and the heat generating layer 13 generates heat. As the heat generating layer 13 generates heat, the water in the heat generating layer 13 evaporates to generate steam. The vapor is released to the outside of the heating implement 1 through the base material layer 10, the sheet 171, and the first sheet 11. In addition, when the base material layer 10 is not provided in the heat generating body, the vapor 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-ventilated layer, the steam generated in the heat generating layer 13 is blocked by the sheet 172 and hardly released from the second sheet 12 to the outside. Thereby, the steam can be released preferentially from the sheet 171, and the steam can be reliably supplied to the skin of the user.
  • the heating implement 1 appropriately makes the volatilization behavior of the cooling agent with respect to the heat generation behavior, which is the idea of the present inventors, and the effect thereof will be described.
  • the heating tool 1 of the present invention does not uniformly spread the cooling agent over the entire heating portion with a solvent or surfactant like the heating tool described in Patent Document 1, but generates heat.
  • the drug layer 16 is provided separately from the layer 13.
  • the medicine layer 16 being arrange
  • the rise of the heat generation temperature as described above becomes favorable, and the speed of rise of the heat generation temperature and the speed of the initial volatilization rate of the cooling agent are appropriate. It is considered to be a combination of In the present invention, in addition to this, the effect of improving the volatilization amount of the cooling agent is also obtained, and by combining all of them, the sense of effect on the application site of coli, fatigue and pain is improved, and the immediate effect is high. It is estimated that the effect which can not be obtained conventionally can be obtained. Furthermore, a gingin sensation can be obtained by the cooling agent, and the user's satisfaction is enhanced.
  • the details of 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 unclear, but the higher the molecular weight of the solvent, the more the solvent becomes an oxidizable metal in the heat generating layer 13 As a result of acting on the carbon component to easily inhibit the oxidation reaction, the rising temperature at the onset of heat generation of the heating tool 1 is decreased, while the molecular weight of the solvent is reduced to 1,000 or less. It is believed that the decrease can be suppressed as well as the decrease in the volatilization amount and rate of the cooling agent.
  • the cooling agent is adsorbed to the water retention layer 19 between the heat generating layer 13 and the first sheet by arranging the drug layer 16 between the heat generating layer 13 and the second sheet 12. It can suppress that the water retention capacity of the water retention layer 19 falls. As a result, good heat generation can be stably obtained. Further, by arranging the drug 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 favorably maintained. . In other words, it is possible to suppress that the cooling agent exuded from the drug layer 16 acts on the first adhesive layer 14 and the second adhesive layer 15 to reduce the adhesiveness.
  • the sheet 172 is the non-permeable layer in the above embodiment, for example, either one of the second sheet 12 and the sheet 172 may be the non-permeable layer, or both may be the non-permeable layer. .
  • a non-air-permeable sheet may be disposed inside the inner bag 17.
  • a non-air-permeable sheet is disposed closer to the sheet 172 than the heat generating layer 13.
  • the non-air-permeable sheet preferably covers the entire heat generating layer 13 in a plan view from the second sheet 12 side.
  • the second sheet 12 and the sheet 172 may be non-ventilated layers or ventilated layers.
  • both ends of the first adhesive layer 14 and both ends of the second adhesive layer 15 reach the outer peripheral edge of the first sheet 11 in plan view from the first sheet side.
  • it is not limited to this.
  • the heating implement 1 may have other fixing portions, such as installing stretchable ear hooks at both ends of the heating implement 1.
  • the heat-generating layer 13 was accommodated in the inner bag 17, the inner bag 17 may not be.
  • the first sheet 11 may be included, and the ventilation layer for supplying air to the heat generating layer 13 may be configured of one first sheet 11.
  • the configuration of the heating tool can be simplified.
  • the heating implement 1 was stuck on the back side of the neck, you may stick not only to this but on the skin surface of the other site
  • the present invention further discloses the following heating implement regarding the embodiment mentioned above.
  • the heating agent, wherein the drug layer comprises a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less.
  • the heating implement according to ⁇ 1> having a water retention layer between the heat generation layer and the first sheet.
  • the cooling agent is preferably menthol, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1,2-propanediol, and N-ethyl-3-p.
  • the content of the solvent is preferably 30% by mass or more and 85% by mass or less based on the total amount of the cooling agent and the solvent in the pharmaceutical composition. The heating implement as described in any one.
  • ⁇ 5> The heating implement according to any one of ⁇ 1> to ⁇ 4>, wherein the solvent preferably contains a polyhydric alcohol.
  • the solvent is preferably one or more selected from polyethylene glycol, glycerin and propylene glycol.
  • ⁇ 7> The heating implement according to any one of ⁇ 1> to ⁇ 6>, wherein the molecular weight of the solvent is preferably 600 or less.
  • a content of the cooling agent with respect to an area in plan view of the heat generating layer is preferably 1.0 mg / cm 2 or more.
  • ⁇ 9> Content relative to the area in plan view of the heat generating layer of the cooling agent preferably is 6.0 mg / cm 2 or less, ⁇ 1> to warming device according to any one of ⁇ 8>.
  • a content of the solvent is preferably 20.0 mg / cm 2 or less per unit area of the heat generating layer in a plan view.
  • ⁇ 12> The heating implement according to any one of ⁇ 1> to ⁇ 11>, wherein the pharmaceutical composition is preferably substantially free of a surfactant.
  • the heat generating layer preferably comprises an oxidizable metal, a water absorbing agent, and water.
  • the heat generating layer preferably contains a thickener.
  • the oxidizable metal is represented by a basis weight, preferably 100 g / m 2 or more and 3,000 g / m 2 or less.
  • the heat generating layer is preferably a coating layer of a heat generating composition.
  • the air permeability from the heat generating layer to the second sheet is preferably 80,000 seconds / 100 ml or more.
  • the heat generating portion has an inner bag, and among the sheets constituting the inner bag, the air permeability of the sheet disposed on the side farther from the skin than the heat generating layer is arranged closer to the skin than the heat generating layer.
  • the air permeability of the sheet disposed on the skin side of the heat generating layer is preferably 40,000 seconds / 100 ml or less and 10 seconds / 100 ml or more, according to ⁇ 18>.
  • the air permeability of the sheet disposed on the side farther from the skin than the heat generating layer is preferably 50,000 seconds / 100 ml or more and 150,000 seconds / 100 ml or less.
  • the heating element is laminated in the order of the base material layer, the drug layer, and the heat generating layer, and the base material layer is disposed to be located on the side farther from the skin than the heat generating layer ⁇ 1> to ⁇ 20>
  • a heat generating body is laminated in the order of the base material layer, the drug layer, the heat generation layer, and the water retention layer, and the base material layer is disposed to be farther from the skin than the heat generation layer, the water retention layer
  • the heating implement according to any one of ⁇ 2> to ⁇ 21>, which is disposed so as to be located on the skin side of the heat generating layer.
  • ⁇ 23> The heating implement according to any one of ⁇ 1> to ⁇ 22>, wherein the volatilization amount of the cooling agent after the start of heat generation of the heat generation layer is preferably 1 mg / 2 hours or more and 5 mg / 2 hours or less.
  • ⁇ 25> The heating implement according to any one of ⁇ 1> to ⁇ 24>, preferably having an adhesive layer on the side opposite to the heat generating layer side of the first sheet.
  • a breathable first sheet The second sheet, A heat generating layer disposed between the first sheet and the second sheet; A drug layer disposed between the heat generating layer and the second sheet; Equipped with A heating element is laminated in order of a base material layer, the drug layer, and the heat generating layer, The base material layer is disposed to be farther from the skin than the heat generating layer, The air permeability from the heat generating layer to the first sheet is configured to be higher than the air permeability from the heat generating layer to the second sheet,
  • the drug layer contains menthol as a cooling agent, and comprises a drug composition containing menthol and a solvent having a molecular weight of 1,000 or less, The said solvent is 30 mass% or more and 85 mass% or less with respect to the total amount of the said cooling agent and the said solvent,
  • the heating implement wherein the weight ratio of the cooling agent to the metal to be oxidized contained in the heat generating layer is 5 or more and 55 or less.
  • ⁇ 27> It is a usage method of the heating implement in any one of ⁇ 1> thru
  • ⁇ 28> The usage method of a heating implement as described in ⁇ 27> which applies thermal steam to a user's skin.
  • a heating tool having a structure as shown in FIG. 1 was produced as follows.
  • Example 1 [Preparation of Heated 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 parts by mass of a thickener were prepared and adjusted in the following procedure.
  • a thickener is dissolved in water, then a reaction accelerator is dissolved to prepare an aqueous solution, while a powder in which an oxidizable metal and a carbon component are pre-mixed is prepared, and the pre-mixed powder is added to the aqueous solution, The mixture was stirred for 10 minutes at 150 rpm with a disk turbine type stirring blade to obtain a slurry of a heat-generating powdery water dispersion.
  • Oxidizable metal Iron powder (iron powder RKH, average particle diameter 45 ⁇ m, manufactured by Dowa IP Creation Ltd.) Carbon component: Activated carbon (Carborafin, average particle size 40 ⁇ m, manufactured by Nippon Envirochemicals Co., Ltd.)
  • Water Tap water reaction promoter: Sodium chloride (general method sodium chloride, manufactured by Otsuka Chemical Co., Ltd.) Thickener: Xanthan gum (Echo Gum BT, DSP Gokyo Food & Chemical Co., Ltd.)
  • a solvent in which a cooling agent is dissolved according to the composition shown in Table 1 is applied (coating amount 60 g / m 2 ), and the above heat is generated on the coated surface.
  • the powder water dispersion was applied in the range of 25 cm 2 (5 cm ⁇ 5 cm) in an amount of 600 g / m 2 .
  • the above-described polymer sheet was disposed on the formed heat generating layer to produce a heat generating portion which is a laminated structure.
  • the air permeability of the first sheet (air permeable sheet placed on the skin side) is 16,000 seconds / 100 ml
  • the air permeability of the second sheet (non air permeable sheet) is 80,000 seconds / 100 ml or more
  • the heat generating part was put in a certain inner bag, and the peripheral part was hermetically sealed. At this time, the heat generating layer was disposed such that the substrate layer side was positioned on the second sheet side. Thus, a heating element was obtained.
  • Needle punched non-woven fabric (air permeability 1 second / 100 ml, basis weight 80 g / m 2 ) is used as the first sheet, and spun bonded non-woven fabric (air permeability 1 second / 100 ml, basis weight 38 g / m 2 ) as the second sheet It was used.
  • two heating elements were spaced apart and arrange
  • Examples 2 to 8 A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used.
  • a raw material composition is as follows. ⁇ Composition of raw material composition> ⁇ Oxidizable metal: Iron powder, manufactured by Dowa IP Creation Co., Ltd., trade name "RKH”: 83% -Fibrous material: Pulp fiber (Fletcher Challenge Canada, trade name: NBKP "Mackenzi (adjusted to 200 ml of CSF)"): 8% ⁇ Reaction accelerator: Activated carbon (made by Nippon Enviro Chemicals Co., Ltd., trade name "Carborafin", average particle diameter 45 ⁇ m) 9%
  • the obtained molded sheet was cut into 49 mm ⁇ 49 mm, three sheets were stacked, and the electrolytic solution was injected so that the amount of the electrolytic solution (5% saline solution) was 45 parts with respect to 100 parts of the molded sheet. Then, the solvent which melt
  • Comparative Example 3 A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used, and the cooling agent was positioned as shown in Table 1. Specifically, after applying the above-mentioned heat-generating powdery water dispersion on a 25 cm 2 (5 cm ⁇ 5 cm) polyethylene laminated paper in an amount of 600 g / m 2 in the range of 25 cm 2 (5 cm ⁇ 5 cm) The solvent which dissolved the cooling agent by composition shown in Table 1 is applied (coating amount 60 g / m 2 ), the above-mentioned polymer sheet is arranged on the application side, and the exothermic part which is a lamination structure is produced. did.
  • Comparative Example 4 A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used, and the cooling agent was positioned as shown in Table 1. Specifically, after applying the above-mentioned heat-generating powdery water dispersion on a 25 cm 2 (5 cm ⁇ 5 cm) polyethylene laminated paper in an amount of 600 g / m 2 in the range of 25 cm 2 (5 cm ⁇ 5 cm) Then, the above-mentioned polymer sheet is disposed on the coated surface, and a solvent in which the cooling agent is dissolved with the composition shown in Table 1 is coated thereon (coating amount 60 g / m 2 ) to produce a laminated structure And the heat generating portion was produced.
  • Comparative Example 5 A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used.
  • Heat generation characteristics (rise of heat generation in the early stage of application)
  • a temperature sensor of the measuring device is attached to the center of the surface of the first sheet of the heating tool with the heat generating part using a measuring device in accordance with JIS S4100, room temperature 20 ° C., absolute humidity 50%, The heat generation of the heat generating portion was started in the presence of oxygen, and the time (minute) required to reach 42 ° C. for feeling a comfortable warm feeling was measured.
  • a 15 cm x 25 cm polyvinyl fluoride resin gas collection bag (Tedlar (registered trademark) bag, manufactured by DuPont) containing a sufficient amount of air enough to cause an oxidation reaction of the heating element is prepared. Then, one end of the gas collection bag was connected to an air supply, and the discharge port at the other end or the tip of a tube connected to the discharge port was immersed in ethanol. Next, the heating element holding menthol was removed from the oxygen blocking bag, placed in the gas collection bag, and placed on a hot plate set at 35 ° C. for 2 hours.
  • the heating element was taken out from the gas collection bag, the inside of the gas collection bag was washed with ethanol, ethanol used for washing was also collected, and the total amount of menthol was volatilized.
  • the analysis of the collected amount of menthol was performed by gas chromatography (Agilent 6890N, manufactured by Agilent Technologies, Inc.). All these operations were performed under atmospheric pressure. Since two heating elements were used for the heating tool, the amount of menthol volatilization of the heating tool was twice the amount measured per heating element.
  • Example 3 since Example 3 uses PEG 400, the rise time at 42 ° C. and the amount of menthol volatilization are further improved by volatilization as compared with Example 8 using PEG 1000. As a result, it is considered that the feeling of effect on pain, the immediate effect, and the feeling of menthol are even better. 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 addition, in Comparative Example 3, since the rise time at 42 ° C. was long, no immediate effect was obtained, and the menthol feeling was also weak.
  • Comparative Example 4 the temperature did not rise up to 42 ° C., and therefore the sense of effect on pain, the immediate effect, and the feeling of menthol were all inadequate.
  • the heating implement of Example 1 when polyethylene glycol having a molecular weight of 2000 is used, the amount of menthol volatilized does not reach 1 mg / 2 hours and is inferior in any of the feeling of effect, immediate effect, and gingin feeling.

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Abstract

A heating tool (1) is provided with: an air-permeable first sheet (11); a second sheet (12); a heat generating layer (13) that is interposed between the first sheet (11) and the second sheet (12); and a medication layer (16) that is interposed between the heat generating layer (13) and the second sheet (12), the heating tool being configured such that the air permeability from the heat generating layer (13) to the first sheet (11) is higher than that from the heat generating layer (13) to the second sheet (12). The medication layer (16) comprises a medication composition including a cooling sensation agent and a solvent having a molecular weight of at most 1,000, and the volatilization amount of the cooling sensation agent after initiation of heat generation in the heat generating layer (13) is 1-5 mg/2 hours.

Description

温熱具Heating tool
　本発明は、温熱具に関する。 The present invention relates to a heating tool.
　従来、鉄粉等の被酸化性金属、塩化ナトリウム等の電解質及び水を含んで構成され、被酸化性金属の酸化反応により生じる酸化熱を利用した蒸気温熱具が利用されている。また、このような蒸気温熱具は薬剤成分を着用者に供給する事ができる事を活用し、温熱付与以外の他の機能を併せ持つ技術が開発されつつある。
　例えば、特許文献１では、夏場など蒸気温熱具特有の暑熱感を感じる場合があるため、これを緩和する事を目的とした蒸気温熱具が開示されている。すなわち、温感と清涼感を同時に付与することで暑熱感を緩和する観点から、メントールなどの冷感剤が発熱部に含有された発熱具が開示されている。 Heretofore, there has been used a steam heater which comprises an oxidizable metal such as iron powder, an electrolyte such as sodium chloride and water, and utilizes the heat of oxidation generated by the oxidation reaction of the oxidizable metal. Moreover, such a steam heating tool utilizes that it can supply a chemical | medical agent component to a wearer, and the technique which has another function other than heat | fever provision is also being developed.
For example, in patent document 1, since there may be a feeling of heat peculiar to a steam heating implement such as a summer season, a steam heating implement for the purpose of alleviating this is disclosed. That is, from the viewpoint of alleviating a hot feeling by simultaneously imparting a warm feeling and a cool feeling, a heat generating tool in which a cooling agent such as menthol is contained in the heat generating portion is disclosed.
　一方、特許文献２には、メントールなどの薬液を含む温熱具において、薬液が塗工された層と、発熱体が塗工された層との層間剥離を抑制する観点から、薬液の未塗工領域を形成することにより、未塗工領域と発熱層との表面張力を利用して、層間剥離を抑制する技術が開示されている。 On the other hand, in Patent Document 2, in the heating tool containing a chemical solution such as menthol, from the viewpoint of suppressing the delamination between the layer coated with the chemical solution and the layer coated with the heating element, By forming the area, a technique is disclosed that suppresses the delamination by utilizing the surface tension of the uncoated area and the heat generating layer.
特開２０１０－１５８５０７号公報JP, 2010-158507, A 特開２０１６－７３４１５号公報JP, 2016-73415, A
　本発明は、
　通気性を有する第一シートと、
　第二シートと、
　前記第一シート及び前記第二シートの間に配置された発熱層と、
　前記発熱層及び前記第二シートの間に配置された薬剤層と、
を備え、
　前記発熱層から前記第一シートまでの通気性が、前記発熱層から前記第二シートまでの通気性よりも高くなるように構成され、
　前記薬剤層は、冷感剤と、分子量が１，０００以下の溶剤とを含む薬剤組成物からなる、温熱具を提供する。 The present invention
A breathable first sheet,
The second sheet,
A heat generating layer disposed between the first sheet and the second sheet;
A drug layer disposed between the heat generating layer and the second sheet;
Equipped with
The air permeability from the heat generating layer to the first sheet is configured to be higher than the air permeability from the heat generating layer to the second sheet,
The drug layer provides a heating tool comprising a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less.
　上述した目的、およびその他の目的、特徴および利点は、以下に述べる好適な実施の形態、およびそれに付随する以下の図面によってさらに明らかになる。 The objects described above, and other objects, features and advantages will become more apparent from the preferred embodiments described below and the following drawings associated therewith.
本発明の実施形態にかかる温熱具を示す断面図である。It is a sectional view showing a heating implement concerning an embodiment of the present invention. 本発明の実施形態にかかる発熱体を示す断面図である。It is sectional drawing which shows the heat generating body concerning embodiment of this invention. 発熱体を示す斜視図である。It is a perspective view showing a heating element. 発熱部の一部を示す断面図である。It is a sectional view showing a part of exothermic part. 温熱具を使用者に着用した状態の一例を示す図である。It is a figure showing an example of a state where a user wears a heating implement.
　近年の使用者は蒸気温熱具を使用した際の心地よさや効果感への要求が高水準化しており、例えば、蒸気温熱具を適用する部位で感じるコリ、疲れ、痛みが軽くなったように感じたい、このような軽減効果を適用後速やかに感じたい等の要求が強くなっている。
　しかし、上記の特許文献１に記載された技術のように暖かい刺激と清涼感を同時に付与するだけでは、使用者のこのような要求を充分に満足させることはできなかった。
　また、特許文献２に開示された技術は、層間剥離に着目したものであり、このような使用者の要求に着目したものではなく、また要求に対しても十分応えたものではなかった。 In recent years, users are demanding higher levels of comfort and feeling when using a steam heating tool. For example, it feels as if the feeling of fatigue, fatigue and pain at the site where the steam heating tool is applied is reduced. There is a growing demand for the need to feel such mitigation effects immediately after application.
However, it has not been possible to sufficiently satisfy such a user's request only by simultaneously applying a warm stimulus and a refreshing feeling as in the technique described in the above-mentioned Patent Document 1.
Further, the technology disclosed in Patent Document 2 focuses on delamination, and does not focus on such a user's request and does not sufficiently meet the request.
　本発明者らが、使用者の高い要求に応えるべく、鋭意検討を行った結果、初期の温熱具の発熱挙動に対する初期の冷感剤の揮散挙動を適切にすることで、コリ、疲れ、及び痛み等に対する効果感と、これらの即効感とが向上することを見出した。そして、これを実現すべくさらに検討を重ねたところ、冷感剤に特定の分子量の溶剤を組み合わせ、かつ温熱具における冷感剤の配置を制御することで、温熱具の使用開始後、早期に冷感剤による心地よい刺激を高められ、さらには、発熱温度の立ち上がりも改善される結果、効果感、即効感が非常に高くなるといった予想外の作用が見出され、本発明が完成された。 As a result of intensive studies conducted by the present inventors in order to meet the high demands of users, it has been found that by appropriately setting the volatilization behavior of the initial cooling agent to the heat generation behavior of the initial heating implement, It has been found that the sense of effect on pain etc. and the sense of immediate effects are improved. Then, when we further studied to realize this, combining the solvent of the specific molecular weight with the cooling agent and controlling the arrangement of the cooling agent in the heating tool, it is possible to start soon after using the heating tool. The present invention completed the present invention by finding out an unexpected effect that the sensation of enhanced sensation by the cooling agent is enhanced and the rise of the heat generation temperature is also improved, resulting in a very high feeling of effect and immediate effect.
　本発明によれば、コリ、疲れ、及び痛み等に対する効果感が高く、これらの即効感に優れた温熱具が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the feeling of effect with respect to coli, fatigue, and pain etc. is high, and the heating tool excellent in these immediate effects is provided.
　以下、本発明の実施形態を図面に基づいて説明する。なお、すべての図面において、同様な構成要素には同一符号を付し、その詳細な説明は重複しないように適宜省略される。 Hereinafter, embodiments of the present invention will be described based on the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the detailed description thereof is appropriately omitted so as not to be repeated.
　本実施形態において、通気度は、ＪＩＳ　Ｐ８１１７によって測定される値であり、一定の圧力のもとで１００ｍｌの空気が６．４５ｃｍ２の面積を通過する時間で定義される。通気度は、王研式通気度計もしくはそれに準じた測定機で測定することができる。
　すなわち、通気度が大きいことは空気の通過に時間がかかること、即ち通気性が低いことを意味している。逆に、通気度が小さいことは通気性が高いことを意味している。このように、通気度の大小と通気性の高低とは逆の関係を示す。
　また本実施形態において、坪量とは、発熱層の平面視における面積に対する質量を意味している。 In the present embodiment, the air permeability is a value measured according to JIS P8117, and is defined as a time in which 100 ml of air passes an area of 6.45 cm 2 under a constant pressure. The air permeability can be measured with an Oken type air permeability meter or a measuring instrument according thereto.
That is, high air permeability means that the passage of air takes time, that is, air permeability is low. Conversely, low air permeability means high air permeability. Thus, the relationship between the degree of air permeability and the degree of air permeability is reversed.
Moreover, in this embodiment, the basis weight means the mass with respect to the area in planar view of a heat-generating layer.
　図１は、本発明の実施形態にかかる温熱具を示す断面図である。図２は、本発明の実施形態にかかる発熱体を示す断面図である。
　図１に示すように、温熱具１は、通気性を有する第一シート１１と、第二シート１２と、第一シート１１及び第二シート１２の間に介在配置され、並列に配置された２つの発熱体１８を備える。すなわち、温熱具１は、第一シート１１と、第二シート１２とからなる外袋を有する。
　また、図２に示すように、発熱体１８は、第二シート１２側から順に、基材層１０、薬剤層１６、発熱層１３、及び保水層１９がこの順で積層された発熱部２０と、発熱部２０を内部に収容する内袋１７と、を備える。なお、内袋１７は、シート１７１と、シート１７２の周縁部を接合することで構成されている。
　これにより、温熱具１は、通気性を有する第一シート１１と、第二シート１２と、第一シート１及び第二シート１２の間に配置された発熱層１３と、発熱層１３及び第二シート１２の間に配置された薬剤層１６と、を備えることになる。
　また、温熱具１は、発熱層１３から第一シート１１までの通気性が、発熱層１３から第二シート１２までの通気性よりも高くなるように構成されている。これにより、発熱層１３で発生した温熱蒸気は、第二シート１２側から外部に放出されにくくなるとともに、第一シート１１側から優先的に放出しやすくなる。これにより、使用者の肌へ、効果的に温熱蒸気及び冷感剤を供給することができる。 FIG. 1 is a cross-sectional view showing a heating implement according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a heating element according to an embodiment of the present invention.
As shown in FIG. 1, the heating implement 1 is disposed between the first sheet 11 having air permeability, the second sheet 12, and the first sheet 11 and the second sheet 12, and is disposed in parallel 2 Provided with two heating elements 18. That is, the heating implement 1 has an outer bag made of the first sheet 11 and the second sheet 12.
Further, as shown in FIG. 2, the heat generating body 18 and the heat generating portion 20 in which the base material layer 10, the drug layer 16, the heat generating layer 13, and the water retention layer 19 are laminated in this order from the second sheet 12 side And the inner bag 17 which accommodates the heat-emitting part 20 in an inside. The inner bag 17 is configured by joining the sheet 171 and the peripheral portion of the sheet 172.
Thereby, the heating implement 1 includes the first sheet 11 having air permeability, the second sheet 12, the heat generating layer 13 disposed between the first sheet 1 and the second sheet 12, the heat generating layer 13 and the second layer. And a drug layer 16 disposed between the sheets 12.
Further, the heating implement 1 is configured such 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. As a result, the thermal steam generated in the heat generating layer 13 is less likely to be released to the outside from the second sheet 12 side, and preferentially released from the first sheet 11 side. Thereby, the thermal steam and the cooling agent can be effectively supplied to the skin of the user.
　さらに、第一シート１１の外面に、第一粘着層１４及び第二粘着層１５が形成され、その上に、剥離紙２１が設けられている。これにより、温熱具１の使用時に剥離紙２１を剥がし、第一粘着層１４及び第二粘着層１５により温熱具１を使用者の肌に固定することができ、使用者が動いても、温熱具１が使用者から離脱することが抑制され、使用者に安定的に温熱蒸気を供給することができる。 Furthermore, the first adhesive layer 14 and the second adhesive layer 15 are formed on the outer surface of the first sheet 11, and the release paper 21 is provided thereon. Thereby, the release paper 21 can be peeled off at the time of use of the heating tool 1, and the heating tool 1 can be fixed to the skin of the user by the first adhesive layer 14 and the second adhesive layer 15; It is suppressed that the tool 1 detaches from the user, and the user can be stably supplied with the thermal steam.
　以下、各構成について詳述する。 Each component will be described in detail below.
［発熱部２０］
　発熱部２０は、基材層１０、薬剤層１６、発熱層１３、及び保水層１９がこの順で積層された構造を有する。 [Heat generation unit 20]
The heat generating portion 20 has a structure in which the base layer 10, the drug layer 16, the heat generating layer 13, and the water retaining layer 19 are laminated in this order.
　発熱層１３は、発熱した際に蒸気を発生するものであり、少なくとも被酸化性金属と水とを含み、例えば、被酸化性金属、炭素成分、及び水等を含有する発熱組成物で構成されている。 The heat generating layer 13 generates steam when it generates 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, etc. ing.
　被酸化性金属は、酸化反応熱を発する金属であり、例えば、鉄、アルミニウム、亜鉛、マンガン、マグネシウム、カルシウム、及びこれらのうち２種以上を混合した混合金属等の粉末や繊維が挙げられる。 The oxidizable metal is a metal that emits the heat of oxidation reaction, and examples thereof include powders and fibers such as iron, aluminum, zinc, manganese, magnesium, calcium, and mixed metals in which two or more of these are mixed.
　被酸化性金属は、酸化反応が効率的に行われるという観点から、粉末状にした場合の平均粒径が好ましくは１０μｍ以上であり、より好ましくは１５μｍ以上であり、さらに好ましくは２０μｍ以上である。同様の観点から、被酸化性金属の平均粒径は好ましくは２００μｍ以下であり、より好ましくは１８０μｍ以下であり、さらに好ましくは１５０μｍ以下である。
　なお、被酸化性金属の粒径は、粉体の形態における最大長さをいい、篩による分級、動的光散乱法、レーザー回折法等により測定することができるが、なかでもレーザー回折法により測定することが好ましい。 The oxidizable metal preferably has an average particle diameter of 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more from the viewpoint of efficient oxidation reaction, when it is powdered. . 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 refers to the maximum length in the form of powder, and can be measured by classification with a sieve, dynamic light scattering method, laser diffraction method, etc., among which laser diffraction method It is preferable to measure.
　発熱層１３中における被酸化性金属の含有量は、薬剤層１６を備える温熱具１において発熱層１３を所望の温度に上昇させることができる観点から、坪量で表して、好ましくは１００ｇ／ｍ２以上であり、より好ましくは２００ｇ／ｍ２以上であり、さらに好ましくは３００ｇ／ｍ２以上であり、さらに好ましくは５００ｇ／ｍ２以上である。また、同様の観点から、発熱層１３中における被酸化性金属の含有量は、好ましくは３，０００ｇ／ｍ２以下であり、より好ましくは２，０００ｇ／ｍ２以下であり、さらに好ましくは１，５００ｇ／ｍ２以下である。
　ここで、発熱層１３中の被酸化性金属の含有量は、ＪＩＳ　Ｐ８１２８に準じる灰分試験や、熱重量測定器で求めることができる。他に外部磁場を印加すると磁化が生じる性質を利用して振動試料型磁化測定試験等により定量することができる。なかでも、熱重量測定器で求めることが好ましい。 The content of the oxidizable metal in the heat generating layer 13 is preferably 100 g / m in terms of basis weight from the viewpoint that the heat generating layer 13 can be raised to a desired temperature in the heating implement 1 provided with the drug layer 16. It is 2 or more, More preferably, it is 200 g / m < 2 > or more, More preferably, it is 300 g / m < 2 > or more, More preferably, it is 500 g / m < 2 > or more. From the same viewpoint, the content of the oxidizable metal in the heat generating layer 13 is preferably not more than 3,000 g / m 2, more preferably not more than 2,000 g / m 2, more preferably 1 , 500 g / m 2 or less.
Here, the content of the oxidizable metal in the heat generating layer 13 can be determined by an ash content test according to JIS P8128 or a thermogravimeter. In addition, when an external magnetic field is applied, it can be quantified by a vibrating sample type magnetization measurement test or the like by utilizing the property of generating magnetization. Among them, it is preferable to use a thermogravimeter.
　炭素成分は、保水能、酸素供給能、及び触媒能を有するものであり、たとえば、活性炭、カーボンブラック、アセチレンブラック、及び黒鉛からなる群から選ばれる１種又は２種以上の材料を用いることができる。なかでも、湿潤時に酸素を吸着しやすいことから、活性炭が好ましく用いられる。また、椰子殻炭、木粉炭、及びピート炭からなる群から選ばれる１種又は２種以上の微細な粉末状物又は小粒状物がより好ましく用いられる。発熱体１８の表面温度を所望の温度に上昇させやすくする観点から、木粉炭がさらに好ましい。 The carbon component has a water holding ability, an oxygen supplying ability, and a catalytic ability, and may use, for example, one or more materials selected from the group consisting of activated carbon, carbon black, acetylene black, and graphite. it can. Among them, activated carbon is preferably used because oxygen is easily adsorbed when wet. In addition, one or two or more types of fine powder or small particles selected from the group consisting of coconut shell charcoal, wood flour charcoal, and peat charcoal are more preferably used. Wood charcoal is more preferable from the viewpoint of facilitating the surface temperature of the heating element 18 to rise to a desired temperature.
　炭素成分は、被酸化性金属と均一に混合される観点から、平均粒径が好ましくは１０μｍ以上であり、より好ましくは１２μｍ以上であり、さらに好ましくは１５μｍ以上である。また、同様の観点から、炭素成分の平均粒径は好ましくは２００μｍ以下であり、より好ましくは１５０μｍ以下であり、さらに好ましくは１００μｍ以下である。
　なお、炭素成分の平均粒径は、粉体の形態における最大長さをいい、動的光散乱法、レーザー回折法等により測定することができるが、なかでもレーザー回折法により測定することが好ましい。炭素成分は粉体状の形態のものを用いることが好ましいが、粉体状以外の形態のものを用いることもでき、たとえば、繊維状の形態のものを用いることもできる。 The carbon component preferably has an average particle diameter of 10 μm or more, more preferably 12 μm or more, and still more preferably 15 μm or more, from the viewpoint of being uniformly mixed with the oxidizable metal. 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 size of the carbon component refers to the maximum length in the form of powder, and can be measured by a dynamic light scattering method, a laser diffraction method, etc., among which it is preferable to measure by a laser diffraction method. . The carbon component is preferably in the form of powder, but may be in the form other than powder, for example, in the form of fiber.
　発熱層１３中における炭素成分の含有量は、発熱層１３への水分供給が十分に得られる観点から、被酸化性金属の含有量１００質量部に対して、好ましくは１質量部以上であり、より好ましくは３質量部以上であり、さらに好ましくは６質量部以上である。また、発熱層１３中における炭素成分の含有量は、発熱層１３への酸素供給が十分に得られる観点から、被酸化性金属の含有量１００質量部に対して、好ましくは４０質量部以下であり、より好ましくは１５質量部以下であり、さらに好ましくは１２質量部以下である。 The content of the carbon component in the heat generating layer 13 is preferably 1 part by mass or more with respect to 100 parts by mass of the content of the oxidizable metal from the viewpoint of sufficient supply of water to the heat generating layer 13. More preferably, it is 3 mass parts or more, More preferably, it is 6 mass parts or more. The content of the carbon component in the heat generating layer 13 is preferably 40 parts by mass or less with respect to 100 parts by mass of the oxidizable metal from the viewpoint that oxygen supply to the heat generating layer 13 is sufficiently obtained. More preferably, it is 15 parts by mass or less, and more preferably 12 parts by mass or less.
　なお、発熱層１３中における炭素成分の含有量は、坪量で表して、好ましくは１０ｇ／ｍ２以上であり、より好ましくは２０ｇ／ｍ２以上であり、さらに好ましくは２５ｇ／ｍ２以上である。また、炭素成分の含有量は、坪量で表して、好ましくは４００ｇ／ｍ２以下であり、より好ましくは２５０ｇ／ｍ２以下であり、さらに好ましくは１２０ｇ／ｍ２以下である。 The content of the carbon component in the heat generating layer 13 is preferably 10 g / m 2 or more, more preferably 20 g / m 2 or more, and still more preferably 25 g / m 2 or more in terms of basis weight. is there. In addition, the content of the carbon component is preferably 400 g / m 2 or less, more preferably 250 g / m 2 or less, and still more preferably 120 g / m 2 or less, in terms of basis weight.
　発熱層１３中の水の含有量は、被酸化性金属の酸化反応を良好に進行させる観点から、被酸化性金属１００質量部に対して、好ましくは２０質量部以上であり、より好ましくは３０質量部以上であり、さらに好ましくは４０質量部以上である。発熱層１３中の水の含有量は、最高到達温度を一定温度以上とする観点から、被酸化性金属１００質量部に対して、好ましくは１００質量部以下であり、より好ましくは９０質量部以下であり、さらに好ましくは８０質量部以下である。発熱層１３中の水は、被酸化性金属の酸化反応による発熱に伴う温度上昇により、その一部が水蒸気となる。 The content of water in the heat generating layer 13 is preferably 20 parts by mass or more, more preferably 30 parts by mass with respect to 100 parts by mass of the oxidizable metal, from the viewpoint of favorably advancing the oxidation reaction of the oxidizable metal. It is at least a part by mass, more preferably at least 40 parts by mass. The content of water in the heat generating layer 13 is preferably 100 parts by mass or less, and more preferably 90 parts by mass or less, with respect to 100 parts by mass of the oxidizable metal, from the viewpoint of setting the highest temperature to a predetermined temperature or higher. More preferably, it is 80 parts by mass or less. A part of water in the heat generating layer 13 becomes water vapor due to the temperature rise accompanying heat generation due to the oxidation reaction of the oxidizable metal.
　発熱層１３中には、水分を保持し、被酸化性金属の酸化反応を効率よく進行させるため、吸水剤を含ませることができる。吸水剤として、吸水性を有するポリマーや、吸水性を有する粉体を用いることができる。 A water absorbing agent can be contained in the heat generating layer 13 in order to retain moisture and efficiently advance the oxidation reaction of the oxidizable metal. As the water absorbing agent, a polymer having water absorbency or a powder having water absorbency can be used.
　吸水性を有するポリマーとしては、自重の２０倍以上の液体を吸収・保持できる架橋構造を有する親水性のポリマーが挙げられ、吸水性を有する粉体としては、バーミキュライト、おがくず、シリカゲル、及びパルプ粉末からなる群から選ばれる１種又は２種以上の粉体が挙げられる。吸水剤を含ませる場合の含有量としては、発熱層１３中の水１００質量部に対して２質量部以上であることが好ましく、また、２０質量部以下であることが好ましく、１５質量部以下であることがより好ましい。 Examples of the polymer having water absorbability include hydrophilic polymers having a cross-linked structure capable of absorbing and holding a liquid 20 times or more of its own weight, and as powder having water absorbency, vermiculite, sawdust, silica gel, and pulp powder And at least one powder selected from the group consisting of The content of the water absorbing agent is preferably 2 parts by mass or more, preferably 20 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass of water in the heat generating layer 13. It is more preferable that
　発熱層１３は、さらに、反応促進剤を含むことができる。反応促進剤を含ませることで、被酸化性金属の酸化反応を持続させやすくすることができる。また、反応促進剤を用いることにより、酸化反応に伴い被酸化性金属に形成される酸化被膜を破壊して、酸化反応を促進することができる。反応促進剤には、例えばアルカリ金属、及びアルカリ土類金属の硫酸塩又は塩化物からなる群から選ばれる１種又は２種以上の材料が挙げられる。中でも、導電性、化学的安定性、生産コストに優れる点から、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、塩化第一鉄、及び塩化第二鉄等の各種塩化物、及び硫酸ナトリウムからなる群から選ばれる１種又は２種以上の材料を用いることが好ましい。 The heat generating layer 13 can further contain a reaction accelerator. By including a reaction accelerator, the oxidation reaction of the oxidizable metal can be easily sustained. In addition, by using a reaction accelerator, the oxide film formed on the oxidizable metal accompanying the oxidation reaction can be destroyed to promote the oxidation reaction. The reaction accelerator includes, for example, one or more materials selected from the group consisting of alkali metal and sulfate or chloride of alkaline earth metal. Among them, various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride, and ferric chloride, and sodium sulfate from the viewpoint of excellent conductivity, chemical stability, and production cost. It is preferable to use one or more materials selected from the group.
　発熱組成物中に増粘剤を含有させると、発熱体１８の保管中における発熱特性の低下を抑制することができる。
　発熱組成物中に含まれる増粘剤としては主として、水分を吸収して稠度を増大させるか、チキソトロピー性を付与する物質を用いることができ、アルギン酸ナトリウム等のアルギン酸塩、アラビアゴム、トラガカントゴム、ローカストビーンガム、グアーガム、アラビアガム、カラギーナン、寒天、及びキサンタンガムなどの多糖類系増粘剤；デキストリン、α化澱粉、及び加工用澱粉などの澱粉系増粘剤；カルボキシメチルセルロース、酢酸エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシメチルセルロース及びヒドロキシプロピルセルロースなどのセルロース誘導体系増粘剤；ステアリン酸塩などの金属石鹸系増粘剤；ベントナイトなどの鉱物系増粘剤等から選ばれる１種又は２種以上を用いることができる。 When a thickener is included in the heat generating composition, it is possible to suppress a decrease in heat generating characteristics during storage of the heat generating body 18.
As the thickener contained in the heat generating composition, a substance which absorbs moisture to increase the consistency or which imparts thixotropy can be used, and alginates such as sodium alginate, gum arabic, gum tragacanth, locust Polysaccharide thickeners such as bean gum, guar gum, gum arabic gum, carrageenan, agar, and xanthan gum; starch thickeners such as dextrin, pregelatinized starch, and starch for processing; carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, Cellulose derivative thickeners such as hydroxymethyl cellulose and hydroxypropyl cellulose; metal soap thickeners such as stearates; mineral thickeners such as bentonite, etc. One or two or more selected from these can be used. .
　発熱組成物中にリン酸塩を含有させると、発熱組成物の流動性を上げる効果があるため、紙等の基材に塗布して発熱層１３を製造する場合に製造が容易となる点から好ましい。リン酸塩としては、第一リン酸カリウム塩、第二リン酸カリウム塩、第三リン酸カリウム塩、第一リン酸ナトリウム塩、及び第二リン酸ナトリウム塩から選ばれる１種又は２種以上を用いることができる。 When the heat generating composition contains a phosphate, it has the effect of increasing the flowability of the heat generating composition, so that it becomes easy to manufacture when the heat generating layer 13 is manufactured by applying it to a substrate such as paper. preferable. As a phosphate, 1 type or 2 types or more selected from a primary phosphate potassium salt, a secondary phosphate potassium salt, a tertiary phosphate potassium salt, a primary phosphate sodium salt, and a secondary phosphate sodium salt Can be used.
　発熱層１３は、粉体や粉体の成形物であってもシート状であってもよく、本実施形態では、平面視において矩形形状（正方形、長方形）のシート状となっている。 The heat generating layer 13 may be a powder or a molded product of powder, or may be a sheet, and in the present embodiment, it is a sheet of a rectangular shape (square, rectangle) in plan view.
　本実施形態においては発熱層１３がシート状である態様を示したが、この発熱層１３は、粉体状であってもよいし、シート状であってもよい。しかしながら、使用感に優れる点から、シート状であることが好ましい。 Although the heat generating layer 13 is in the form of a sheet in this embodiment, the heat generating layer 13 may be in the form of powder or in the form of a sheet. However, it is preferable to be in the form of a sheet from the viewpoint of being excellent in the feeling in use.
　発熱層１３の製造方法としては、たとえば、発熱組成物を湿式抄造してなるもの、発熱組成物をプレスしてなるもの、発熱組成物を後述する基材層１０で挟持してなるもの、発熱組成物を水中に分散させて発熱粉体水分散物として、当該発熱粉体水分散物を基材層１０上に塗布してなるもの等が挙げられる。なかでも、使用感に優れる点、容易に製造できる点から、発熱組成物を水中に分散させて発熱粉体水分散物として、当該発熱粉体水分散物を基材層１０上に塗布する方法であることが好ましい。 As a method of producing the heat generating layer 13, for example, one obtained by wet forming a heat generating composition, one formed by pressing the heat generating composition, one formed by sandwiching the heat generating composition with the substrate layer 10 described later, heat generation What disperse | distributes a composition in water, and apply | coats the said heat-generating powder water dispersion on the base material layer 10 as a heat-generating powder water dispersion etc. are mentioned. Above all, a method of dispersing the heat generating composition in water and applying the heat generating powder water dispersion on the substrate layer 10 as a heat generating powder water dispersion from the viewpoint of excellent feeling in use and easy production. Is preferred.
　基材層１０は、一方の面が水分の吸収保持が可能であり、他方の面が水分不透過性であることが好ましい。基材層１０の坪量は、好ましくは１０ｇ／ｍ２以上２００ｇ／ｍ２以下であり、より好ましくは３５ｇ／ｍ２以上１５０ｇ／ｍ２以下である。 It is preferable that one surface of the base material layer 10 can absorb and retain water, and the other surface is water impermeable. The basis weight of the base material layer 10 is preferably 10 g / m 2 or more and 200 g / m 2 or less, and more preferably 35 g / m 2 or more and 150 g / m 2 or less.
　図２に示すように、基材層１０は、親水層１０ａと、液不透過層１０ｂと、が積層し、ラミネートされたシートが用いられている。 As shown in FIG. 2, in the base material layer 10, a sheet in which a hydrophilic layer 10 a and a liquid impermeable layer 10 b are laminated and laminated is used.
　親水層１０ａとは、親水性繊維を含む層である。
　基材層１０に全体に含まれる親水性繊維の割合は、２０質量％以上９９．９質量％以下であることが好ましく、５０質量％以上９９．５質量％以下であることがより好ましい。 The hydrophilic layer 10a is a layer containing hydrophilic fibers.
It is preferable that it is 20 to 99.9 mass%, and, as for the ratio of the hydrophilic fiber contained in the whole in the base material layer 10, it is more preferable that it is 50 to 99.5 mass%.
　親水性繊維としては、たとえば、セルロース繊維を用いることが好ましい。セルロース繊維としては、化学繊維（合成繊維）及び天然繊維を用いることができる。セルロースの化学繊維としては、例えば、レーヨン及びアセテートを用いることができる。一方、天然のセルロース繊維としては、各種の植物繊維、例えば、木材パルプ、非木材パルプ、木綿、麻、麦藁、ヘンプ、ジュート、カポック、やし、及びいぐさ等が挙げられる。これらのセルロース繊維のうち、太い繊維を容易に入手できる等の観点から、木材パルプを用いることが好ましい。 As the hydrophilic fiber, for example, it is preferable to use a cellulose fiber. As the cellulose fiber, chemical fiber (synthetic fiber) and natural fiber can be used. For example, rayon and acetate can be used as the chemical fiber of cellulose. On the other hand, natural cellulose fibers include various plant fibers such as wood pulp, non-wood pulp, cotton, hemp, wheat straw, hemp, jute, kapok, coconut, and rag. Among these cellulose fibers, wood pulp is preferably used from the viewpoint that thick fibers can be easily obtained.
　液不透過層１０ｂを構成する樹脂としては、ポリエチレン、及びポリプロピレン等のポリオレフィン、ポリエステル、ポリアミド、ポリウレタン、ポリスチレン、ナイロン、ポリ塩化ビニリデン、及びポリエチレン－酢酸ビニル共重合体等の樹脂が挙げられる。 Examples of the resin constituting the liquid impermeable layer 10 b include resins such as polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrenes, nylons, polyvinylidene chlorides, and polyethylene-vinyl acetate copolymers.
　親水層１０ａと、液不透過層１０ｂとのラミネート方法は、公知のラミネート加工を用いることができる。 A known laminating process can be used as a laminating method of the hydrophilic layer 10a and the liquid impermeable layer 10b.
　なお、基材層１０は、発熱層１３よりも肌から遠い側に位置することが好ましく、親水層１０ａが発熱層１３に近い側であることが好ましい。 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 10 a is preferably on the side closer to the heat generating layer 13.
　薬剤層１６は、冷感剤、及び分子量が１，０００以下の溶剤を含む薬剤組成物からなる。すなわち、薬剤組成物を発熱部中に含浸させた従来技術とは異なる。また、薬剤層１６は、温熱具１の使用時に、温熱蒸気とともに冷感剤を使用者に供給するものである。温熱具１は、薬剤層１６を備えることにより、冷感剤の揮散性を向上させることができる。
　薬剤層１６は任意の方法により形成されるが、図２のように発熱部２０が基材層１０を有する場合、薬剤層１６は、冷感剤、及び分子量が１，０００以下の溶剤を含む薬剤組成物を、基材層１０上に、塗工することにより形成されるのが好ましい。これにより、基材層１０の表面が薬剤層１６により被覆される。なお、被覆とは、連続している場合に限られず、一部が非連続であってもよい。
　また、冷感剤の一部は、薬剤層１６に隣接する基材層１０又は発熱層１３の内部に浸透してもよい。この場合、たとえば、発熱層１３の薬剤層１６に接する面の冷感剤の濃度が最も高い。 The drug layer 16 is composed of a cooling agent and a drug composition containing a solvent having a molecular weight of 1,000 or less. That is, it is different from the prior art in which the drug composition is impregnated into the heat generating portion. In addition, the drug layer 16 supplies the cooling agent to the user together with the thermal steam when the thermal implement 1 is used. The heating implement 1 can improve the volatilization of the cooling agent by including the drug layer 16.
Although the drug layer 16 is formed by any method, as shown in FIG. 2, when the heat generating portion 20 has the base layer 10, the drug layer 16 includes a cooling agent and a solvent having a molecular weight of 1,000 or less. The drug composition is preferably formed on the substrate layer 10 by coating. Thereby, the surface of the base material layer 10 is covered with the drug layer 16. In addition, with covering, it is not restricted to the case where it is continuous, and one part may be discontinuous.
In addition, a part of the cooling agent may penetrate into the inside of the base material layer 10 or the heat generating layer 13 adjacent to the drug layer 16. In this case, for example, the concentration of the cooling agent on the surface of the heat generating layer 13 in contact with the drug layer 16 is the highest.
　薬剤層１６は、公知の機器分析法により、反応前の発熱層１３中の冷感剤の分布を測定することで確認する事ができる。たとえば、三次元計測Ｘ線コンピューター断層撮影（ＣＴ）装置を用いて、薬剤層１６を含む発熱部２０を断面方向で分析し、元素分析を行うことで確認できる。また、発熱部２０の両面を赤外線吸収スペクトル法により、冷感剤の存在量が多い面側に薬剤層１６があることを確認できる。 The drug 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 instrumental analysis method. For example, the heat generation part 20 including the drug layer 16 can be analyzed in the cross-sectional direction using a three-dimensional measurement X-ray computed tomography (CT) apparatus, and can be confirmed by performing elemental analysis. In addition, it can be confirmed that the drug layer 16 is present on the side of the heat generating portion 20 on the side where the amount of the cooling agent is large, by infrared absorption spectroscopy.
　冷感剤としては、メントール、１，８－シネオール、乳酸メンチル、酢酸メンチル、コハク酸モノメンチル、３－（ｌ－メントキシ）－１，２－プロパンジオール、及びＮ－エチル－３－ｐ－メンタンカルボキサミドよりなる群から選ばれる１種又は２種以上の化合物を挙げることができる。これにより、冷感を持続させやすくなったり、香気の組み合わせにより冷感の感覚の改良などができるようになる。冷感剤による心地よい刺激を高め、取扱性を良好にする観点から、メントールであることが好ましい。
　冷感剤は、後述する分子量が１，０００以下の溶剤に溶解している。 As a cooling agent, menthol, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1,2-propanediol, and N-ethyl-3-p-menthancarboxamide One or two or more compounds selected from the group consisting of As a result, it becomes easy to maintain a cold sensation, and it is possible to improve the sensation of a cold sensation by combining an aroma. It is preferable that it is menthol from a viewpoint of raising the comfortable irritation | stimulation by a cooling agent and making a handling property favorable.
The cooling agent is dissolved in a solvent having a molecular weight of 1,000 or less described later.
　なお、本明細書において、「メントール」はｌ－メントールのほか、ｄｌ－メントールも合わせたものとして、その量などを特定することができる。また、本明細書において、冷感剤とは、使用者の皮膚、粘膜等に作用して使用者に冷たい感覚、すなわち冷感を与えるものである。 In the present specification, “menthol” can be specified as a combination of l-menthol and dl-menthol. Further, in the present specification, the cooling agent is something which acts on the skin, mucous membrane, etc. of the user to give the user a cold feeling, that is, a cold feeling.
　分子量が１，０００以下の溶剤としては、多価アルコールが好ましく、ポリエチレングリコール（ＰＥＧ）、グリセリン、及びプロピレングリコールの中から選ばれる１種又は２種以上であることがより好ましい。なかでも、冷感剤の良好な揮散性を保持し、良好な発熱性を得る観点、及び適用部位への効果感の向上と高い即効感を得る観点から、ポリエチレングリコールであることが好ましい。
　また、溶剤の分子量は、１，０００以下であるが、冷感剤による心地よい刺激を効果的に得つつ、良好な発熱性を得る観点、冷感剤の含有量をできるだけ少なくできる観点、及び冷感剤の良好な揮散性を保持する観点から、６００以下であることが好ましく、４５０以下であることがより好ましい。また、下限値は特に規定しないが、５０以上が好ましく、１００以上がより好ましい。
　なお、本明細書でいう分子量は、ポリエチレングリコールのように分子量に分布が生じる場合には重量平均分子量を意味する。また、発熱体１８にＰＥＧが含まれる場合、後述する発熱体１８中の溶剤の含有量を求める際に行う溶媒抽出法により、発熱体１８中の溶剤を抽出し、その抽出液をＧＰＣで分析することで、重量平均分子量を特定する。 The solvent having a molecular weight of 1,000 or less is preferably a polyhydric alcohol, and more preferably one or more selected from polyethylene glycol (PEG), glycerin and propylene glycol. Among them, polyethylene glycol is preferable from the viewpoint of maintaining good volatilization of the cooling agent and obtaining good heat buildup, and from the viewpoint of improving the feeling of effect on the application site and obtaining a high immediate effect.
In addition, although the molecular weight of the solvent is 1,000 or less, the viewpoint of obtaining good heat buildup, the viewpoint of being able to reduce the content of the cooling agent as much as possible, and effectively obtaining the comfortable stimulation by the cooling agent, From the viewpoint of maintaining the good volatility of the photosensitive agent, it is preferably 600 or less, and more preferably 450 or less. The lower limit value is not particularly limited, but is preferably 50 or more, and more preferably 100 or more.
In addition, molecular weight as used in this specification means a weight average molecular weight, when distribution arises in molecular weight like polyethylene glycol. When PEG is contained in the heating element 18, the solvent in the heating element 18 is extracted by a solvent extraction method performed when determining the content of the solvent in the heating element 18 described later, and the extract is analyzed by GPC Identify the weight average molecular weight.
　分子量が１，０００以下の溶剤の含有量は、使用開始後すぐに良好な温感を付与しつつ、冷感剤による心地よい刺激を効果的に得る観点から、薬剤組成物中の冷感剤と該溶剤の合計量に対して、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましい。
　一方、分子量が１，０００以下の溶剤の含有量は、安全性を確保しつつ、冷感剤による心地よい刺激を付与する観点から、薬剤組成物中の冷感剤と該溶剤の合計量に対して、８５質量％以下であることが好ましく、７０質量％以下であることがより好ましい。 The content of the solvent having a molecular weight of 1,000 or less, from the viewpoint of effectively obtaining a comfortable stimulus by the cooling agent while providing a good feeling of warmth immediately after the start of use, with the cooling agent in the pharmaceutical composition It is preferable that it is 30 mass% or more with respect to the total amount of this solvent, and it is more preferable that it is 50 mass% or more.
On the other hand, the content of the solvent having a molecular weight of 1,000 or less is relative to the total amount of the cooling agent and the solvent in the pharmaceutical composition from the viewpoint of imparting a comfortable stimulus by the cooling agent while securing safety. The content is preferably 85% by mass or less, and more preferably 70% by mass or less.
　また、発熱部２０において、分子量が１，０００以下の溶剤の含有量は、使用開始後すぐに良好な温感を付与しつつ、冷感剤による心地よい刺激を効果的に得る観点から、発熱層１３の平面視における単位面積当たり、２．０ｍｇ／ｃｍ２以上であることが好ましく、４．０ｍｇ／ｃｍ２以上であることがより好ましい。
　一方、発熱部２０において、分子量が１，０００以下の溶剤の含有量は、安全性を確保しつつ、冷感剤による心地よい刺激を付与する観点から、発熱層１３の平面視における単位面積当たり、２０ｍｇ／ｃｍ２以下であることが好ましく、１５ｍｇ／ｃｍ２以下であることがより好ましい。
　なお、分子量が１，０００以下の溶剤の含有量は、発熱部２０に含まれる分子量が１，０００以下の溶剤の質量を発熱層１３の平面視における面積で割った値として求められる。
　また、発熱体１８に含まれる分子量が１，０００以下の溶剤の含有量は、溶媒抽出法により得た抽出液をガスクロマトグラフィーにより分析し定量することで求められる。具体的には、発熱体１８を温熱具１から取り出し、発熱体１８を溶媒（好ましくは、エタノール）に浸し、密封したまま室温で９時間放置したのち、抽出液を得る。その後、得られた抽出液を、ガスクロマトグラフィーで分析する。 Further, in the heat generating portion 20, the content of the solvent having a molecular weight of 1,000 or less is a heat generating layer from the viewpoint of effectively obtaining a comfortable stimulus by the cooling agent while imparting a good thermal sensation immediately after the start of use. It is preferable that it is 2.0 mg / cm < 2 > or more per unit area in planar view of 13, and it is more preferable that it is 4.0 mg / cm < 2 > or more.
On the other hand, in the heat generating portion 20, the content of the solvent having a molecular weight of 1,000 or less per unit area in plan view of the heat generating layer 13 from the viewpoint of providing a comfortable stimulus by the cooling agent while securing safety. It is preferably 20 mg / cm 2 or less, more preferably 15 mg / cm 2 or less.
The content of the solvent having a molecular weight of 1,000 or less is obtained 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 plan view.
Further, the content of the solvent having a molecular weight of 1,000 or less contained in the heating element 18 can be determined by analyzing and quantifying the extract obtained by the solvent extraction method by gas chromatography. Specifically, the heating element 18 is taken out of the heating tool 1, and the heating element 18 is immersed in a solvent (preferably ethanol), and left sealed at room temperature for 9 hours while being sealed to obtain an extract. Thereafter, the extract obtained is analyzed by gas chromatography.
　冷感剤の発熱層１３の平面視における面積に対する含有量は、冷感剤による心地よい刺激を効果的に得る観点から、好ましくは１．０ｍｇ／ｃｍ２以上、より好ましくは１．５ｍｇ／ｃｍ２以上、さらに好ましくは１．７ｍｇ／ｃｍ２以上である。
　一方、冷感剤の発熱層１３の平面視における面積に対する含有量は、安全性を確保しつつ、冷感剤による心地よい刺激を付与する観点、及び良好な発熱特性を維持する観点から、好ましくは６．０ｍｇ／ｃｍ２以下、より好ましくは４．５ｍｇ／ｃｍ２以下、さらに好ましくは３．２ｇ／ｃｍ２以下である。
　なお、冷感剤の含有量は、発熱部２０に含まれる冷感剤の量を発熱層１３の平面視における面積で割った値で求められる。
　また、発熱体１８に含まれる冷感剤の量は、溶媒抽出法により得た抽出液をガスクロマトグラフィーにより分析し定量する。具体的には、発熱体１８を温熱具１から取り出し、発熱体１８を溶媒（エタノールが好ましい）に浸し、密封して室温で９時間放置する。このようにして得られた抽出液を、ガスクロマトグラフィーで分析する。 The content of the cooling agent relative to the area of the heat generating layer 13 in plan view is preferably 1.0 mg / cm 2 or more, more preferably 1.5 mg / cm 2 from the viewpoint of effectively obtaining a comfortable stimulus by the cooling agent. The above, more preferably 1.7 mg / cm 2 or more.
On the other hand, the content of the cooling agent relative to the area of the heat generating layer 13 in plan view is preferably from the viewpoint of providing a comfortable stimulus by the cooling agent while maintaining safety, and from the viewpoint of maintaining good heat generation characteristics. 6.0 mg / cm 2 or less, more preferably 4.5 mg / cm 2 or less, more preferably 3.2 g / cm 2 or less.
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 in plan view.
The amount of cooling agent contained in the heating element 18 is quantified by analyzing the extract obtained by the solvent extraction method by gas chromatography. Specifically, the heating element 18 is taken out of the heating tool 1, the heating element 18 is immersed in a solvent (ethanol is preferred), sealed, and left at room temperature for 9 hours. The extract obtained in this way is analyzed by gas chromatography.
　また、被酸化性金属と、温熱具１中に含まれる冷感剤の重量比（被酸化性金属/冷感剤）は、５以上５５以下が好ましく、１０以上５０以下であることがより好ましく、１０以上４０以下であることが更に好ましい。
　なかでも、より効果的に効果感および即効感を得る観点から、被酸化性金属と、メントールの重量比が、５以上５５以下が好ましく、１０以上５０以下であることがより好ましく、１０以上４０以下であることが更に好ましい。 The weight ratio of the oxidizable metal to the cooling agent contained in the heating tool 1 (oxidizable metal / cooling agent) is preferably 5 or more and 55 or less, and more preferably 10 or more and 50 or less. More preferably, it is 10 or more and 40 or less.
Among them, 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 more preferably 10 or more and 40 or less from the viewpoint of obtaining effect and immediate effect more effectively. It is more preferable that it is the following.
　また、冷感剤の揮散量は、例えば１ｍｇ／２時間以上、５ｍｇ／２時間以下である。冷感剤による痛みへの効果感及び即効性を得る観点とから、好ましくは１．３ｍｇ／２時間以上であり、ジンジン感を得る観点から、より好ましくは１．７ｍｇ／２時間以上であり、さらに好ましくは１．９ｍｇ／２時間以上である。一方、冷感剤の揮散量は、安全性を確保しつつ、冷感剤による心地よい刺激を付与する観点、及び良好な発熱特性を維持し、効果感及び即効感を向上する観点から、好ましくは３．５ｍｇ／２時間以下であり、より好ましくは３．０ｍｇ／２時間以下であり、さらに好ましくは２．８ｍｇ／２時間である。 The volatilization amount of the cooling agent is, for example, 1 mg / 2 hours or more and 5 mg / 2 hours or less. It is preferably 1.3 mg / 2 hours or more from the viewpoint of obtaining a feeling of effect on pain by a cooling agent and immediate effect, and is preferably 1.7 mg / 2 hours or more from the viewpoint of obtaining a gingin feeling. More preferably, it is 1.9 mg / 2 hours or more. On the other hand, the volatilization amount of the cooling agent is preferably from the viewpoint of providing a comfortable stimulus by the cooling agent while maintaining safety and maintaining good heat generation characteristics to improve the feeling of effect and the immediate effect. It is 3.5 mg / 2 hours or less, more preferably 3.0 mg / 2 hours or less, still more preferably 2.8 mg / 2 hours.
　冷感剤の揮散量は、以下のように測定することができる。
　まず、冷感剤を含んだ発熱体１８又は温熱具１が酸化反応を行う程度に充分な量の空気が入った１５ｃｍ×２５ｃｍのポリフッ化ビニル樹脂の気体捕集バッグ（テドラー（商標登録）バッグ、デュポン社製）を用意し、気体捕集バッグの一方の端部を空気供給源に接続し、他方の端部の吐出口又は吐出口に連結したチューブの先端をエタノール中に浸漬させる。
　次に、冷感剤を含んだ発熱体１８又は温熱具１を酸素遮断袋から取り出し、当該気体捕集バッグにいれて、３５℃に設定したホットプレート上に２時間載置する。ホットプレート上に載置している間、空気供給源から気体捕集バッグ内に一定スピードで（１００ｍＬ／ｍｉｎ）空気を流入させ、気体捕集バッグの他方の端部の吐出口又は吐出口に連結したチューブの先端から空気を排出させることで、揮散した冷感剤をエタノール中に捕集する。また、気体捕集バッグ内に流入した空気が適切に排出されるよう、気体捕集バッグ上に重りを載せ、気体捕集バッグの周囲は、ホットプレートによる加温が保持されるように、断熱材により断熱する。
　２時間の載置後、気体捕集バッグから発熱体１８又は温熱具１を取り出し、気体捕集バッグ内をエタノールで洗浄し、洗浄に用いたエタノールも捕集して、メントールの揮散量に合計する。メントールの捕集量の分析は、ガスクロマトグラフィーにより行う。
　これらの作業は全て大気圧下で行う。 The volatilization amount of the cooling agent can be measured as follows.
First, a 15 cm × 25 cm polyvinyl fluoride resin gas collection bag (Tedlar (registered trademark) bag) containing a sufficient amount of air to cause an oxidation reaction between the heating element 18 containing a cooling agent or the heating implement 1. Dupont Co., Ltd. is prepared, one end of the gas collection bag is connected to the air supply source, and the discharge port of the other end is immersed in ethanol at the tip of the tube connected to the discharge port.
Next, the heating element 18 or the heating tool 1 containing a cooling agent is taken out from the oxygen blocking bag, put in the gas collecting bag, and placed on a hot plate set at 35 ° C. for 2 hours. While placed on the hot plate, air is allowed to flow into the gas collection bag from the air supply source at a constant speed (100 mL / min), and the discharge port or discharge port at the other end of the gas collection bag By discharging air from the tip of the connected tube, the volatilized cooling agent is collected in ethanol. In addition, a weight is placed on the gas collection bag so that the air flowing into the gas collection bag is properly discharged, and the surroundings of the gas collection bag are thermally insulated so that the heating by the hot plate is maintained. Insulate with materials.
After placing for 2 hours, take out the heating element 18 or the heating tool 1 from the gas collection bag, wash the inside of the gas collection bag with ethanol, also collect the ethanol used for washing, and total the volatilization amount of menthol. Do. The analysis of the amount of menthol collected is carried out by gas chromatography.
All these operations are performed under atmospheric pressure.
　なお、薬剤組成物は、上述した冷感剤、溶剤のほか、本発明の効果を損なわない範囲で、他の成分を含んでもよい。なお、冷感剤の揮散速度をより向上させる観点から、薬剤組成物には、界面活性剤が実質的に含まれていないことが好ましい。また、上述の冷感剤以外の香料成分を薬剤組成物中に含む場合には、冷感剤に対して少ない量である事が好ましいが、薬剤組成物中に実質的に含まれていない事がより好ましい。
　ここで、薬剤組成物中に実質的に含まれていないとは、薬剤層中における対象化合物の含有量が、冷感剤と分子量１，０００以下の溶剤との合計量に対して、好ましくは０．１％未満、より好ましくは０．０１％未満、更に好ましくは薬剤層中に含有しないことをいう。 In addition to the cooling agent and solvent described above, the pharmaceutical composition may contain other components as long as the effects of the present invention are not impaired. From the viewpoint of further improving the volatilization rate of the cooling agent, the drug composition preferably contains substantially no surfactant. Moreover, when it is preferable that it is a small amount with respect to a cooling agent, when it contains fragrance components other than the above-mentioned cooling agent in a pharmaceutical composition, it is not substantially contained in a pharmaceutical composition. Is more preferred.
Here, the phrase “not substantially contained in the drug composition” means that the content of the target compound in the drug layer is preferably relative to the total amount of the cooling agent and the solvent having a molecular weight of 1,000 or less. Less than 0.1%, more preferably less than 0.01%, more preferably not contained in the drug layer.
　保水層１９は、水分を含み、これにより、温熱蒸気を供給したり、発熱特性を良好に保持できるようになる。
　保水層１９に含まれる水の含有量は、保水層１９の最大吸水量の１０～４５質量％であることが好ましく、１２～４０質量％であることがより好ましく、１３～３０質量％であることが、発熱部２０の製造時、発熱組成物が１つの発熱部２０に何らかの理由で多量に充填されたり、特定の箇所に多量に偏在したりする場合でも、異常発熱が防止され、良好な発熱特性が安定して得られる点でさらに好ましい。
　同様の観点から、保水層１９に含まれる水の含有量は、保水層１９の最大吸水量の１２質量％以上であることが好ましく、１３質量％以上であることがより好ましい。
　また、保水層１９に含まれる水の含有量は、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。 The water-retaining layer 19 contains moisture, which enables it to supply thermal steam and maintain its heat generation characteristics well.
The content of water contained in the water retention layer 19 is preferably 10 to 45% by mass, more preferably 12 to 40% by mass, and more preferably 13 to 30% by mass of the maximum water absorption amount of the water retention layer 19. Even when the heat generating composition is filled in a large amount in one heat generating portion 20 for some reason or unevenly distributed in a specific place at a large amount at the time of manufacturing the heat generating portion 20, abnormal heat generation is prevented and good. It is further preferable in that the heat generation characteristics can be stably obtained.
From the same viewpoint, the content of water contained in the water retention layer 19 is preferably 12% by mass or more of the maximum water absorption amount of the water retention layer 19, and more preferably 13% by mass or more.
Moreover, it is preferable that it is 40 mass% or less, and, as for content of the water contained in the water holding layer 19, it is more preferable that it is 30 mass% or less.
　なお、最大吸水量は、次のようにして測定することができる。
　保水層の最大吸水量（Ｗｍａｘ）は下記のとおり、ＪＩＳ　Ｌ１９０６の記載の測定方法を用いることができる。具体的には、保水層１９の質量（Ｗ０）を測定し、保水層１９を５質量％塩化ナトリウム水溶液に５分間浸漬した後、ピンセットで取り出して、１分間空気中に吊り下げ放置して抱えきれない水分をしたたり落とした後、質量（Ｗ１）を測定し、下記の式より最大吸水量（Ｗｍａｘ）を算出する。
　　　　Ｗｍａｘ＝Ｗ１－Ｗ０ The maximum water absorption can be measured as follows.
As the maximum water absorption (W max ) of the water retention layer, the measurement method described in JIS L1906 can be used as described below. Specifically, the mass (W 0 ) of the water retention layer 19 is measured, and after immersing the water retention layer 19 in a 5% by mass sodium chloride aqueous solution for 5 minutes, it is taken out with tweezers and suspended in air for 1 minute After dripping or dropping water which can not be held, the mass (W 1 ) is measured, and the maximum water absorption (W max ) is calculated from the following equation.
W max = W 1 -W 0
　保水層１９は、最大吸水量の１０～４５質量％の水を吸収保持できる吸水性があることが好ましく、通気性の有無を問わないが、通気性を有するものが好ましい。 The water-retaining layer 19 preferably has water absorbency capable of absorbing and holding 10 to 45% by mass of water of the maximum water absorption amount, regardless of the presence or absence of the air permeability, but preferably the one having the air permeability.
　最大吸水量の１０～４５質量％の水を吸収した状態での保水層１９の通気度は、５００秒／１００ｍｌ以下が好ましく、１～３００秒／１００ｍｌがより好ましい。このような通気度とすることで、発熱部２０の通気性が十分に確保されるため、酸素供給が十分に得られて高い発熱効率が得られ、被酸化性金属の酸化反応が良好となる上、多量の水蒸気を発生することを可能とし得る。また、３００秒／１００ｍｌ以下であることがより好ましく、過度な温度上昇を防止する観点からは、１秒／１００ｍｌ以上であることがさらに好ましい。 The air permeability of the water-retaining layer 19 in the state of absorbing 10 to 45% by mass of the maximum water absorption is preferably 500 seconds / 100 ml or less, and more preferably 1 to 300 seconds / 100 ml. With such an air permeability, air permeability of the heat generating portion 20 is sufficiently ensured, so that oxygen supply is sufficiently obtained, high heat generation efficiency is obtained, and oxidation reaction of the oxidizable metal becomes good. Also, it may be possible to generate a large amount of water vapor. Further, it is more preferably 300 seconds / 100 ml or less, and from the viewpoint of preventing an excessive temperature rise, it is more preferably 1 second / 100 ml or more.
　図４には、発熱層１３と、保水層１９とが積層され、成分（ａ）繊維材料、及び、成分（ｂ）吸水性ポリマーを含むものを保水層１９とした例が示されている。また、保水層１９は、吸水シート１０２から形成されている。図４中、発熱層１３には、被酸化性金属（Ｍ）と炭素成分（Ｃ）とが示されている。 FIG. 4 shows an example in which the heat retention layer 13 and the water retention layer 19 are laminated, and the material including the component (a) fiber material and the component (b) water absorbent polymer is used as the water retention layer 19. In addition, the water retaining layer 19 is formed of a water absorbing sheet 102. In FIG. 4, the heat generating layer 13 shows the oxidizable metal (M) and the carbon component (C).
　保水層１９は、成分（ａ）を含むシート、例えば、一層の繊維シートから構成されていてもよいし、二層以上が積層されていてもよい。繊維シートとしては、具体的には、後述する繊維材料から製造される紙、不織布、又は紙と不織布の積層したものなどが挙げられる。成分（ａ）を含むシートとしては、具体的には、ポリエチレン繊維、ポリプロピレン繊維、ポリエチレンシート、ポリプロピレンシートなど吸水性のない素材に繊維材料を積層又はラミネートした紙、不織布などのシート材でもよく、パルプ繊維やレーヨン繊維などの繊維材料に、さらに別の繊維材料を積層又は混合した抄紙、不織布などのシート材でもよい。保水層１９に成分（ａ）を含むシートを用いることで、保水層１９に含まれる水の含有量の調整がしやすく、発熱層中の水分量を適切にし、良好な発熱の立ち上がりと温感を良好に持続させる点から好ましい。 The water retention layer 19 may be composed of a sheet containing the component (a), for example, a single fiber sheet, or two or more layers may be laminated. Specifically as a fiber sheet, the paper, the nonwoven fabric manufactured from the fiber material mentioned later, or what laminated paper and a nonwoven fabric etc. are mentioned. Specifically, the sheet containing the component (a) may be a sheet material such as paper or non-woven fabric in which a fiber material is laminated or laminated on a material having no water absorbency such as polyethylene fiber, polypropylene fiber, polyethylene sheet, polypropylene sheet, It may be a sheet material such as paper making, non-woven fabric, etc., in which another fiber material is laminated or mixed with fiber material such as pulp fiber or rayon fiber. By using a sheet containing the component (a) in the water retention layer 19, the content of water contained in the water retention layer 19 can be easily adjusted, the water content in the heat generation layer is made appropriate, and good heat buildup and warmth It is preferable from the point of maintaining well.
　保水層１９は、さらに成分（ｂ）を含んでいてもよい。保水層１９に成分（ｂ）を含む場合、保水層１９の形態は、（ｉ）成分（ａ）及び成分（ｂ）が均一に混合された状態で１枚シートとしたもの、（ｉｉ）成分（ａ）を含む同一の又は異なるシート間に、成分（ｂ）が配置されたもの、（ｉｉｉ）成分（ｂ）を散布してシート状としたものを例示することができる。中でも、発熱層１３の含水量のコントロールを容易に行うことができるため保水層１９に含まれる水の含有量を保水層１９の水分量を容易に調整でき、好ましいものは、（ｉｉ）の形態のものである。なお、（ｉｉ）の形態の保水層１９は、例えば、成分（ａ）を含むシート上に成分（ｂ）を均一に散布し、その上から２００ｇ／ｍ２の量の水を噴霧した後、さらにその上に成分（ａ）を含む同一の又は異なるシートを積層し、１００±０．５℃、５ｋｇ／ｃｍ２の圧力にてプレスして、含水率が５質量％以下になるまで乾燥して製造することが可能である。 The water retention layer 19 may further contain the component (b). When the water retaining layer 19 contains the component (b), the form of the water retaining layer 19 is (i) one sheet in which the component (a) and the component (b) are uniformly mixed, (ii) the component Among the same or different sheets including (a), those in which the component (b) is disposed, and (iii) those in which the component (b) is dispersed to form a sheet can be exemplified. Among them, since the water content of the heat generating layer 13 can be easily controlled, the water content of the water holding layer 19 can be easily adjusted, and the preferable amount is the form of (ii) belongs to. In addition, the water retention layer 19 of the form of (ii) spreads the component (b) uniformly on the sheet | seat containing a component (a), for example, after spraying the water of the quantity of 200 g / m < 2 > on it, Furthermore, the same or different sheets containing the component (a) are laminated thereon and pressed at 100 ± 0.5 ° C., a pressure of 5 kg / cm 2 , and dried until the water content becomes 5% by mass or less. It is possible to manufacture.
　成分（ａ）としては、親水性繊維及び疎水性繊維のいずれをも用いることができるが、親水性繊維を用いることが好ましく、中でもセルロース繊維を用いることが保水層１９への水分移動を促し、保水層１９に含まれる水の含有量の調整がしやすく、発熱層中の水分量を適切にし、良好な発熱の立ち上がりと温感を良好に持続させる点から、より好ましい。セルロース繊維としては、化学繊維（合成繊維）や天然繊維を用いることができる。 As the component (a), any of hydrophilic fibers and hydrophobic fibers can be used, but it is preferable to use hydrophilic fibers. Among them, using cellulose fibers promotes the water transfer to the water retention layer 19, It is more preferable from the point of being easy to adjust the content of the water contained in the water retention layer 19, to make the water content in the heat generating layer appropriate, and to favorably maintain the rise of good heat generation and the warm feeling. As a cellulose fiber, a chemical fiber (synthetic fiber) or a natural fiber can be used.
　セルロース繊維のうち化学繊維としては、例えばレーヨンやアセテートを用いることができる。一方、セルロース繊維のうち天然繊維としては、例えば、各種の植物繊維、木材パルプ繊維、非木材パルプ繊維、木綿繊維、麻繊維、麦藁繊維、ヘンプ繊維、ジュート繊維、カポック繊維、やし繊維、及びいぐさ繊維から選択される１種又は２種以上を用いることができる。これらのセルロース繊維のうち、木材パルプ繊維を用いることが、保水層１９に含まれる水の含有量の調整がしやすく、発熱層中の水分量を適切にし、発熱の立ち上がりと温感を良好に持続させる点から好ましい。 Among the cellulose fibers, for example, rayon and acetate can be used as chemical fibers. On the other hand, natural fibers among cellulose fibers include, for example, various plant fibers, wood pulp fibers, non-wood pulp fibers, cotton fibers, hemp fibers, wheat straw fibers, hemp fibers, jute fibers, kapok fibers, palm fibers, and One or more selected from rag fiber can be used. Among these cellulose fibers, using wood pulp fibers makes it easy to adjust the content of water contained in the water retaining layer 19, makes the amount of water in the heat generating layer appropriate, and makes the rise of heat generation and the sense of warmth favorable. It is preferable from the point of sustaining.
　各種の繊維材料は、その繊維長が０．５～６ｍｍであることが好ましく、０．８～４ｍｍであることがより好ましい。なかでも繊維材料は、繊維長が０．５ｍｍ以上であることが好ましく、０．８ｍｍ以上であることがより好ましい。また、繊維材料は、繊維長が６ｍｍ以下であることが好ましく、４ｍｍ以下であることがより好ましい。 The fiber length of various fiber materials is preferably 0.5 to 6 mm, and more preferably 0.8 to 4 mm. Among them, the fiber length of the fiber material is preferably 0.5 mm or more, and more preferably 0.8 mm or more. The fiber length of the fiber material is preferably 6 mm or less, more preferably 4 mm or less.
　保水層１９には、親水性繊維に加え、必要に応じて疎水性繊維、中でも熱融着性繊維を含有してもよい。熱融着性繊維の含有量は、保水層１９における繊維の全量に対して０．１～１０質量％であることが好ましく、０．５～５質量％であることがより好ましい。
　また、熱融着性繊維の含有量は、保水層１９における繊維の全量に対して０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましい。また、熱融着性繊維の含有量は、保水層１９における繊維の全量に対して１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。 In addition to hydrophilic fibers, the water-retaining layer 19 may contain hydrophobic fibers, particularly heat-fusible fibers, if necessary. The content of the heat-fusible fiber is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, with respect to the total amount of fibers in the water retention layer 19.
In addition, the content of the heat-fusible fiber is preferably 0.1% by mass or more with respect to the total amount of fibers in the water retention layer 19, and more preferably 0.5% by mass or more. In addition, the content of the heat-fusible fiber is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of fibers in the water retention layer 19.
　成分（ｂ）として、上述の成分（ａ）と同様、自重の２０倍以上の液体を吸収・保持できる架橋構造を持つ親水性のポリマーを用いることで、保水層１９に含まれる水の含有量を適切に調整でき好ましい。
　成分（ｂ）の形状としては、球状、塊状、ブドウ房状、繊維状から選択される１種又は２種以上が挙げられる。成分（ｂ）の平均粒径は、１～１０００μｍであることが好ましく、１０～５００μｍであることがより好ましい。成分（ｂ）の平均粒径は、１μｍ以上であることが好ましく、１０μｍ以上であることがより好ましい。また、成分（ｂ）の平均粒径は、１０００μｍ以下であることが好ましく、５００μｍ以下であることがより好ましい。
　なお、成分（ｂ）の平均粒径は、動的光散乱法、レーザー回折法等により測定される。 The content of water contained in the water retention layer 19 by using, as the component (b), a hydrophilic polymer having a crosslinked structure capable of absorbing and holding a liquid 20 times or more its own weight, as in the above component (a) Can be properly adjusted.
As a shape of a component (b), 1 type (s) or 2 or more types selected from spherical shape, lump shape, grape-tuft shape, and fibrous form are mentioned. The average particle diameter of the component (b) is preferably 1 to 1000 μm, and more preferably 10 to 500 μm. The average particle diameter of the component (b) is preferably 1 μm or more, and more preferably 10 μm or more. The average particle diameter of the component (b) is preferably 1000 μm or less, 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.
　成分（ｂ）の具体例としては、例えば、デンプン、架橋カルボキシルメチル化セルロース、アクリル酸又はアクリル酸アルカリ金属塩の重合体又は共重合体等、ポリアクリル酸及びその塩並びにポリアクリル酸塩グラフト重合体から選択される１種又は２種以上が挙げられる。中でも、アクリル酸又はアクリル酸アルカリ金属塩の重合体又は共重合体等、ポリアクリル酸及びその塩並びにポリアクリル酸塩グラフト重合体を用いることが、保水層１９に含まれる水の含有量の調整がしやすく、発熱層中の水分量を適切にし、良好な発熱の立ち上がりと温感を良好に持続させる点から好ましい。 Specific examples of the component (b) include, for example, starch, crosslinked carboxylmethylated cellulose, a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid, polyacrylic acid and its salt, and polyacrylate graft weight 1 type, or 2 or more types selected from union are mentioned. Among them, the use of polyacrylic acid and its salt and polyacrylate graft polymer, such as a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid, adjustment of the content of water contained in water retention layer 19 It is preferable from the viewpoint of facilitating peeling, making the amount of water in the heat generating layer appropriate, and maintaining good heat build-up and warm feeling favorably.
　保水層１９に占める成分（ｂ）の割合は、乾燥状態で、１０～７０質量％であることが好ましく、さらに２０～６５質量％であることが、保水層１９への速やかな水分移動を促し、保水層１９に含まれる水の含有量の調整がしやすく、発熱層中の水分量を適切にし、良好な発熱の立ち上がりと温感を良好に持続させる点からより好ましい。
　同様の観点から、保水層１９に占める成分（ｂ）の割合は、乾燥状態で、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、一方、７０質量％以下であることが好ましく、６５質量％以下であることがより好ましい。 The proportion of the component (b) in the water retaining layer 19 is preferably 10 to 70% by mass in the dry state, and further 20 to 65% by mass promotes rapid water transfer to the water retaining layer 19 The water content of the water retention layer 19 can be easily adjusted, and the amount of water in the heat generation layer can be appropriately adjusted, which is preferable from the viewpoint of maintaining good rising of heat generation and good feeling of warmth.
From the same viewpoint, the proportion 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 70% by mass or less in the dry state. It is preferable that it is 65 mass% or less.
　保水層１９は、保水層１９に含まれる水の含有の調整がしやすく、発熱層中の水分量を適切にし、良好な発熱の立ち上がりと温感を良好に持続させる点から、乾燥状態でその坪量が２０～２００ｇ／ｍ２であることが好ましく、３５～１５０ｇ／ｍ２であることがより好ましく、５０～１４０ｇ／ｍ２であることがさらに好ましい。
　保水層１９に含まれる成分（ｂ）の坪量は、保水層１９に含まれる水の含有量の調整がしやすく、発熱層中の水分量を適切にし、良好な発熱の立ち上がりと温感を良好に持続させる点から乾燥状態で５～１５０ｇ／ｍ２であることが好ましく、１０～１００ｇ／ｍ２であることがより好ましく、３０～９０ｇ／ｍ２であることがさらに好ましい。
　保水層１９は、乾燥状態でその坪量が２０ｇ／ｍ２以上であることが好ましく、３５ｇ／ｍ２以上であることがより好ましく、５０ｇ／ｍ２以上であることがさらに好ましい。また、保水層１９は、乾燥状態でその坪量が２００ｇ／ｍ２以下であることが好ましく、１５０ｇ／ｍ２以下であることがより好ましく、１４０ｇ／ｍ２以下であることがさらに好ましい。
　保水層１９に含まれる成分（ｂ）の坪量は、乾燥状態でその坪量が５ｇ／ｍ２以上であることが好ましく、１０ｇ／ｍ２以上であることがより好ましく、３０ｇ／ｍ２以上であることがさらに好ましい。また、保水層１９は、乾燥状態でその坪量が１５０ｇ／ｍ２以下であることが好ましく、１００ｇ／ｍ２以下であることがより好ましく、９０ｇ／ｍ２以下であることがさらに好ましい。 The water retaining layer 19 is easy to adjust the content of water contained in the water retaining layer 19 and makes the amount of water in the heat generating layer appropriate, and in order to maintain good rising heat generation and a good sense of warmth, The basis weight is preferably 20 to 200 g / m 2 , more preferably 35 to 150 g / m 2 , and still more preferably 50 to 140 g / m 2 .
The basis weight of the component (b) contained in the water retention layer 19 makes it easy to adjust the content of water contained in the water retention layer 19, makes the water content in the heat generation layer appropriate, and makes good heat buildup and warmth It is preferably 5 to 150 g / m 2 in a dry state, more preferably 10 to 100 g / m 2 , and still more preferably 30 to 90 g / m 2 from the viewpoint of maintaining excellently.
The water retention layer 19 preferably has a basis weight of 20 g / m 2 or more in a dry state, more preferably 35 g / m 2 or more, and still more preferably 50 g / m 2 or more. The water retention layer 19 preferably has a basis weight of 200 g / m 2 or less in a dry state, more preferably 150 g / m 2 or less, and still more preferably 140 g / m 2 or less.
The basis weight of the component (b) contained in the water retention layer 19 is preferably 5 g / m 2 or more, more preferably 10 g / m 2 or more, and more preferably 30 g / m 2 or more in the dry state. It is further preferred that The water retention layer 19 preferably has a basis weight of 150 g / m 2 or less in a dry state, more preferably 100 g / m 2 or less, and still more preferably 90 g / m 2 or less.
　保水層１９は、図４に示すように発熱層１３が保水層１９の片面に形成されたものであってもよく、発熱層１３が保水層１９の両面に形成されたものであってもよい。 The water retaining layer 19 may have the heat generating layer 13 formed on one side of the water retaining layer 19 as shown in FIG. 4 or may have the heat generating layer 13 formed on both sides of the water retaining layer 19. .
　次に、発熱部２０の製造方法について説明する。
　まず、基材層１０を用意し、基材層１０上に、冷感剤と分子量が１，０００以下の溶剤を含む薬剤組成物を塗工して薬剤層１６を形成する。
　薬剤組成物の塗工方法は、特に限定されず、ダイコータ、ローラ塗布、スクリーン印刷、ローラグラビア、ナイフコーティング、及びカーテンコーター等を用いてもよい。
　また、薬剤組成物の塗工時の温度付近における粘度は、５～１００ｍＰａ・ｓであることが好ましく、１０～５０ｍＰａ・ｓであることが塗工のし易さや薬液の拡がり性の観点からより好ましい。たとえば、冷感剤としてメントールを使用する場合には、薬剤組成物として５０℃・５０ＲＨの条件下での粘度が上述の範囲であることが好ましい。なお、当該粘度の測定は、Ｂ型粘度計の４号ローターを用い、ローター回転速度を６０ｒｐｍで行う。 Next, a method of manufacturing the heat generating portion 20 will be described.
First, the base layer 10 is prepared, and a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less is coated on the base layer 10 to form the drug layer 16.
The coating method of the drug composition is not particularly limited, and a die coater, roller coating, screen printing, roller gravure, knife coating, curtain coater, or the like may be used.
The viscosity of the drug composition in the vicinity of the coating temperature is preferably 5 to 100 mPa · s, and it is preferably 10 to 50 mPa · s from the viewpoint of ease of coating and the spreadability of the chemical solution. preferable. For example, when menthol is used as a cooling agent, it is preferable that the viscosity under the conditions of 50 ° C. and 50 RH be in the above-mentioned range as a pharmaceutical composition. In addition, the measurement of the said viscosity is performed at 60 rpm of rotor rotational speeds using the No. 4 rotor of a Brookfield viscometer.
　次に、薬剤層１６上に発熱組成物が水中に分散した発熱粉体水分散物を塗工して発熱層１３を形成する。すなわち、発熱層１３は、発熱組成物の塗工層である。発熱粉体水分散物の塗工方法は、特に限定されず、たとえば、ダイコータ等が挙げられる。 Next, a heat generating powder water dispersion in which the heat generating composition is dispersed in water is coated on the drug layer 16 to form the heat generating layer 13. That is, the heat generating layer 13 is a coating layer of the heat generating composition. The coating method of the heat-generating powder water dispersion is not particularly limited, and examples thereof include a die coater and the like.
　上記の発熱粉体水分散物は、攪拌器により攪拌して、被酸化性金属、炭素成分、水に不溶な成分等をより均一に分散させることで得られる。また、発熱粉体水分散物は、前述した成分を全て一度に混合することで調製されてもよいが、予め、増粘剤を水に溶解したものに反応促進剤を溶解して水溶液を準備し、次に被酸化性金属と炭素成分とをプレ混合したものを水溶液と混合してもよい。 The heat-generating powder water dispersion can be obtained by uniformly dispersing the oxidizable metal, the carbon component, the water-insoluble component and the like by stirring with a stirrer. In addition, although the heat-generating powder water dispersion may be prepared by mixing all the components mentioned above at one time, the reaction accelerator is previously dissolved in a solution in which a thickener is dissolved in water to prepare an aqueous solution. Then, a pre-mixed oxidizable metal and carbon component may be mixed with the aqueous solution.
　その後、発熱層１３上に保水層１９を形成することによって、発熱部２０が製造される。保水層１９の形成方法は、特に限定されないが、たとえば、吸水性ポリマーの粒子を含む層を配してもよい。
　これにより、基材層１０と発熱層１３との間に、薬剤層１６が形成された発熱部２０を製造できる。 Thereafter, the water retention layer 19 is formed on the heat generating layer 13, whereby the heat generating portion 20 is manufactured. Although the formation method of the water holding layer 19 is not specifically limited, For example, you may distribute the layer containing the particle | grains of a water absorbing polymer.
Thus, the heat generating portion 20 in which the drug layer 16 is formed between the base layer 10 and the heat generating layer 13 can be manufactured.
［発熱体１８］
　発熱体１８は、発熱部２０と、発熱部２０を内部に収容する内袋１７とを備える。
　内袋１７は、シート１７１と、シート１７２の周縁部を接合することで構成されている。シート１７１と、シート１７２の周縁部以外の領域は非接合領域であり、非接合領域内に発熱層１３が配置される。 [Heating element 18]
The heat generating body 18 includes a heat generating portion 20 and an inner bag 17 accommodating the heat generating portion 20 therein.
The inner bag 17 is configured by joining the sheet 171 and the peripheral portion of the sheet 172. An area other than the sheet 171 and the peripheral portion of the sheet 172 is a non-joining area, and the heat generating layer 13 is disposed in the non-joining area.
　シート１７１は、温熱具１を使用者が肌に着用した際、発熱層１３よりも肌側に配置される。
　シート１７１は、通気性シートであり、その通気度は、４０，０００秒／１００ｍｌ以下であることが好ましく、２５，０００秒／１００ｍｌ以下であることがより好ましい。
　シート１７１の通気度を４０，０００秒／１００ｍｌ以下とすることで、シート１７１の通気性を確保し、発熱層１３からの蒸気をシート１７１外部に放出しやすくすることができる。
　一方で、シート１７１の通気度は、１０秒／１００ｍｌ以上であることが好ましく、１００秒／１００ｍｌ以上であることがより好ましい。シート１７１の通気度を１０秒／１００ｍｌ以上とすることで、発熱温度を制御し、異常発熱を防ぐことができる。 The sheet 171 is disposed closer to the skin than the heat generating layer 13 when the user wears the heating implement 1 on the skin.
The sheet 171 is a breathable sheet, and the air permeability thereof is preferably 40,000 seconds / 100 ml or less, 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 secured, and the vapor 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.
　このような通気度を有するシート１７１としては、例えば、透湿性は有するが透水性を有さない合成樹脂製の多孔性シートを用いることが好適である。具体的には、ポリエチレンに炭酸カルシウム等を含有させ延伸したフィルムを用いることができる。 As the sheet 171 having such an air permeability, for example, it is preferable to use a porous sheet made of a synthetic resin having moisture permeability but not water permeability. Specifically, a film obtained by containing calcium carbonate or the like in polyethylene and stretched can be used.
　シート１７２は、温熱具１を使用者が肌に着用した際、発熱層１３よりも肌よりも遠い側に位置する。
　シート１７１の外部に蒸気を放出しやすくする観点から、シート１７２の通気度は、シート１７１の通気度よりも高いことが好ましい。
　また、シート１７２の通気度は、酸素を少量ずつ取り込み、良好な発熱特性を保持する観点から、１５０，０００秒／１００ｍｌ以下が好ましく、１００，０００秒／１００ｍｌ以下がより好ましく、８５，０００秒／１００ｍｌ以下がさらに好ましい。一方、蒸気を外部に逃がさず、使用者に効率よく蒸気を付与する観点から、５０，０００秒／１００ｍｌ以上が好ましく、６０，０００秒／１００ｍｌ以上がより好ましい。 When the user wears the heating tool 1 on the skin, the sheet 172 is located on the side farther than the heat generation layer 13 than the skin.
It is preferable that the air permeability of the sheet 172 be higher than the air permeability 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, from the viewpoint of capturing oxygen little by little and maintaining good heat generation characteristics, and more preferably 85,000 seconds. It is more preferable that the amount be less than / 100 ml. On the other hand, from the viewpoint of efficiently applying the vapor to the user without letting the vapor escape to the outside, 50,000 seconds / 100 ml or more is preferable, and 60,000 seconds / 100 ml or more is more preferable.
　このような通気性を有するシート１７２としては、例えば、透湿性は有するが透水性を有さない合成樹脂製の多孔性シートを用いることが好適である。具体的には、ポリエチレンに炭酸カルシウム等を含有させ延伸したフィルムを用いることができる。 As the sheet 172 having such air permeability, for example, it is preferable to use a porous sheet made of a synthetic resin having moisture permeability but not water permeability. Specifically, a film obtained by containing calcium carbonate or the like in polyethylene and stretched can be used.
　ここで、温熱具１が通気性のシート１７２を有することで、第二シート１２及びシート１７２で構成されるシート層全体の通気性は、第一シート１１、シート１７１、基材層１０で構成されるシート層全体の通気性よりも低くなっている。換言すると、第二シート１２を最外層とし、第二シート１２から発熱層１３に至るまでのシート層全体の通気度は、第一シート１１を最外層とし、第一シート１１から発熱層１３に至るまでのシート層全体の通気度よりも高くなっている。具体的には、第二シート１２から発熱層１３に至るまでのシート層全体の通気度は、８０，０００秒／１００ｍｌ以上であることが好ましい。 Here, when the heating implement 1 has the breathable sheet 172, the breathability of the entire sheet layer configured of the second sheet 12 and the sheet 172 is configured of the first sheet 11, the sheet 171, and the base material layer 10. Is lower than the breathability of the entire sheet layer. 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 the first sheet 11 as the outermost layer, and the first sheet 11 to the heat generating layer 13 It is higher than the air permeability of the entire sheet 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.
　また、発熱体１８の平面形状は、好ましくは矩形形状であり、より好ましくは正方形形状である。 Moreover, the planar shape of the heat generating body 18 is preferably a rectangular shape, more preferably a square shape.
　発熱体１８は、第一シート１１及び第二シート１２で構成される外袋内部に収容される。また、発熱体１８のシート１７２の一部は、ホットメルト系接着剤等の接着剤により、第二シート１２に固定されていてもよい。これにより、外袋内で、発熱体２０が移動することを抑制できる。 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 heat generating body 18 may be fixed to the second sheet 12 by an adhesive such as a hot melt adhesive. Thus, movement of the heat generating body 20 can be suppressed in the outer bag.
　本実施形態の発熱体１８の表面最高温度は、使用者に気持ちよい温感と冷感を両立させる観点から、好ましくは３６℃以上であり、より好ましくは３８℃以上であり、さらに好ましくは４１℃以上である。
　また、発熱体１８の表面最高温度は、使用者に心地よい温感を与える観点から、好ましくは６０℃以下であり、より好ましくは５５℃以下であり、さらに好ましくは５０℃以下である。
　表面最高温度は、ＪＩＳ　Ｓ４１００に準拠した測定機を用いて測定することができる。 The surface maximum temperature of the heat generating body 18 according to the present embodiment is preferably 36 ° C. or more, more preferably 38 ° C. or more, and still more preferably 41 ° C., from the viewpoint of achieving both warmth and coolness comfortable for the user. It is above.
Further, the surface maximum temperature of the heating element 18 is preferably 60 ° C. or less, more preferably 55 ° C. or less, and still more preferably 50 ° C. or less, from the viewpoint of giving a comfortable warmth to the user.
The surface maximum temperature can be measured using a measuring device in accordance with JIS S4100.
［外袋］
　つぎに、外袋、すなわち、温熱具１の外郭を構成する第一シート１１及び第二シート１２について説明する。
　本実施形態では、第一シート１１及び第二シート１２はいずれも同一の大きさであり、同一平面形状である。本実施形態では、温熱具１は、第一シート１１側からの平面視において、長手方向Ｘとこれに直交する幅方向Ｙを有する横長の形状をしている。
　このように、温熱具１を、第一シート１１側からの平面視において、横長の扁平形状とすることで、温熱具１を、使用者の左右方向に延在するように、貼り付けることができる。 [Outer bag]
Next, an outer bag, that is, the first sheet 11 and the second sheet 12 constituting the outer shell of the heating implement 1 will be described.
In the present embodiment, the first sheet 11 and the second sheet 12 both have the same size and the same planar shape. In the present embodiment, the heating implement 1 has a laterally long shape having a longitudinal direction X and a width direction Y orthogonal to the longitudinal direction X in a plan view from the first sheet 11 side.
As described above, by making the heating tool 1 into a horizontally long flat shape in plan view from the first sheet 11 side, the heating tool 1 can be attached so as to extend in the left-right direction of the user it can.
　なお、前述のとおり、第一シート１１と第二シート１２とを別体のシートで構成し、互いの外周縁を貼り合わせることで、袋体を構成してもよく、また、第一シート１１と第二シート１２とを一連のシートで構成し、この一連のシートを折って、対向する外周縁同士を貼り合わせることで袋体を構成してもよい。 As described above, the first sheet 11 and the second sheet 12 may be configured as separate sheets, and the outer peripheral edge may be pasted together to configure a bag body. And the second sheet 12 may be configured as a series of sheets, the series of sheets may be folded, and the bag body may be configured by bonding the opposing outer peripheral edges to each other.
　第一シート１１は、温熱具１を使用者が着用した際に、使用者の肌側に位置する。第一シート１１は、通気性シートであり、その通気度は、８０００秒／１００ｍｌ以下である。なかでも、発熱層１３で発熱した蒸気の通気性を確実に確保する観点から、第一シート１１の通気度は、６，０００秒／１００ｍｌ以下であり、１，０００秒／１００ｍｌ以下であることがより好ましい。また、第一シート１１の通気度の下限値は特に限定されない。ただし、第一シート１１の内側、中でも内側に位置する内袋１７が透けて見えてしまうことを防止するための坪量等を考慮すると、１秒／１００ｍｌ以上であることが好ましい。 The first sheet 11 is positioned on the skin side of the user when the user wears the heating implement 1. The first sheet 11 is a breathable sheet, and the air permeability thereof is 8000 seconds / 100 ml or less. Above all, in order to ensure the air permeability of the steam generated by the heat generating layer 13, the air permeability of the first sheet 11 is 6,000 seconds / 100 ml or less and 1,000 seconds / 100 ml or less Is more preferred. Further, the lower limit value of the air permeability of the first sheet 11 is not particularly limited. However, in consideration of the basis weight and the like for preventing the inner bag 17 positioned inside the first sheet 11 from being seen through, in particular, it is preferably 1 second / 100 ml or more.
　第一シート１１としては、不織布をはじめとする繊維シートを使用できる。 As the first sheet 11, a fiber sheet including non-woven fabric can be used.
　第二シート１２は、本実施形態では、第一シート１１と同様の通気性を有するシートで構成されている。ただし、美観の観点から第一シート１１と同様、不織布で構成することが好ましい。 In the present embodiment, the second sheet 12 is configured of a sheet having the same air permeability as the first sheet 11. However, it is preferable to comprise with a nonwoven fabric like the 1st sheet | seat 11 from an aesthetic viewpoint.
　ここで、温熱具１は、少なくともＸ軸方向に伸縮可能な構成としてもよい。たとえば、第一シート１１及び第二シート１２を上述した通気性を有し、かつ、Ｘ軸方向に伸縮する伸縮性シートとしてもよい。伸縮性シートとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン、ポリアミド、ポリアクリル等から選択される合成繊維；セルロース、シルク、コットン、ウール等から選択される天然繊維；又はそれらを複合した繊維等から構成されるシートがあげられる。或いは、伸縮性シートとしては、２種以上の繊維を用いて、エアスルー法、スパンボンド法、ニードルパンチ法、メルトブローン法、カード法、熱融着法、水流交絡法、溶剤接着法から選択される方法により製造された不織布を用いることもできる。また、不織布以外に、編み布等も使用できる。特に、風合いや、弾力性の観点から、伸縮性シートとして伸縮性を有する不織布を用いることが好ましい。伸縮性を有する不織布としては、構成繊維として弾性繊維（例えば、ポリウレタン、ポリエステル）を含むエアスルー不織布やスパンボンド不織布等が好ましく、風合いの観点から不織布をシリコーンや界面活性剤等で表面処理したものを使用することもできる。なお、第一シート１１と第二シート１２とを同種材料で構成された伸縮性シートとしてもよく、異種材料で構成された伸縮性シートとしてもよい。 Here, the heating tool 1 may be configured to be extensible and contractable at least in the X-axis direction. For example, the first sheet 11 and the second sheet 12 may be the above-described breathable and stretchable sheets that expand and contract in the X-axis direction. Examples of the stretch sheet include synthetic fibers selected from polyesters such as polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), polyamides, polyacrylics, etc .; cellulose, silk, cotton, wool, etc. And a sheet composed of a natural fiber selected from Alternatively, the stretch sheet is selected from air through method, spun bond method, needle punch method, melt blown method, card method, heat fusion method, water entanglement method, solvent adhesion method using two or more kinds of fibers. Nonwoven fabrics produced by the method can also be used. In addition to non-woven fabrics, knitted fabrics can also be used. In particular, it is preferable to use a non-woven fabric having stretchability as the stretchable sheet from the viewpoint of texture and elasticity. As the non-woven fabric having elasticity, an air through non-woven fabric or a spun-bonded non-woven fabric containing elastic fibers (for example, polyurethane, polyester) as constituent fibers is preferable, and from the viewpoint of texture the non-woven fabric is surface-treated with silicone or surfactant It can also be used. The first sheet 11 and the second sheet 12 may be stretchable sheets made of the same material, or may be stretchable sheets made of different materials.
　次に、第一粘着層１４と第二粘着層１５について説明する。
　第一粘着層１４及び第二粘着層１５は、第一シート１１の外面に設けられている。第一粘着層１４及び第二粘着層１５は、温熱具１を使用者の肌に取り付けるためのものである。
　第一粘着層１４は一対からなり、該一対の第一粘着層１４は第一シート１１の外面に並列して一方向に延在するとともに離間配置され、好ましくは第一シート１１のＸ軸方向の端部にそれぞれ配置されている。第一シート１１の外面側からの平面視において、一対の第一粘着層１４は、発熱層１３と重なっていないことが発熱特性の点で好ましい。 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 for attaching the heating implement 1 to the skin of the user.
The first adhesive layer 14 is a pair, and the pair of first adhesive layers 14 extend in one direction parallel to the outer surface of the first sheet 11 and are spaced apart, preferably in the X-axis direction of the first sheet 11 Are arranged at the ends of the In a plan view from the outer surface side of the first sheet 11, the pair of first adhesive layers 14 preferably do not overlap with the heat generating layer 13 from the viewpoint of heat generation characteristics.
　一方で、第二粘着層１５は、第一シート１１側からの平面視において、一対の第一粘着層１４間の領域に配置され、第一粘着層１４に倣って同方向に延在している。本実施形態では、第二粘着層１５は、第一シート側からの平面視において、矩形形状となっている。 On the other hand, the second adhesive layer 15 is disposed in the region between the pair of first adhesive layers 14 in a plan view from the first sheet 11 side, and extends in the same direction following the first adhesive layers 14. There is. In the present embodiment, the second adhesive layer 15 has a rectangular shape in plan view from the first sheet side.
　第一粘着層１４及び第二粘着層１５は、アクリル系樹脂、酢酸ビニル系樹脂、オレフィン系樹脂から選択される少なくとも１種以上を含む粘着剤を、第一シート１１の外面に塗布することで形成される。 The first adhesive layer 14 and the second adhesive layer 15 are formed by applying an adhesive containing at least one or more selected from an acrylic resin, a vinyl acetate resin, and an olefin resin to the outer surface of the first sheet 11 It is formed.
　以上のような温熱具１は、酸素遮断性の袋に封入されることが望ましい。
　温熱具１を使用する際には、酸素遮断性の袋を開封し、温熱具１を取り出す。その後、剥離紙２１を取り外し、第一粘着層１４及び第二粘着層１５により、温熱具１を使用者の首の後ろ側に貼り付ける。これにより、温熱具１が使用者に固定されることとなる。 It is desirable that the above-mentioned heating implement 1 be enclosed in an oxygen barrier bag.
When the heating tool 1 is used, the oxygen barrier bag is opened and the heating tool 1 is taken out. Thereafter, the release paper 21 is removed, and the heating implement 1 is attached to the back side of the user's neck by the first adhesive layer 14 and the second adhesive layer 15. As a result, the heating implement 1 is fixed to the user.
　発熱層１３中の被酸化性金属が、空気と接触することで、被酸化性金属が酸化し、発熱層１３が発熱する。発熱層１３が発熱することで、発熱層１３中の水分が蒸発し、蒸気が発生する。蒸気は、基材層１０、シート１７１、第一シート１１を通じて温熱具１の外部に放出される。
　なお、発熱体に基材層１０が設けられていない場合には、シート１７１、第一シート１１を介して蒸気が外部に放出される。
　一方で、内袋１７のシート１７２は非通気層であるため、発熱層１３で発生した蒸気は、シート１７２により遮断されて、第二シート１２側から外部へはほとんど放出されない。これにより、シート１７１から優先的に蒸気を放出させることができ、使用者の肌に確実に蒸気を供給することができる。 When the oxidizable metal in the heat generating layer 13 contacts air, the oxidizable metal is oxidized and the heat generating layer 13 generates heat. As the heat generating layer 13 generates heat, the water in the heat generating layer 13 evaporates to generate steam. The vapor is released to the outside of the heating implement 1 through the base material layer 10, the sheet 171, and the first sheet 11.
In addition, when the base material layer 10 is not provided in the heat generating body, the vapor 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-ventilated layer, the steam generated in the heat generating layer 13 is blocked by the sheet 172 and hardly released from the second sheet 12 to the outside. Thereby, the steam can be released preferentially from the sheet 171, and the steam can be reliably supplied to the skin of the user.
　つぎに、温熱具１が本発明者らの着想である発熱挙動に対する冷感剤の揮散挙動を適切にすることが実現できた理由及びその効果について説明する。
　上述したように、本発明の温熱具１は特許文献１に記載された発熱具のように、溶剤や界面活性剤により冷感剤を発熱部の全体に均一に行きわたらせるものではなく、発熱層１３とは別に薬剤層１６を備えるものである。これにより、冷感剤による発熱特性への影響を効果的に抑制し、温熱具１の使用開始後すぐに良好な温感を付与できるようになるともに、冷感効果が得られやすくなる。そして、薬剤層１６が発熱層１３及び第二シート１２の間に配置されることにより、冷感剤が第一シート１１の通気性を低下させることで十分な発熱が得られなくなることを抑制でき、発熱時の立ち上がりの良さを安定的に得られるようになる。さらに、配置が制御された薬剤層１６において、分子量１，０００以下の溶剤を含むことによって、冷感剤の揮散速度が向上し、使用開始後すぐの発熱温度の上昇に伴って、冷感剤もスムーズに揮散されるようになり、かつ十分な量の冷感剤を揮散させることができる。これらが総合的に作用した結果、温熱具１においては、上記のような発熱温度の立ち上がりが良好になり、かつ、発熱温度の立ち上がりの早さと冷感剤の初期の揮散速度の速さとが適切に組み合わさったものと考えられる。本発明では、これに加え、さらに冷感剤の揮散量が向上される効果も得られ、これら全てが合わさることで、適用部位のコリや疲れ、痛みに対する効果感が向上し、即効感も高くなるといった、従来にはない効果が得られると推測される。さらには、冷感剤によるジンジン感も得られ、使用者の満足感が高まる。
　また、分子量１，０００以下の溶剤とすることで冷感剤の揮散挙動を制御できるメカニズムの詳細は明らかではないが、溶剤の分子量が高いほど、溶剤が発熱層１３中の被酸化性金属や炭素成分に作用して酸化反応を阻害しやすくなる結果、温熱具１の発熱開始時の立ち上がり温度を低下させるのに対し、溶剤の分子量を１，０００以下に小さくすることで、かかる立ち上がり温度の低下、ならびに冷感剤の揮散量及び速度の低下を抑制できると考えられる。 Next, the reason why it has been realized that the heating implement 1 appropriately makes the volatilization behavior of the cooling agent with respect to the heat generation behavior, which is the idea of the present inventors, and the effect thereof will be described.
As described above, the heating tool 1 of the present invention does not uniformly spread the cooling agent over the entire heating portion with a solvent or surfactant like the heating tool described in Patent Document 1, but generates heat. The drug layer 16 is provided separately from the layer 13. As a result, the influence of the cooling agent on the heat generation characteristics can be effectively suppressed, and a good sense of warmth can be imparted immediately after the start of use of the heating tool 1, and a cooling sensation effect can be easily obtained. And by the medicine layer 16 being arrange | positioned between the heat-generating layer 13 and the 2nd sheet 12, when a cooling agent reduces the air permeability of the 1st sheet 11, it can suppress that sufficient heat generation is no longer obtained. , It becomes possible to stably obtain good rise at the time of heat generation. Furthermore, 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 is improved, and the cooling agent is accompanied by the rise of the heat generation temperature immediately after the start of use. Can be volatilized smoothly, and a sufficient amount of cooling agent can be volatilized. As a result of these functions acting comprehensively, in the heating tool 1, the rise of the heat generation temperature as described above becomes favorable, and the speed of rise of the heat generation temperature and the speed of the initial volatilization rate of the cooling agent are appropriate. It is considered to be a combination of In the present invention, in addition to this, the effect of improving the volatilization amount of the cooling agent is also obtained, and by combining all of them, the sense of effect on the application site of coli, fatigue and pain is improved, and the immediate effect is high. It is estimated that the effect which can not be obtained conventionally can be obtained. Furthermore, a gingin sensation can be obtained by the cooling agent, and the user's satisfaction is enhanced.
Further, the details of 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 unclear, but the higher the molecular weight of the solvent, the more the solvent becomes an oxidizable metal in the heat generating layer 13 As a result of acting on the carbon component to easily inhibit the oxidation reaction, the rising temperature at the onset of heat generation of the heating tool 1 is decreased, while the molecular weight of the solvent is reduced to 1,000 or less. It is believed that the decrease can be suppressed as well as the decrease in the volatilization amount and rate of the cooling agent.
　さらに、温熱具１において、薬剤層１６が発熱層１３及び第二シート１２の間に配置されることにより、発熱層１３と第一シートの間にある保水層１９に冷感剤が吸着することで保水層１９の保水性が低下することを抑制できる。その結果、良好な発熱安定的に得られるようになる。
　また、薬剤層１６が発熱層１３及び第二シート１２の間に配置されることにより、第一シート１１に配置された第一粘着層１４及び第二粘着層１５の粘着性を良好に保持できる。言い換えると、薬剤層１６から染み出した冷感剤が第一粘着層１４及び第二粘着層１５に作用してその粘着性を低下させることを抑制できる。 Furthermore, in the heating implement 1, the cooling agent is adsorbed to the water retention layer 19 between the heat generating layer 13 and the first sheet by arranging the drug layer 16 between the heat generating layer 13 and the second sheet 12. It can suppress that the water retention capacity of the water retention layer 19 falls. As a result, good heat generation can be stably obtained.
Further, by arranging the drug 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 favorably maintained. . In other words, it is possible to suppress that the cooling agent exuded from the drug layer 16 acts on the first adhesive layer 14 and the second adhesive layer 15 to reduce the adhesiveness.
　なお、本発明は前述の実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれるものである。 Note that the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like as long as the object of the present invention can be achieved are included in the present invention.
　たとえば、上記実施形態では、シート１７２が非通気層であるとしたが、たとえば、第二シート１２、シート１７２のうち、いずれか一方を非通気層としてもよく、双方を非通気層としてもよい。 For example, although the sheet 172 is the non-permeable layer in the above embodiment, for example, either one of the second sheet 12 and the sheet 172 may be the non-permeable layer, or both may be the non-permeable layer. .
　さらには、内袋１７内部に、非通気性のシートを配置してもよい。この場合には、発熱層１３よりもシート１７２側に非通気性のシートを配置する。この非通気性のシートは、第二シート１２側からの平面視において、発熱層１３全体を被覆するものであることが好ましい。この場合、第二シート１２、シート１７２は非通気層であってもよく、通気層であってもよい。 Furthermore, a non-air-permeable sheet may be disposed inside the inner bag 17. In this case, a non-air-permeable sheet is disposed closer to the sheet 172 than the heat generating layer 13. The non-air-permeable sheet preferably covers the entire heat generating layer 13 in a plan view from the second sheet 12 side. In this case, the second sheet 12 and the sheet 172 may be non-ventilated layers or ventilated layers.
　さらには、上記実施形態では、第一シート側からの平面視において、第一粘着層１４の両端部、第二粘着層１５の両端部は、いずれも第一シート１１の外周縁に達していたが、これに限られるものではない。 Furthermore, in the above embodiment, both ends of the first adhesive layer 14 and both ends of the second adhesive layer 15 reach the outer peripheral edge of the first sheet 11 in plan view from the first sheet side. However, it is not limited to this.
　上記実施形態では、第一シート１１の外面に、第一粘着層１４及び第二粘着層１５が形成されている例について説明したが、第一粘着層１４及び第二粘着層１５は形成されていなくてもよい。この場合、温熱具１は、温熱具１の両端部に伸縮性の耳かけ部を設置するなど、他の固定部を有していてもよい。 Although the said embodiment demonstrated the example in which the 1st adhesion layer 14 and the 2nd adhesion layer 15 are formed in the outer surface of the 1st sheet 11, the 1st adhesion layer 14 and the 2nd adhesion layer 15 are formed It does not have to be. In this case, the heating implement 1 may have other fixing portions, such as installing stretchable ear hooks at both ends of the heating implement 1.
　また、上記実施形態では、発熱層１３は、内袋１７に収容されていたが、内袋１７は無くてもよい。この場合には、第一シート１１を含むとともに、上記発熱層１３に空気を供給するための通気層は、第一シート１１一枚で構成されていてもよい。このようにすることで、温熱具の構成を簡素化できる。
　また、上記実施形態では、温熱具１を首の後ろ側に貼り付けていたが、これに限らず、使用者の他の部位の肌面に貼り付けてもよい。 Moreover, in the said embodiment, although the heat-generating layer 13 was accommodated in the inner bag 17, the inner bag 17 may not be. In this case, the first sheet 11 may be included, and the ventilation layer for supplying air to the heat generating layer 13 may be configured of one first sheet 11. By doing this, the configuration of the heating tool can be simplified.
Moreover, in the said embodiment, although the heating implement 1 was stuck on the back side of the neck, you may stick not only to this but on the skin surface of the other site | part of a user.
　上述した実施形態に関し、本発明はさらに以下の温熱具を開示する。
＜１＞
　通気性を有する第一シートと、
　第二シートと、
　前記第一シート及び前記第二シートの間に配置された発熱層と、
　前記発熱層及び前記第二シートの間に配置された薬剤層と、
を備え、
　前記発熱層から前記第一シートまでの通気性が、前記発熱層から前記第二シートまでの通気性よりも高くなるように構成され、
　前記薬剤層は、冷感剤と、分子量が１，０００以下の溶剤とを含む薬剤組成物からなる温熱具。
＜２＞
　好ましくは、前記発熱層及び前記第一シートの間に保水層を有する、＜１＞に記載の温熱具。
＜３＞
　前記冷感剤は、好ましくは、メントール、１，８－シネオール、乳酸メンチル、酢酸メンチル、コハク酸モノメンチル、３－（ｌ－メントキシ）－１，２－プロパンジオール、及びＮ－エチル－３－ｐ－メンタンカルボキサミドよりなる群から選ばれる１種又は２種以上の化合物を含む、＜１＞又は＜２＞に記載の温熱具。
＜４＞
　前記溶剤の含有量は、前記薬剤組成物中の前記冷感剤と前記溶剤の合計量に対して、好ましくは、３０質量％以上、８５質量％以下である、＜１＞乃至＜３＞のいずれかに記載の温熱具。
＜５＞
　前記溶剤は、好ましくは、多価アルコールを含む、＜１＞乃至＜４＞のいずれかに記載の温熱具。
＜６＞
　前記溶剤は、好ましくは、ポリエチレングリコール、グリセリン、及びプロピレングリコールの中から選ばれる１種又は２種以上である、＜１＞乃至＜５＞のいずれかに記載の温熱具。
＜７＞
　前記溶剤の分子量は、好ましくは、６００以下である、＜１＞乃至＜６＞のいずれかに記載の温熱具。
＜８＞
　前記冷感剤の前記発熱層の平面視における面積に対する含有量は、好ましくは１．０ｍｇ／ｃｍ２以上である、＜１＞乃至＜７＞のいずれかに記載の温熱具。
＜９＞
　前記冷感剤の前記発熱層の平面視における面積に対する含有量は、好ましくは６．０ｍｇ／ｃｍ２以下である、＜１＞乃至＜８＞のいずれかに記載の温熱具。
＜１０＞
　前記溶剤の含有量は、前記発熱層の平面視における単位面積当たり、好ましくは２．０ｍｇ／ｃｍ２以上である、＜１＞乃至＜９＞のいずれかに記載の温熱具。
＜１１＞
　前記溶剤の含有量は、前記発熱層の平面視における単位面積当たり、好ましくは２０．０ｍｇ／ｃｍ２以下である、＜１＞乃至＜１０＞のいずれかに記載の温熱具。
＜１２＞
　前記薬剤組成物は、好ましくは、界面活性剤を実質的に含まない、＜１＞乃至＜１１＞のいずれかに記載の温熱具。
＜１３＞
　前記発熱層が、好ましくは、被酸化性金属、吸水剤及び水を備える、＜１＞乃至＜１２＞のいずれかに記載の温熱具。
＜１４＞
　前記発熱層が、好ましくは、増粘剤を含む、＜１＞乃至＜１３＞のいずれかに記載の温熱具。
＜１５＞
　前記被酸化性金属が、坪量で表して、好ましくは、１００ｇ／ｍ２以上、３，０００ｇ／ｍ２以下である、＜１３＞または＜１４＞に記載の温熱具。
＜１６＞
　前記発熱層が、好ましくは、発熱組成物の塗工層である、＜１＞乃至＜１５＞のいずれかに記載の温熱具。
＜１７＞
　前記発熱層から前記第二シートまでの通気度が、好ましくは、８０，０００秒／１００ｍｌ以上である、＜１＞乃至＜１６＞のいずれかに記載の温熱具。
＜１８＞
　好ましくは前記発熱部が内袋を有しており、前記内袋を構成するシートの内、発熱層より肌から遠い側に配されるシートの通気度が、発熱層より肌側に配されるシートの通気度の通気度よりも高い、＜１＞乃至＜１７＞のいずれかに記載の温熱具。
＜１９＞
　前記内袋を構成するシートの内、前記発熱層より肌側に配されるシートの通気度が、好ましくは、４０，０００秒／１００ｍｌ以下、１０秒／１００ｍｌ以上である、＜１８＞に記載の温熱具。
＜２０＞
　前記内袋を構成するシートの内、前記発熱層より肌から遠い側に配されるシートの通気度が、好ましくは、５０，０００秒／１００ｍｌ以上、１５０，０００秒／１００ｍｌ以下である、＜１８＞または＜１９＞に記載の温熱具。
＜２１＞
　発熱体が基材層、前記薬剤層、前記発熱層の順に積層されており、前記基材層は発熱層よりも肌から遠い側に位置するように配されている＜１＞乃至＜２０＞のいずれかに記載の温熱具。
＜２２＞
　発熱体が前記基材層、前記薬剤層、前記発熱層、前記保水層の順に積層されており、前記基材層は発熱層よりも肌から遠い側に位置するように配され、前記保水層が発熱層よりも肌側に位置するように配されている＜２＞乃至＜２１＞のいずれかに記載の温熱具。
＜２３＞
　前記発熱層の発熱開始後の前記冷感剤の揮散量が、好ましくは１ｍｇ／２時間以上、５ｍｇ／２時間以下である＜１＞乃至＜２２＞のいずれかに記載の温熱具。
＜２４＞
　発熱体の表面最高温度が好ましくは３８℃以上５５℃以下である＜１＞乃至＜２３＞のいずれかに記載の温熱具。
＜２５＞
　前記第一シートの前記発熱層側とは反対側の面に、好ましくは、粘着層を有する、＜１＞乃至＜２４＞のいずれかに記載の温熱具。
＜２６＞
　通気性を有する第一シートと、
　第二シートと、
　前記第一シート及び前記第二シートの間に配置された発熱層と、
　前記発熱層及び前記第二シートの間に配置された薬剤層と、
を備え、
　発熱体が基材層、前記薬剤層、前記発熱層の順に積層されており、
　前記基材層は前記発熱層よりも肌から遠い側に位置するように配され、
　前記発熱層から前記第一シートまでの通気性が、前記発熱層から前記第二シートまでの通気性よりも高くなるように構成され、
　前記薬剤層は、冷感剤としてメントールを含有し、メントールと分子量が１，０００以下の溶剤とを含む薬剤組成物からなり、
　前記溶剤は、前記冷感剤と前記溶剤の合計量に対して、３０質量％以上、８５質量％以下であり、
　前記冷感剤と前記発熱層に含有される被酸化金属との重量比が５以上５５以下である温熱具。
＜２７＞
　＜１＞乃至＜２５＞のいずれかに記載の温熱具の使用方法であって、好ましくは、前記第一シートを使用者の肌に適用する、温熱具の使用方法。
＜２８＞
　使用者の肌に温熱蒸気を適用するものである＜２７＞に記載に温熱具の使用方法。
＜２９＞
　＜１＞乃至＜２６＞のいずれかに記載の温熱具の、使用者の肌に冷感剤と温熱蒸気を同時に提供するための使用。 The present invention further discloses the following heating implement regarding the embodiment mentioned above.
<1>
A breathable first sheet,
The second sheet,
A heat generating layer disposed between the first sheet and the second sheet;
A drug layer disposed between the heat generating layer and the second sheet;
Equipped with
The air permeability from the heat generating layer to the first sheet is configured to be higher than the air permeability from the heat generating layer to the second sheet,
The heating agent, wherein the drug layer comprises a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less.
<2>
Preferably, the heating implement according to <1>, having a water retention layer between the heat generation layer and the first sheet.
<3>
The cooling agent is preferably menthol, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1,2-propanediol, and N-ethyl-3-p. -The heating implement according to <1> or <2>, comprising one or more compounds selected from the group consisting of menthancarboxamides.
<4>
The content of the solvent is preferably 30% by mass or more and 85% by mass or less based on the total amount of the cooling agent and the solvent in the pharmaceutical composition. The heating implement as described in any one.
<5>
The heating implement according to any one of <1> to <4>, wherein the solvent preferably contains a polyhydric alcohol.
<6>
The heating implement according to any one of <1> to <5>, wherein the solvent is preferably one or more selected from polyethylene glycol, glycerin and propylene glycol.
<7>
The heating implement according to any one of <1> to <6>, wherein the molecular weight of the solvent is preferably 600 or less.
<8>
The heating implement according to any one of <1> to <7>, wherein a content of the cooling agent with respect to an area in plan view of the heat generating layer is preferably 1.0 mg / cm 2 or more.
<9>
Content relative to the area in plan view of the heat generating layer of the cooling agent, preferably is 6.0 mg / cm 2 or less, <1> to warming device according to any one of <8>.
<10>
The heating implement according to any one of <1> to <9>, wherein a content of the solvent is preferably 2.0 mg / cm 2 or more per unit area in a plan view of the heat generating layer.
<11>
The heating implement according to any one of <1> to <10>, wherein a content of the solvent is preferably 20.0 mg / cm 2 or less per unit area of the heat generating layer in a plan view.
<12>
The heating implement according to any one of <1> to <11>, wherein the pharmaceutical composition is preferably substantially free of a surfactant.
<13>
The heating implement according to any one of <1> to <12>, wherein the heat generating layer preferably comprises an oxidizable metal, a water absorbing agent, and water.
<14>
The heating implement according to any one of <1> to <13>, wherein the heat generating layer preferably contains a thickener.
<15>
The heating implement according to <13> or <14>, wherein the oxidizable metal is represented by a basis weight, preferably 100 g / m 2 or more and 3,000 g / m 2 or less.
<16>
The heating implement according to any one of <1> to <15>, wherein the heat generating layer is preferably a coating layer of a heat generating composition.
<17>
The heating implement according to any one of <1> to <16>, wherein the air permeability from the heat generating layer to the second sheet is preferably 80,000 seconds / 100 ml or more.
<18>
Preferably, the heat generating portion has an inner bag, and among the sheets constituting the inner bag, the air permeability of the sheet disposed on the side farther from the skin than the heat generating layer is arranged closer to the skin than the heat generating layer. The heating implement according to any one of <1> to <17>, which is higher than the air permeability of the sheet.
<19>
Among the sheets constituting the inner bag, the air permeability of the sheet disposed on the skin side of the heat generating layer is preferably 40,000 seconds / 100 ml or less and 10 seconds / 100 ml or more, according to <18>. Heating tool.
<20>
Among the sheets constituting the inner bag, the air permeability of the sheet disposed on the side farther from the skin than the heat generating layer is preferably 50,000 seconds / 100 ml or more and 150,000 seconds / 100 ml or less. The heating implement as described in 18> or <19>.
<21>
The heating element is laminated in the order of the base material layer, the drug layer, and the heat generating layer, and the base material layer is disposed to be located on the side farther from the skin than the heat generating layer <1> to <20> The heating implement according to any of the above.
<22>
A heat generating body is laminated in the order of the base material layer, the drug layer, the heat generation layer, and the water retention layer, and the base material layer is disposed to be farther from the skin than the heat generation layer, the water retention layer The heating implement according to any one of <2> to <21>, which is disposed so as to be located on the skin side of the heat generating layer.
<23>
The heating implement according to any one of <1> to <22>, wherein the volatilization amount of the cooling agent after the start of heat generation of the heat generation layer is preferably 1 mg / 2 hours or more and 5 mg / 2 hours or less.
<24>
The heating implement according to any one of <1> to <23>, wherein the maximum surface temperature of the heating element is preferably 38 ° C. or more and 55 ° C. or less.
<25>
The heating implement according to any one of <1> to <24>, preferably having an adhesive layer on the side opposite to the heat generating layer side of the first sheet.
<26>
A breathable first sheet,
The second sheet,
A heat generating layer disposed between the first sheet and the second sheet;
A drug layer disposed between the heat generating layer and the second sheet;
Equipped with
A heating element is laminated in order of a base material layer, the drug layer, and the heat generating layer,
The base material layer is disposed to be farther from the skin than the heat generating layer,
The air permeability from the heat generating layer to the first sheet is configured to be higher than the air permeability from the heat generating layer to the second sheet,
The drug layer contains menthol as a cooling agent, and comprises a drug composition containing menthol and a solvent having a molecular weight of 1,000 or less,
The said solvent is 30 mass% or more and 85 mass% or less with respect to the total amount of the said cooling agent and the said solvent,
The heating implement wherein the weight ratio of the cooling agent to the metal to be oxidized contained in the heat generating layer is 5 or more and 55 or less.
<27>
It is a usage method of the heating implement in any one of <1> thru | or <25>, Comprising: Preferably, the usage method of the heating implement which applies said 1st sheet to a user's skin.
<28>
The usage method of a heating implement as described in <27> which applies thermal steam to a user's skin.
<29>
Use of the heating implement according to any one of <1> to <26> for simultaneously providing a cooling agent and a thermal vapor to a user's skin.
　以下、実施例により本発明をさらに詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」及び「部」はそれぞれ「質量％」及び「質量部」を意味する。 Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited to such embodiments. Unless otherwise specified, "%" and "parts" mean "mass%" and "parts by mass", respectively.
　図１に示すような構造の温熱具を以下のようにして作製した。
＜実施例１＞
〔発熱粉体水分散物の調製〕
　被酸化性金属１００質量部、炭素成分８質量部、水６２質量部、反応促進剤１１質量部、増粘剤０．２質量部、を用意し、次の手順で調整した。増粘剤を水に溶解し、次いで反応促進剤を溶解して水溶液を用意し、一方で被酸化性金属、炭素成分をプレ混合した粉体を用意し、水溶液にプレ混合粉体を入れ、ディスクタービン型攪拌羽根で１５０ｒｐｍ、１０分間攪拌してスラリー状の発熱粉体水分散物を得た。 A heating tool having a structure as shown in FIG. 1 was produced as follows.
Example 1
[Preparation of Heated 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 parts by mass of a thickener were prepared and adjusted in the following procedure. A thickener is dissolved in water, then a reaction accelerator is dissolved to prepare an aqueous solution, while a powder in which an oxidizable metal and a carbon component are pre-mixed is prepared, and the pre-mixed powder is added to the aqueous solution, The mixture was stirred for 10 minutes at 150 rpm with a disk turbine type stirring blade to obtain a slurry of a heat-generating powdery water dispersion.
　なお、被酸化性金属、炭素成分、水、反応促進剤、及び増粘剤の種類、製品名及び製造元は以下のとおりである。
＜原料組成物＞
被酸化性金属：鉄粉（鉄粉ＲＫＨ、平均粒径４５μｍ、ＤＯＷＡ　ＩＰ　クリエイション株式会社製）
炭素成分：活性炭（カルボラフィン、平均粒径４０μｍ、日本エンバイロケミカルズ株式会社製）
水：水道水
反応促進剤：塩化ナトリウム（局方塩化ナトリウム、大塚化学株式会社製）
増粘剤：キサンタンガム（エコーガムＢＴ、ＤＳＰ五協フード＆ケミカル株式会社製） The types of oxidizable metals, carbon components, water, reaction accelerators and thickeners, product names and manufacturers are as follows.
<Raw material composition>
Oxidizable metal: Iron powder (iron powder RKH, average particle diameter 45 μm, manufactured by Dowa IP Creation Ltd.)
Carbon component: Activated carbon (Carborafin, average particle size 40 μm, manufactured by Nippon Envirochemicals Co., Ltd.)
Water: Tap water reaction promoter: Sodium chloride (general method sodium chloride, manufactured by Otsuka Chemical Co., Ltd.)
Thickener: Xanthan gum (Echo Gum BT, DSP Gokyo Food & Chemical Co., Ltd.)
〔発熱部の作製〕
　保水層として、木材パルプ製の紙Ａ（２０ｇ／ｍ２、伊野紙株式会社製）と吸水性ポリマー（ポリアクリル酸ナトリウム、球状、平均粒子径３００μｍ、５０ｇ／ｍ２、アクアリックＣＡ、株式会社日本触媒製）と木材パルプ製の紙Ｂ（３０ｇ／ｍ２、伊野紙株式会社製）をこの順に積層して一体化したポリマーシートを使用した。また、基材層としてポリエチレンラミネート紙（大昭和紙工産業株式会社製）を準備した。
　２５ｃｍ２（５ｃｍ×５ｃｍ）のポリエチレンラミネート紙の上に、表１に示す組成で冷感剤を溶解した溶剤を塗布し（塗工量６０ｇ／ｍ２）、その塗布面上に、上記の発熱粉体水分散物を２５ｃｍ２（５ｃｍ×５ｃｍ）の範囲に６００ｇ／ｍ２の量にて塗布した。その後、形成された発熱層上に上述のポリマーシートを配して積層構造体である発熱部を作製した。 [Fabrication of heat generating portion]
As a water holding layer, wood pulp paper A (20 g / m 2 , manufactured by Ino Paper Co., Ltd.) and a water absorbing polymer (sodium polyacrylate, spherical, average particle diameter 300 μm, 50 g / m 2 , Aquaric CA, Ltd. A polymer sheet was used in which a paper manufactured by Nippon Shokuhin Co., Ltd. and paper B (30 g / m 2 , manufactured by Ino Paper Co., Ltd.) made by wood pulp were laminated in this order and integrated. Moreover, polyethylene laminated paper (made by Daishowa Paper Industry Co., Ltd.) was prepared as a base material layer.
On a 25 cm 2 (5 cm × 5 cm) polyethylene laminated paper, a solvent in which a cooling agent is dissolved according to the composition shown in Table 1 is applied (coating amount 60 g / m 2 ), and the above heat is generated on the coated surface. The powder water dispersion was applied in the range of 25 cm 2 (5 cm × 5 cm) in an amount of 600 g / m 2 . Thereafter, the above-described polymer sheet was disposed on the formed heat generating layer to produce a heat generating portion which is a laminated structure.
〔発熱体の作製〕
　第一シート（肌側に配される通気性のあるシート）の通気度が１６，０００秒／１００ｍｌであり、第二シート（非通気性シート）の通気度が８０，０００秒／１００ｍｌ以上である内袋内に発熱部を入れて、周縁部を密閉シールした。このとき、基材層側が、第二シート側に位置するように、発熱層を配置した。これにより、発熱体を得た。 [Preparation of heating element]
The air permeability of the first sheet (air permeable sheet placed on the skin side) is 16,000 seconds / 100 ml, and the air permeability of the second sheet (non air permeable sheet) is 80,000 seconds / 100 ml or more The heat generating part was put in a certain inner bag, and the peripheral part was hermetically sealed. At this time, the heat generating layer was disposed such that the substrate layer side was positioned on the second sheet side. Thus, a heating element was obtained.
〔温熱具の製造〕
　第一シートとして、ニードルパンチ不織布（通気度１秒／１００ｍｌ、坪量８０ｇ／ｍ２）を使用し、第二シートとして、スパンボンド不織布（通気度１秒／１００ｍｌ、坪量３８ｇ／ｍ２）を使用した。そして、第一シート、第二シートの内側に、発熱体を２つ離間配置した。その後、第一シート及び第二シートを重ね、周縁部を密閉シールした。
　さらに、第一シート側に、粘着層を配置し、温熱具を得た。 [Manufacturing of heating tools]
Needle punched non-woven fabric (air permeability 1 second / 100 ml, basis weight 80 g / m 2 ) is used as the first sheet, and spun bonded non-woven fabric (air permeability 1 second / 100 ml, basis weight 38 g / m 2 ) as the second sheet It was used. And two heating elements were spaced apart and arrange | positioned inside the 1st sheet | seat and the 2nd sheet | seat. Thereafter, the first sheet and the second sheet were stacked, and the peripheral edge was hermetically sealed.
Further, an adhesive layer was disposed on the first sheet side to obtain a heating tool.
＜実施例２～８＞
　表１に示す組成の冷感剤及び溶剤とした以外は、実施例１と同様にして、温熱具を得た。 Examples 2 to 8
A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used.
＜比較例１、２＞
　原料組成物の固形分（被酸化性金属、繊維状物及び活性炭の合計）１００部に対し、カチオン系凝集剤であるポリアミドエピクロロヒドリン樹脂（星光ＰＭＣ株式会社製、商品名「ＷＳ４０２０」）０．７部及びアニオン系凝集剤であるカルボキシメチルセルロースナトリウム（第一工業製薬株式会社製、商品名「ＨＥ１５００Ｆ」０．１８部を添加した。更に、水（工業用水）を、固形分濃度が１２％となるまで添加しスラリーを得た。 Comparative Examples 1 and 2
Polyamide epichlorohydrin resin (product of Starlight PMC Co., Ltd., trade name "WS 4020"), which is a cationic flocculant, relative to 100 parts of the solid content of the raw material composition (total of oxidizable metal, fibrous material and activated carbon) 0.7 part and 0.18 part of carboxymethylcellulose sodium (trade name "HE1500F" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "HE1500F", which is an anionic flocculant, were added. Furthermore, the solid content concentration was 12 It added until it became%, and the slurry was obtained.
　なお、原料組成物は、以下のとおりである。
＜原料組成物配合＞
・被酸化性金属：鉄粉、ＤＯＷＡ　ＩＰ　クリエイション株式会社製、商品名「ＲＫＨ」：８３％
・繊維状物：パルプ繊維（フレッチャー　チャレンジ　カナダ社製、商品名 ＮＢＫＰ「Ｍａｃｋｅｎｚｉ（ＣＳＦ２００ｍｌに調整）」）：８％
・反応促進剤：活性炭（日本エンバイロケミカルズ株式会社製、商品名「カルボラフィン」、平均粒径４５μｍ）９％ In addition, a raw material composition is as follows.
<Composition of raw material composition>
・ Oxidizable metal: Iron powder, manufactured by Dowa IP Creation Co., Ltd., trade name "RKH": 83%
-Fibrous material: Pulp fiber (Fletcher Challenge Canada, trade name: NBKP "Mackenzi (adjusted to 200 ml of CSF)"): 8%
・ Reaction accelerator: Activated carbon (made by Nippon Enviro Chemicals Co., Ltd., trade name "Carborafin", average particle diameter 45 μm) 9%
　前記スラリーを用い、これを抄紙ヘッドの直前で０．３％に水希釈し、傾斜型短網抄紙機によって、ライン速度１５ｍ／分にて抄紙して湿潤状態の成形シートを作製した。
　成形シートをフェルトで挟持して加圧脱水し、そのまま１４０℃の加熱ロール間に通し、含水率が５％以下になるまで乾燥した。乾燥後の坪量は４５０ｇ／ｍ2、厚さは０．４５ｍｍであった。このようにして得られた成形シートの組成を熱重量測定装置（セイコーインスツルメンツ社製、ＴＧ／ＤＴＡ６２００）を用いて測定した結果、鉄８３％、活性炭９％、パルプ８％であった。
　得られた成形シートを４９ｍｍ×４９ｍｍに切り取り、３枚を重ね合わせ、該成形シート１００部に対し電解液量（５％食塩水）が４５部となるように、電解液を注入した。
　その後、表１に示す組成で冷感剤を溶解した溶剤を、当該成形シートに注入し、毛管現象を利用して、成形シート全体に浸透させ、発熱部を得た。
　得られた発熱部を用いて、実施例１と同様に、発熱体を作製し、温熱具を得た。 Using the above slurry, it was diluted with water to 0.3% immediately before the paper making head, and papermaking was carried out at a line speed of 15 m / min by a inclined short wire paper machine to prepare a wet-formed sheet.
The formed sheet was sandwiched between felts, pressurized and dewatered, passed as it was between 140 ° C. heating rolls, and dried until the water content became 5% or less. The basis weight after drying was 450 g / m 2 and the thickness was 0.45 mm. The composition of the molded sheet thus obtained was measured using a thermogravimetric analyzer (TG / DTA6200, manufactured by Seiko Instruments Inc.). As a result, it was 83% iron, 9% activated carbon, and 8% pulp.
The obtained molded sheet was cut into 49 mm × 49 mm, three sheets were stacked, and the electrolytic solution was injected so that the amount of the electrolytic solution (5% saline solution) was 45 parts with respect to 100 parts of the molded sheet.
Then, the solvent which melt | dissolved the cooling agent by the composition shown in Table 1 was inject | poured into the said shaping | molding sheet, and it made it penetrate the whole shaping | molding sheet using capillary phenomenon, and obtained the heat-emitting part.
A heat generating body was produced using the obtained heat generating portion in the same manner as in Example 1 to obtain a heating tool.
＜比較例３＞
　表１に示す組成の冷感剤及び溶剤とし、冷感剤が表１に示す位置となるようにした以外は、実施例１と同様にして、温熱具を得た。
　具体的には、２５ｃｍ２（５ｃｍ×５ｃｍ）のポリエチレンラミネート紙の上に、上記の発熱粉体水分散物を２５ｃｍ２（５ｃｍ×５ｃｍ）の範囲に６００ｇ／ｍ２の量にて塗布した後、表１に示す組成で冷感剤を溶解した溶剤を塗布し（塗工量６０ｇ／ｍ２）、その塗布面上に、上述のポリマーシートを配して積層構造体である発熱部を作製した。 Comparative Example 3
A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used, and the cooling agent was positioned as shown in Table 1.
Specifically, after applying the above-mentioned heat-generating powdery water dispersion on a 25 cm 2 (5 cm × 5 cm) polyethylene laminated paper in an amount of 600 g / m 2 in the range of 25 cm 2 (5 cm × 5 cm) The solvent which dissolved the cooling agent by composition shown in Table 1 is applied (coating amount 60 g / m 2 ), the above-mentioned polymer sheet is arranged on the application side, and the exothermic part which is a lamination structure is produced. did.
＜比較例４＞
　表１に示す組成の冷感剤及び溶剤とし、冷感剤が表１に示す位置となるようにした以外は、実施例１と同様にして、温熱具を得た。
　具体的には、２５ｃｍ２（５ｃｍ×５ｃｍ）のポリエチレンラミネート紙の上に、上記の発熱粉体水分散物を２５ｃｍ２（５ｃｍ×５ｃｍ）の範囲に６００ｇ／ｍ２の量にて塗布した後、その塗布面上に、上述のポリマーシートを配し、その上に、表１に示す組成で冷感剤を溶解した溶剤を塗布し（塗工量６０ｇ／ｍ２）て積層構造体を作製し、発熱部を作製した。 Comparative Example 4
A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used, and the cooling agent was positioned as shown in Table 1.
Specifically, after applying the above-mentioned heat-generating powdery water dispersion on a 25 cm 2 (5 cm × 5 cm) polyethylene laminated paper in an amount of 600 g / m 2 in the range of 25 cm 2 (5 cm × 5 cm) Then, the above-mentioned polymer sheet is disposed on the coated surface, and a solvent in which the cooling agent is dissolved with the composition shown in Table 1 is coated thereon (coating amount 60 g / m 2 ) to produce a laminated structure And the heat generating portion was produced.
＜比較例５＞
　表１に示す組成の冷感剤及び溶剤とした以外は、実施例１と同様にして、温熱具を得た。 Comparative Example 5
A heating tool was obtained in the same manner as in Example 1 except that the cooling agent and the solvent having the composition shown in Table 1 were used.
　上記の実施例及び比較例で得られた温熱具を用いて、以下の評価を行った。結果を表１に示す。なお、温熱具は、評価を行う直前まで、酸素遮断性の袋内に密閉しておいた。 The following evaluation was performed using the heating implement obtained by said Example and comparative example. The results are shown in Table 1. The heating tool was sealed in an oxygen barrier bag until immediately before the evaluation.
（評価）
・発熱特性（適用初期の発熱の立ち上がり）
　ＪＩＳ　Ｓ４１００に準拠した測定機を用いて、温熱具の第一シートの外面のうち、発熱部がある面の中心に、測定機の温度センサーを貼り付けて、室温２０℃、絶対湿度５０％、酸素存在下で発熱部の発熱を開始させ、心地よい温感を感じる４２℃に到達するまでに要する時間（分）を測定した。 (Evaluation)
· Heat generation characteristics (rise of heat generation in the early stage of application)
A temperature sensor of the measuring device is attached to the center of the surface of the first sheet of the heating tool with the heat generating part using a measuring device in accordance with JIS S4100, room temperature 20 ° C., absolute humidity 50%, The heat generation of the heat generating portion was started in the presence of oxygen, and the time (minute) required to reach 42 ° C. for feeling a comfortable warm feeling was measured.
・メントール揮散量
　まず、発熱体が酸化反応を行う程度に充分な量の空気が入った１５ｃｍ×２５ｃｍのポリフッ化ビニル樹脂の気体捕集バッグ（テドラー（商標登録）バッグ、デュポン社製）を用意し、気体捕集バッグの一方の端部を空気供給源に接続し、他方の端部の吐出口又は吐出口に連結したチューブの先端をエタノール中に浸漬させた。
　次に、メントールが保持された発熱体を酸素遮断袋から取り出し、当該気体捕集バッグにいれて、３５℃に設定したホットプレート上に２時間載置した。ホットプレート上に載置している間、空気供給源から気体捕集バッグ内に一定スピードで（１００ｍＬ／ｍｉｎ）空気を流入させ、気体捕集バッグの他方の端部の吐出口又は吐出口に連結したチューブの先端から空気を排出させることで、発熱体から揮散したメントールをエタノール中に捕集した。また、気体捕集バッグ内に流入した空気が適切に排出されるよう、気体捕集バッグ上に重りを載せ、気体捕集バッグの周囲は、ホットプレートによる加温が保持されるように、断熱材により断熱した。
　２時間の載置後、気体捕集バッグから発熱体を取り出し、気体捕集バッグ内をエタノールで洗浄し、洗浄に用いたエタノールも捕集して、メントールの揮散量に合計した。
　メントールの捕集量の分析は、ガスクロマトグラフィー（Ａｇｉｌｅｎｔ　６８９０Ｎ、アジレント・テクノロジー株式会社製）により行った。
　これらの作業は全て大気圧下で行った。
　なお、温熱具は発熱体を２つ用いているため、温熱具のメントール揮散量は、発熱体一つあたりで測定された量の２倍とした。 -Volume of menthol volatilization First, a 15 cm x 25 cm polyvinyl fluoride resin gas collection bag (Tedlar (registered trademark) bag, manufactured by DuPont) containing a sufficient amount of air enough to cause an oxidation reaction of the heating element is prepared. Then, one end of the gas collection bag was connected to an air supply, and the discharge port at the other end or the tip of a tube connected to the discharge port was immersed in ethanol.
Next, the heating element holding menthol was removed from the oxygen blocking bag, placed in the gas collection bag, and placed on a hot plate set at 35 ° C. for 2 hours. While placed on the hot plate, air is allowed to flow into the gas collection bag from the air supply source at a constant speed (100 mL / min), and the discharge port or discharge port at the other end of the gas collection bag By discharging air from the tip of the connected tube, menthol volatilized from the heating element was collected in ethanol. In addition, a weight is placed on the gas collection bag so that the air flowing into the gas collection bag is properly discharged, and the surroundings of the gas collection bag are thermally insulated so that the heating by the hot plate is maintained. The material was thermally insulated.
After placing for 2 hours, the heating element was taken out from the gas collection bag, the inside of the gas collection bag was washed with ethanol, ethanol used for washing was also collected, and the total amount of menthol was volatilized.
The analysis of the collected amount of menthol was performed by gas chromatography (Agilent 6890N, manufactured by Agilent Technologies, Inc.).
All these operations were performed under atmospheric pressure.
Since two heating elements were used for the heating tool, the amount of menthol volatilization of the heating tool was twice the amount measured per heating element.
・官能評価
〔肩と腰の痛みへの効果感〕
　肩又は腰への痛みを感じている被験者５名に各温熱具を適用し、８時間適用した後において、コリや痛みがどの程度改善したのかを、以下の５段階の基準で評価させ、その平均値をとった。
５：痛みが緩和されとても軽くなるような効果感を感じる
４：痛みが緩和され、効果感を感じる。
３：装着時痛みが緩和されるような感覚を感じるが効果感についてはどちらも言えない。
２：痛みに対する効果感をあまり感じない
１：痛みに対する効果感を全く感じない ・ Sensory evaluation (effect on shoulder and lower back pain)
After applying each heating tool to five subjects who feel pain in the shoulders or lower back and applying it for 8 hours, the extent of improvement of colitis and pain is evaluated according to the following five-step criteria, I took an average value.
5: A feeling of effect that pain is relieved and it is very lightened 4: Pain is relieved and a feeling of effect is felt.
3: I feel a feeling that pain is relieved at the time of wearing, but neither can be said about a feeling of effect.
2: I do not feel much effect on pain 1: I do not feel at all effect on pain
〔即効感〕
　肩又は腰への痛みを感じている被験者５名に各温熱具を適用し、適用後10～30分経過時点において、コリや痛みが軽減すると感じたかどうかを、以下の５段階の基準で評価させ、その平均値をとった。
５：痛みが軽減する感覚を非常に感じる
４：痛みが軽減する感覚を感じる
３：やや痛みが軽減する感覚を感じる
２：どちらとも言えない
１：痛みが軽減する感じはしない。 [Immediate effect]
Apply each heating tool to 5 subjects who feel pain in the shoulders or lower back, and evaluate whether they felt that they would be relieved from pain or pain 10 to 30 minutes after the application, based on the following 5 criteria: Let me take that average.
5: I feel a sense of pain relieved very much 4: I feel a sense of pain alleviated 3: Slightly feel a sensation of diminished pain 2: I can not say either of them 1: I do not feel pain relieved.
〔メントール実感の評価〕
　被験者５名に各温熱具を適用し、６時間適用後メントールのジンジンする感覚の強さについて、以下の５段階の基準で評価させ、その平均値をとった。
５：とても優れている（メントールのジンジン感もちょうど良い。メントール感も早期に感じられ、それが持続した。）
４：優れている（メントール感はちょうど良いが、メントールを感じるまでやや時間がかかる或いはメントールの持続時間がやや短い）
３：問題ない（メントール感は感じるがメントールの強さやメントール感の持続時間がやや物足りない。）
２：メントール感が明らかに弱い
１：メントール感が全くしない。 [Evaluation of menthol feeling]
Each heating tool was applied to five subjects, and after applying for 6 hours, the strength of the feeling of gindine menthol was evaluated according to the following five-step criteria, and the average value was taken.
5: Very good (Menthol's ginzine is just right. Menthol also felt early and it lasted.)
4: Excellent (Menthol feeling is just right, but it takes some time to feel menthol or the duration of menthol is rather short)
3: No problem (I feel a sense of menthol, but the strength of menthol and the duration of the menthol feeling are somewhat inadequate.)
2: The feeling of menthol is obviously weak 1: The feeling of menthol is not at all.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例３と、実施例８とを比較すると、実施例３はＰＥＧ４００を用いているために、ＰＥＧ１０００を用いた実施例８に比べて、４２℃立ち上がり時間、及びメントール揮発量がより一層揮発向上し、その結果、痛みへの効果感、即効感、メントール実感がより一層優れたものと考えられる。すなわち、溶剤の分子量を低くすることによって、本発明の効果が得られやすくなるものと推測される。
　また、比較例３は、４２℃の立ち上がり時間が長いため、即効感が得られず、メントール実感も弱いものであった。また、比較例４は、４２℃まで温度が上がらなかったため、痛みへの効果感、即効感、メントール実感すべてにおいて、不十分なものであった。
　なお、実施例１の温熱具において、分子量２０００のポリエチレングリコールを用いた場合、メントールの揮散量が１ｍｇ／２時間に到達せず、効果感、即効感、ジンジン感のいずれにおいても劣るものであった。 Comparing Example 3 with Example 8, since Example 3 uses PEG 400, the rise time at 42 ° C. and the amount of menthol volatilization are further improved by volatilization as compared with Example 8 using PEG 1000. As a result, it is considered that the feeling of effect on pain, the immediate effect, and the feeling of menthol are even better. 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 addition, in Comparative Example 3, since the rise time at 42 ° C. was long, no immediate effect was obtained, and the menthol feeling was also weak. Further, in Comparative Example 4, the temperature did not rise up to 42 ° C., and therefore the sense of effect on pain, the immediate effect, and the feeling of menthol were all inadequate.
In the heating implement of Example 1, when polyethylene glycol having a molecular weight of 2000 is used, the amount of menthol volatilized does not reach 1 mg / 2 hours and is inferior in any of the feeling of effect, immediate effect, and gingin feeling. The

Claims (10)

  1. 　通気性を有する第一シートと、
    　第二シートと、
    　前記第一シート及び前記第二シートの間に配置された発熱層と、
    　前記発熱層及び前記第二シートの間に配置された薬剤層と、
    を備え、
    　前記発熱層から前記第一シートまでの通気性が、前記発熱層から前記第二シートまでの通気性よりも高くなるように構成され、
    　前記薬剤層は、冷感剤と、分子量が１，０００以下の溶剤とを含む薬剤組成物からなる温熱具。     A breathable first sheet,
    The second sheet,
    A heat generating layer disposed between the first sheet and the second sheet;
    A drug layer disposed between the heat generating layer and the second sheet;
    Equipped with
    The air permeability from the heat generating layer to the first sheet is configured to be higher than the air permeability from the heat generating layer to the second sheet,
    The heating agent, wherein the drug layer comprises a drug composition containing a cooling agent and a solvent having a molecular weight of 1,000 or less.
  2. 　前記発熱層及び前記第一シートの間に保水層を有する、請求項１に記載の温熱具。 The heating implement according to claim 1 which has a water holding layer between said exothermic layer and said 1st sheet.
  3. 　前記冷感剤は、メントール、１，８－シネオール、乳酸メンチル、酢酸メンチル、コハク酸モノメンチル、３－（ｌ－メントキシ）－１，２－プロパンジオール、及びＮ－エチル－３－ｐ－メンタンカルボキサミドよりなる群から選ばれる１種又は２種以上の化合物を含む、請求項１又は２に記載の温熱具。 The cooling agent is menthol, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1,2-propanediol, and N-ethyl-3-p-menthancarboxamide The heating implement according to claim 1 or 2, comprising one or more compounds selected from the group consisting of
  4. 　前記溶剤の含有量は、前記薬剤組成物全量に対して、３０質量％以上、８５質量％以下である、請求項１乃至３のいずれか一項に記載の温熱具。 The heating implement according to any one of claims 1 to 3, wherein a content of the solvent is 30% by mass or more and 85% by mass or less with respect to the total amount of the drug composition.
  5. 　前記溶剤は、ポリエチレングリコール、グリセリン、及びプロピレングリコールの中から選ばれる１種又は２種以上である、請求項１乃至４のいずれか一項に記載の温熱具。 The heating implement according to any one of claims 1 to 4, wherein the solvent is one or more selected from polyethylene glycol, glycerin and propylene glycol.
  6. 　前記発熱層から前記第二シートまでの通気度が、８０，０００秒／１００ｍｌ以上である、請求項１乃至５のいずれか一項に記載の温熱具。 The heating implement 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. 　前記第一シートの前記発熱層側とは反対側の面に、粘着層を有する、請求項１乃至６のいずれか一項に記載の温熱具。 The heating implement according to any one of claims 1 to 6, further comprising an adhesive layer on the side opposite to the heat generating layer side of the first sheet.
  8. 　前記発熱層が被酸化性金属を含み、前記被酸化性金属と、前記温熱具中に含まれる前記冷感剤との重量比（被酸化性金属/冷感剤）が、５以上５５以下である、請求項１乃至７のいずれか一項に記載の温熱具。 The heat generating layer contains an oxidizable metal, and the weight ratio of the oxidizable metal to the cooling agent contained in the heating tool (oxidizing metal / cooling agent) is 5 or more and 55 or less The heating implement according to any one of claims 1 to 7, which is one.
  9. 　請求項１乃至８に記載の温熱具の使用方法であって、前記第一シートを使用者の肌に適用する、温熱具の使用方法。 A method of using the heating implement according to any one of claims 1 to 8, wherein the first sheet is applied to the skin of the user.
  10. 　使用者の肌に冷感剤と温熱蒸気を同時に提供するための請求項1乃至８に記載の温熱具の使用。 9. Use of a heating implement according to claims 1 to 8 for simultaneously providing a cooling agent and a thermal vapor to the skin of a user.
PCT/JP2018/030926 2017-08-23 2018-08-22 Heating tool WO2019039497A1 (en)

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