WO2013094746A1 - 蒸気温熱具 - Google Patents
蒸気温熱具 Download PDFInfo
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- WO2013094746A1 WO2013094746A1 PCT/JP2012/083311 JP2012083311W WO2013094746A1 WO 2013094746 A1 WO2013094746 A1 WO 2013094746A1 JP 2012083311 W JP2012083311 W JP 2012083311W WO 2013094746 A1 WO2013094746 A1 WO 2013094746A1
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- water
- mass
- sheet
- parts
- steam heating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24V—COLLECTION, PRODUCTION OR USE OF HEAT NOT OTHERWISE PROVIDED FOR
- F24V30/00—Apparatus or devices using heat produced by exothermal chemical reactions other than combustion
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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
- A61F7/032—Compresses or poultices for effecting heating or cooling thermophore, i.e. self-heating, e.g. using a chemical reaction using oxygen from the air, e.g. pocket-stoves
- A61F7/034—Flameless
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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
- A61F2007/0001—Body part
- A61F2007/0002—Head or parts thereof
- A61F2007/0003—Face
-
- 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
- A61F2007/0001—Body part
- A61F2007/0002—Head or parts thereof
- A61F2007/0004—Eyes or part of the face surrounding the eyes
-
- 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
- A61F2007/0059—Heating or cooling appliances for medical or therapeutic treatment of the human body with an open fluid circuit
- A61F2007/006—Heating or cooling appliances for medical or therapeutic treatment of the human body with an open fluid circuit of gas
- A61F2007/0062—Heating or cooling appliances for medical or therapeutic treatment of the human body with an open fluid circuit of gas the gas being steam or water vapour
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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
- A61F2007/0098—Heating or cooling appliances for medical or therapeutic treatment of the human body ways of manufacturing heating or cooling devices for therapy
-
- 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
- A61F2007/0203—Cataplasms, poultices or compresses, characterised by their contents; Bags therefor
- A61F2007/0206—Cataplasms, poultices or compresses, characterised by their contents; Bags therefor containing organic solids or fibres
- A61F2007/0209—Synthetics, e.g. plastics
- A61F2007/0214—Polymers, e.g. water absorbing
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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
- A61F2007/0203—Cataplasms, poultices or compresses, characterised by their contents; Bags therefor
- A61F2007/022—Bags therefor
-
- 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
- A61F2007/0225—Compresses or poultices for effecting heating or cooling connected to the body or a part thereof
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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
- A61F2007/0244—Compresses or poultices for effecting heating or cooling with layers
- A61F2007/0258—Compresses or poultices for effecting heating or cooling with layers with a fluid permeable layer
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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
- A61F2007/0244—Compresses or poultices for effecting heating or cooling with layers
- A61F2007/026—Compresses or poultices for effecting heating or cooling with layers with a fluid absorbing layer
Definitions
- the present invention relates to a steam heating device.
- Patent Document 1 discloses a steam heating device that includes a steam temperature generation unit and a water retention sheet disposed adjacent to the steam temperature generation unit.
- a heat generating part formed by laminating a heat generating layer made of a heat generating composition containing an oxidizable metal, water, and a water retention agent, and a water retaining sheet containing a polymer, A steam heating tool having air permeability at least in part, and a bag body containing the heat generating part,
- the amount of water contained in the steam heating tool is 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the content of the water retention agent is 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the amount of water contained in the heat generating layer is 8 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- a steam heating apparatus is provided in which the amount of water contained in the water retaining sheet is 15 to 30% by mass of the maximum water absorption amount of the water retaining sheet.
- the steam heating tool 100 is a steam heating tool having a heating part 121 in which a heating layer 121A made of a heating composition containing an oxidizable metal, water, and a water retention agent and a water retention sheet 121C are laminated.
- This steam heating tool 100 is (A) The amount of water contained in the steam heating device 100 is 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. (B) The content of the water retaining agent contained in the heat generating layer 121A is 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the amount of water contained in the heat generating layer 121A is 8 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the amount of water contained in the water retention sheet 121C is 15 to 30% by mass of the maximum water absorption amount of the water retention sheet.
- the steam heating device 100 generates heat by an oxidation reaction of an oxidizable metal and gives a sufficient heating effect, and can have a performance of an exothermic temperature of 38 to 70 ° C. in the measurement according to JIS standard S4100. .
- the amount of water vapor generated from the steam heating device 100 is preferably 0.01 mg / (cm 2 ⁇ min) or more, and more preferably 0.03 mg / (cm 2 ⁇ min) or more. Further, the upper limit value of the amount of water vapor generated is, for example, preferably 0.8 mg / (cm 2 ⁇ min) or less, and more preferably 0.4 mg / (cm 2 ⁇ min) or less.
- the steam heating tool 100 has a heating element 120 shown in FIG.
- the heating element 120 includes a heating part 121 and a first bag body 122 that encloses the heating part 121.
- the heat generating part 121 includes a heat generating layer 121A, a water retention sheet 121C, and a sheet 121B.
- the heat generating layer 121A is made of a heat generating composition containing an oxidizable metal, water, and a water retention agent.
- the oxidizable metal is a metal that generates heat of oxidation reaction, and examples thereof include powders and fibers of iron, aluminum, zinc, manganese, magnesium, calcium, and mixed metals in which two or more of these are mixed. Of these, one or more can be used. Among these, iron powder is preferable from the viewpoints of handleability, safety, manufacturing cost, storage stability, and stability. Examples of the iron powder include reduced iron powder and atomized iron powder.
- the average particle size is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, from the viewpoint that the oxidation reaction is efficiently performed. More preferably, it is 20 to 100 ⁇ m.
- the particle size of the oxidizable metal refers to the maximum length in the form of powder, and is measured by classification using a sieve, dynamic light scattering method, laser diffraction method or the like. From the same viewpoint, when the oxidizable metal is a powder, the average particle size is preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more.
- the average particle size is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
- the content of the oxidizable metal in the exothermic composition constituting the exothermic layer 121A is preferably 100 to 3,000 g / m 2 , particularly 200 to 1,500 g / m 2 in terms of basis weight.
- the heat generation temperature of the heat generating body 120 can be raised to a desired temperature.
- the content of the iron powder in the heating element 120 can be obtained by an ash content test according to JIS P8128 or a thermogravimetric measuring instrument.
- it can be quantified by a vibration sample type magnetization measurement test or the like using the property that magnetization occurs when an external magnetic field is applied.
- the content of the oxidizable metal in the exothermic composition constituting the exothermic layer 121A is preferably 100 g / m 2 or more, more preferably 200 g / m 2 or more, expressed as basis weight. Further, it is preferably 3,000 g / m 2 or less, and more preferably 1500 g / m 2 or less.
- the water retention agent has water retention ability, and examples thereof include one or more selected from carbon components, fiber materials, water absorbent polymers, and water absorbent powders.
- the carbon component has water retention ability, oxygen supply ability, and catalytic ability.
- one or more kinds selected from activated carbon, acetylene black, and graphite can be used.
- Activated carbon is preferably used. More preferably, 1 type, or 2 or more types of fine powder or small granular materials selected from coconut shell charcoal, wood charcoal, and peat charcoal are used. Among them, wood charcoal is preferable because the water content in the water retaining sheet is maintained at 15 to 30% by mass of the maximum water absorption amount by keeping the moisture in the heat generating layer constant.
- the carbon component is not only from the viewpoint of being uniformly mixed with the oxidizable metal, but also from the viewpoint of maintaining the water content in the water retention sheet at 15 to 30% by mass of the maximum water absorption of the water retention sheet. Those having a diameter of 10 to 200 ⁇ m are preferably used, and those having an average particle diameter of 12 to 100 ⁇ m are more preferable.
- the average particle size of the carbon component refers to the maximum length in the form of powder and is measured by a dynamic light scattering method, a laser diffraction method, or the like.
- the carbon component is preferably used in a powder form, but a form other than the powder form can also be used, for example, a fibrous form can be used. From the same viewpoint, the carbon component preferably has an average particle size of 10 ⁇ m or more, and more preferably 12 ⁇ m or more.
- the carbon component preferably has an average particle size of 200 ⁇ m or less, and more preferably 100 ⁇ m or less.
- hydrophilic fibers especially cellulose fibers.
- cellulose fiber chemical fiber (synthetic fiber) or natural fiber can be used.
- water-absorbing polymer examples include hydrophilic polymers having a crosslinked structure capable of absorbing and retaining a liquid having a weight 20 times or more of its own weight.
- water-absorbing powder examples include one or more selected from vermiculite, sawdust, silica gel, and pulp powder.
- the content of the water retention agent is 0.3 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 3 to 13 parts by mass with respect to 100 parts by mass of the oxidizable metal. By doing so, moisture necessary for sustaining the oxidation reaction can be accumulated in the obtained heating element. In addition, it is possible to obtain a heating element that can sufficiently supply oxygen to the heating element and has high heat generation efficiency. In addition, since the heat capacity of the heating element with respect to the amount of generated heat can be kept small, an increase in the exothermic temperature increases, a desired temperature increase can be obtained, and an exothermic reaction can be promoted.
- the content of the water retention agent is preferably 4 to 290 g / m 2 , more preferably 7 to 160 g / m 2 in terms of basis weight.
- the thickness of the heat generating layer 121A can be reduced, and the product is not bulky and flexible.
- the thickness of the heat generating layer 121A can be 0.1 mm or more and 1 mm or less.
- content of a water retention agent is 1 mass part or more with respect to 100 mass parts of oxidizable metals, Furthermore, it is preferable that it is 3 mass parts or more.
- content of a water retention agent is represented by basic weight, and it is preferable that it is 4 g / m ⁇ 2 > or more, Furthermore, it is preferable that it is 7 g / m ⁇ 2 > or more.
- the content of the water retaining agent is preferably 290 g / m 2 or less, more preferably 160 g / m 2 or less, expressed as basis weight.
- the content of the carbon component is preferably 90% by mass or more with respect to the total mass of the water retention agent in terms of controlling the moisture in the heat generating layer, more preferably 95% by mass or more, More preferably, it is 98 to 100% by mass, and still more preferably, the water retention agent is composed of a carbon component.
- the content of the water-absorbing polymer and / or cellulose fiber is 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, with respect to the total amount of the water retention agent.
- the absence of the water-absorbing polymer and / or cellulose fiber in the layer 121A can suppress the heat generation layer 121A from excessively absorbing moisture, and can suppress the heat capacity of the heat generating element with respect to the heat generation amount obtained. Therefore, it is more preferable in that the exothermic temperature rises and a desired temperature rise can be obtained.
- the water-absorbing polymer and the cellulose fiber content in the water retention agent are preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the water retention agent.
- the total content of the water-absorbing polymer and the cellulose fiber is more preferably 2% by mass or less based on the total amount of the water retaining agent.
- it is preferable that both the water-absorbing polymer and the cellulose fiber are not included in the heat generating layer 121A.
- the heat generating layer 121A contains water.
- Water may be derived from an aqueous electrolyte solution (for example, an aqueous solution of alkali metal, alkaline earth metal, etc.), or may be water alone and added to the heat generating layer 121A, and is not particularly limited.
- the moisture content in the heat generating layer 121A is 8 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the heat generation layer 121A in a good heat generation state can be obtained by setting the moisture content of the heat generation layer 121A to 8 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. That is, the amount of moisture in the heat generating layer 121A affects the heat generation rate.
- the water content is 8 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the oxidizable metal, heat is generated satisfactorily, the rise of the exothermic temperature is fast, and the exothermic temperature is sustained.
- the heat generating layer in order to increase the amount of water vapor generated at the beginning of heat generation (about 5 minutes), the heat generating layer is brought into a high heat generation state in a short time, so that the heat generation is performed at the beginning of heat generation (about 5 minutes). Since the moisture on the heat generating layer 121A side is made as low as possible, the rise of the heat generation temperature can be improved. Especially, it is more preferable that the moisture content of the heat generating layer 121A is 15 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the heat generating layer 121A may contain a reaction accelerator in addition to the components described above.
- the reaction accelerator is used for the purpose of maintaining the oxidation reaction of the oxidizable metal. Moreover, by using a reaction accelerator, the oxidation film of an oxidizable metal can be destroyed and the oxidation reaction can be promoted.
- the reaction accelerator include one or more selected from alkali metals, alkaline earth metal sulfates, and chlorides. Above all, it is selected from various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride and ferric chloride, and sodium sulfate because of its excellent conductivity, chemical stability and production cost. It is preferable to use 1 type (s) or 2 or more types.
- the content of the reaction accelerator is preferably 2 to 15 parts by mass, more preferably 3 to 12 parts by mass with respect to 100 parts by mass of the oxidizable metal from the viewpoint that a sufficient calorific value is maintained for a long time.
- the content of the reaction accelerator is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and 15 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. It is preferable that there is, more preferably 12 parts by mass or less.
- the heat generating layer 121A may contain a thickener in addition to the components described above.
- a thickener a substance that absorbs moisture and increases consistency or imparts thixotropic properties can be used.
- Alginate such as sodium alginate, gum arabic, tragacanth gum, locust bean gum, guar gum, gum arabic
- Polysaccharide thickeners such as carrageenan, agar and xanthan gum
- starch thickeners such as dextrin, pregelatinized starch and starch for processing
- cellulose such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose or hydroxypropylcellulose Derivative thickener
- Thickener such as polyvinyl alcohol (PVA); Metal soap thickener such as stearate; Mineral thickener such as bentonite, etc.
- PVA polyvinyl alcohol
- Mineral thickener such as bentonite, etc.
- the content of the thickener is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the oxidizable metal.
- the content of the thickener is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the oxidizable metal.
- By setting it as 0.05 mass part or more viscosity can be improved and stability of exothermic powder water dispersion can be made favorable.
- By setting it as 5 mass parts or less it can suppress that it becomes a cause of the fall of a heat-generating characteristic (fall of the maximum temperature).
- the content of water contained in the water retention sheet is set to the maximum of the water retention sheet. The water absorption can be maintained at 15 to 30% by mass.
- polysaccharide-based thickeners are preferable because the coating performance and the water content contained in the water retaining sheet can be maintained at 15 to 30% by mass of the maximum water absorption of the water retaining sheet.
- a polysaccharide thickener having a molecular weight of 2,000,000 or more and 50,000,000 or less is preferable, and a polysaccharide thickener having a molecular weight of 2,000,000 or more and 40,000,000 or less is particularly preferable.
- Xanthan gum is preferred from the viewpoint of coating performance and salt resistance.
- the content of the thickener is preferably 0.05 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the oxidizable metal. Moreover, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of oxidizable metals, and, as for content of a thickener, it is preferable that it is 3 mass parts or less.
- the polysaccharide thickener preferably has a molecular weight of 1,000,000 or more, and more preferably a molecular weight of 2,000,000 or more. The polysaccharide thickener preferably has a molecular weight of 50,000,000 or less, and preferably 40,000,000 or less.
- a polysaccharide thickener having a molecular weight of 1,000,000 or more and 50,000,000 or less in an amount of 0.05 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the water retaining sheet 121C is disposed so as to be in direct contact with the heat generating layer 121A.
- the water retention sheet 121C contains water.
- the water content is 15% by mass or more and 30% by mass or less of the maximum water absorption amount of the water retention sheet 121C.
- the water content of the water retention sheet 121C is 30% by mass or less of the maximum water absorption amount of the water retention sheet 121C, it is possible to ensure the breathability of the water retention sheet 121C, and to generate steam from the water retention sheet 121C. Easy to release. Since steam can be released from the water retention sheet 121C, moisture in the heat generation layer 121A can be mainly used for heat generation, and moisture in the water retention sheet 121C can be used for steam. Thereby, the steam heating tool 100 having a desired steam amount can be obtained while the heat generation state of the heat generation layer 121A is kept in a good state.
- the water content is more preferably 20% by mass or more and 25% by mass or less of the maximum water absorption amount of the water retention sheet 121C.
- the heat capacity of the water retention sheet 121C becomes excessively large by setting the water content to 30% by mass or less of the maximum water absorption amount of the water retention sheet 121C under the conditions of the structural requirements (A) and (C). And it can suppress that a temperature increase rate falls.
- the water content contained in the water retaining sheet 121C is 50 to 350 g / m 2 in terms of basis weight, and more preferably 180 to 260 g / m 2 . Since the amount of water contained in the water retaining sheet serves as a water vapor generation source, the amount of steam generated can be ensured by expressing the amount of water contained in the water retaining sheet in terms of basis weight to 50 g / m 2 or more. In addition, the water retaining sheet generates air resistance due to water absorption (because of the water absorption swelling, the air permeability is lowered compared to the time of drying). Therefore, the water retaining sheet expresses steam from the water retaining sheet by setting the basis weight to 350 g / m 2 or less.
- the water content contained in the water retention sheet 121C is preferably 50 g / m 2 or more, more preferably 180 g / m 2 or more, expressed as basis weight.
- the water content contained in the water retaining sheet 121C is expressed as basis weight, and is preferably 350 g / m 2 or less, and more preferably 260 g / m 2 or less.
- the air permeability of the water retaining sheet 121C is preferably 500 seconds / 100 ml or less in terms of moisture content, 300 seconds / 100 ml or less in consideration of air permeability and ease of vapor passage, More preferably, it is 50 seconds / 100 ml or less.
- the lower limit value of air permeability in a state containing moisture that is, the moisture amount is 15% by mass or more and 30% by mass or less of the maximum water absorption amount of the water retention sheet 121C) is, for example, 1 second / 100 ml.
- the air permeability can be measured as follows.
- the air permeability is a value measured by JIS P8117 (1998), and is defined as the time required for 100 ml of air to pass through an area of 6.42 cm 2 under a constant pressure. Therefore, a high air permeability means that it takes time to pass air, that is, the air permeability is low. Conversely, a low air permeability means high air permeability.
- the air permeability can be measured with a Oken type air permeability meter.
- the water retaining sheet 121C a sheet material that can absorb and retain moisture and has flexibility is used.
- a material include fiber sheets such as paper, non-woven fabric, woven fabric, and knitted fabric made from fibers.
- porous bodies, such as sponge, etc. are mentioned.
- the fibers include those mainly composed of natural fibers such as plant fibers and animal fibers, and those mainly composed of chemical fibers.
- plant fibers include cotton, kabok, wood pulp, non-wood pulp, peanut protein fiber, corn protein fiber, soy protein fiber, mannan fiber, rubber fiber, hemp, Manila hemp, sisal hemp, New Zealand hemp, Rafu hemp, eggplant, One type or two or more types selected from igusa and straw are mentioned.
- animal fibers include one or more selected from wool, goat hair, mohair, cashmere, alpaca, Angola, camel, vicu ⁇ a, silk, feathers, down, feather, algin fiber, chitin fiber, and casein fiber.
- chemical fiber for example, one or more selected from rayon, acetate, and cellulose can be used.
- the water retaining sheet 121C preferably includes a fiber material composed of the above-described fibers and a water-absorbing polymer.
- FIG. 5 shows the water retention sheet 121C and the heat generation layer 121A.
- Component (A) is an oxidizable metal
- component (B) is a water retention agent.
- FIG. 5 shows an example in which the water retaining sheet 121C includes the component (a) fiber material and the component (b) containing the water-absorbing polymer.
- the form of the water retention sheet 121C is (i) a sheet in which the component (a) and the component (b) are uniformly mixed, (ii) component Examples in which the component (b) is disposed between the same or different sheets including (a) (iii) the component (b) is dispersed to form a sheet.
- the water content of the heat generating layer 121A can be easily controlled, the water content contained in the water retaining sheet 121C can be easily set to 15 to 30% by mass of the maximum water absorption amount of the water retaining sheet 121C.
- a thing of the form of (ii) is preferable.
- the same or different sheet containing the component (a) is further laminated thereon and press dried at a pressure of 100 ⁇ 0.5 ° C. and 5 kg / cm 2 so that the water content becomes 5% by mass or less. It is possible to manufacture by drying.
- the water-absorbing polymer a hydrogel material capable of absorbing and holding a liquid 20 times or more of its own weight and capable of gelling is used.
- the water content contained in the water retaining sheet 121C is 15 to 15% of the maximum water absorbing capacity of the water retaining sheet 121C. It can maintain at 30 mass%, and is preferable.
- Examples of the shape of the water-absorbing polymer particles include a spherical shape, a lump shape, a grape bunch shape, and a fiber shape.
- the particle diameter of the water-absorbing polymer particles is preferably 1 to 1,000 ⁇ m, particularly 10 to 500 ⁇ m.
- the particle diameter of the water-absorbing polymer particles is measured by a dynamic light scattering method, a laser diffraction method, or the like.
- the particle diameter of the water-absorbing polymer particles is preferably 1 ⁇ m or more, and more preferably 10 ⁇ m or more.
- the particle diameter of the water-absorbing polymer particles is preferably 1000 ⁇ m or less, and more preferably 500 ⁇ m or less.
- the water-absorbing polymer are selected from starch, cross-linked carboxymethylated cellulose, polymer or copolymer of acrylic acid or alkali metal acrylate, polyacrylic acid and salts thereof, and polyacrylate graft polymer. 1 type or 2 types or more to be mentioned. Among them, the use of polyacrylic acid and a salt thereof and a polyacrylate graft polymer such as a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid, the content of water contained in the water retention sheet 121C, The water retention sheet 121C is preferably maintained at 15 to 30% by mass of the maximum water absorption amount, which is preferable.
- the ratio of the component (b) water-absorbing polymer particles in the water-retaining sheet 121C is 10 to 70% by mass, and further 20 to 65% by mass in the dry state, which promotes quick water movement to the water-retaining sheet 121C,
- the content of water contained in the sheet 121C is preferably maintained at 15 to 30% by mass of the maximum water absorption amount of the water retaining sheet 121C.
- the proportion of the component (b) water-absorbing polymer particles in the water retention sheet 121C is preferably 10% by mass or more, and more preferably 20% by mass or more in the dry state. Further, the proportion of the component (b) water-absorbing polymer particles in the water retention sheet 121C is preferably 70% by mass or less, and more preferably 65% by mass or less in the dry state.
- the sheet 121B is provided on the surface of the heat generating layer 121A opposite to the water retention sheet 121C.
- the sheet 121B directly contacts the heat generating layer 121A and covers the heat generating layer 121A.
- the sheet 121B is preferably a non-breathable or non-breathable sheet.
- a resin sheet is preferably used.
- a non-breathable or non-breathable sheet 50,000 seconds / 100 ml or more, preferably 80,000 seconds / 100 ml or more
- Examples of the sheet 121B include a synthetic resin film, such as a polyethylene film and a polyethylene terephthalate film.
- the heat generating part 121 as described above is accommodated in the first bag body 122, and the heat generating part 121 and the bag body 122 constitute the heat generating body 120.
- the 1st bag body 122 is comprised including the 1st sheet
- the bag body 122 is comprised by preferably airtightly joining the peripheral part of these sheets 122A and 122B. . Regions other than the peripheral portions of the sheets 122A and 122B are non-joining regions, and the heat generating portion 121 is disposed in the non-joining regions.
- the ventilation of the first sheet 122A The degree is preferably 1,000 to 7,000 seconds / 100 ml, more preferably 1,500 to 6,000 seconds / 100 ml, and still more preferably 1,800 to 5,000 seconds / 100 ml. .
- the air permeability of the first sheet 122A is secured, and a large amount of vapor from the water retaining sheet 121C is easily released to the outside of the bag body 122. Can do.
- the heat generation temperature can be controlled and abnormal heat generation can be prevented.
- a porous sheet made of a synthetic resin that has moisture permeability but does not have water permeability is suitable.
- a stretched film containing calcium carbonate or the like in polyethylene can be used.
- various fiber sheets including one or more nonwoven fabrics selected from needle punched nonwoven fabric, air-through nonwoven fabric, and spunbonded nonwoven fabric are laminated on the outer surface of the porous sheet. Then, the texture of the first sheet 122A may be enhanced.
- the first sheet 122A may be a part or all of a breathable sheet that is breathable or may be a non-breathable sheet that does not have breathability, but is more breathable than the second sheet 122B. It is preferable that it is a sheet
- the air permeability JIS P8117 is preferably 7,000 seconds / 100 ml or less, more preferably 6,000 seconds / 100 ml or less, especially 5,000 seconds / 100 ml or less.
- the air permeability (JIS P8117) of the first bag sheet 20a is preferably 1,000 seconds / 100 ml or more, more preferably 1500 seconds / 100 ml or more, and particularly 1800 seconds / It is preferably 100 ml or more.
- the second sheet 122B may be a part or all of a breathable sheet having a breathability or a non-breathable sheet having no breathability, but is more breathable than the first sheet 122A. It is preferable that it is a sheet
- the second sheet 122B is made of a non-breathable sheet, a single layer or multilayer synthetic resin film, or a needle punch nonwoven fabric, an air-through nonwoven fabric, or a spunbond nonwoven fabric is selected on the outer surface of the single layer or multilayer synthetic resin film.
- Various fiber sheets including one or two or more kinds of nonwoven fabrics may be laminated to enhance the texture of the second sheet 122B.
- a two-layer film composed of a polyethylene film and a polyethylene terephthalate film, a laminate film composed of a polyethylene film and a nonwoven fabric, a laminate film composed of a polyethylene film and a pulp sheet, etc. are used. A film is even more preferred.
- the second sheet 122B is a breathable sheet
- the same sheet as the first sheet 122A can be used, or a different sheet can be used.
- the second sheet 122B has a breathability of 50,000 seconds / 100 ml or more, more preferably 80,000 seconds / 100 ml or more, on condition that the breathability of the first sheet 122A is lower. It is preferable.
- the first sheet 122A has an air permeability of 2,000 to 4,000 seconds / 100 ml and the second sheet 122B has an air permeability of 100,000 seconds / 100 ml or more.
- the heat generation part 121 is arrange
- the water retention sheet 121C is disposed on the first sheet 122A side
- the sheet 121B is disposed on the second sheet 122B side. Thereby, the steam from the water retaining sheet 121C can be efficiently discharged from the first sheet 122A.
- the heat generating layer may directly contact the second sheet 122B.
- the second sheet 122B is preferably a non-breathable sheet.
- the heating element 120 accommodated in the bag body 122 may be one sheet, or may be housed in a multilayer state in which a plurality of sheets are laminated.
- the heating element 120 can be produced by, for example, applying a heating powder water dispersion containing an oxidizable metal, a water retention agent, and water to the water retention sheet 120C.
- the exothermic powder water dispersion may be prepared by mixing all the above-mentioned components at once, but prepare an aqueous solution by dissolving the reaction accelerator in advance in a thickener dissolved in water, Next, a premixed oxidizable metal and water retention agent may be mixed with the aqueous solution.
- the reaction accelerator may be mixed with other components in the exothermic powder water dispersion at the same time. However, after coating the exothermic powder water dispersion, a reaction accelerator separately dissolved in water or the like is infiltrated and sprayed. Or you may add by dripping etc. and you may sprinkle the powder of a reaction accelerator.
- the above-described exothermic powder water dispersion is applied to at least one surface of the water retention sheet 121C, at least a part of the water in the exothermic powder water dispersion is absorbed by the water retention sheet 121C, and the water retention sheet 121C is absorbed.
- a heat generating layer 121A is formed.
- the heat generating layer 121A is composed of the remaining components that are not absorbed by the water retention sheet 121C.
- the heat generation layer 121A may exist on the water retention sheet 121C, or the lower portion of the heat generation layer 121A may be at least partially embedded in the water retention sheet 121C.
- the heat generation layer 121A may be provided on one surface of the water retention sheet 121C, or may be provided between the water retention sheet 121C and the sheet 121B.
- FIG. 1 shows an example in which the heat generation layer 121A is provided between the water retention sheet 121C and the sheet 121B.
- FIG. 6 is a diagram for explaining this manufacturing method more specifically.
- an exothermic powder water dispersion 302 containing the raw material constituting the exothermic layer 121A is prepared in the coating tank 301.
- the exothermic powder water dispersion 302 may be stirred by the stirrer 303 to more uniformly disperse the oxidizable metal, the water retention agent, and the water-insoluble component.
- the exothermic powder water dispersion 302 is pumped up to the die head 305 by the pump 304.
- the heated exothermic powder water dispersion 302 is applied to the water retention sheet 121C using the die head 305 while pressing and extruding.
- the coating basis weight of the exothermic powder aqueous dispersion 302 is preferably 160 ⁇ 4,800g / m 2, and more preferably to 320 ⁇ 2,200g / m 2.
- the coating by die coating was illustrated, the coating method is not limited to this, For example, roll coating, screen printing, roll gravure, knife coding, a curtain coater, etc. can also be used. .
- the steam heating device 100 generates heat by an oxidation reaction of an oxidizable metal and gives a sufficient heating effect, and can have a performance of an exothermic temperature of 40 to 70 ° C. in measurement according to JIS standard S4100. .
- the steam heating tool 100 is a steam heating tool accompanied by the generation of water vapor.
- the steam heating device 100 is of a so-called eye mask type, and is heated to a predetermined temperature in contact with the human eye and its surroundings (hereinafter also referred to as “steam temperature heat”). Is used to apply to the eyes and their surroundings.
- the steam heating device 100 includes a main body 101 and an ear hooking portion 102 in which a hole 104 into which an ear is inserted is formed.
- the main body 101 has a horizontally long shape having a longitudinal direction X and a width direction Y orthogonal thereto.
- the main body 101 has a substantially oval shape.
- the ear hooks 102 are used as a pair, and each ear hook 102 is attached to each end of the main body 101 in the longitudinal direction (X direction).
- the steam heating tool 100 is mounted so that each ear hook 102 is hung on the wearer's ear and the main body 101 is covered with both eyes of the wearer. Under this wearing condition, steam heat generated from the steam heating device 100 is applied to the wearer's eyes, and eye fatigue, redness, and eye strain are alleviated, and a relaxed feeling is obtained. In addition, a feeling of falling asleep is also induced.
- FIG. 3 shows an exploded perspective view of the steam heating device 100.
- the ear hooking portion 102 is disposed on the main body portion 101.
- 4 shows a cross-sectional view of the steam heating device 100 along the X direction.
- the main body 101 of the steam heating device 100 includes the above-described heating element 120 and a second bag body 110 that houses the heating element 120.
- the second bag body 110 includes a second bag body first sheet 110A located on the side close to the wearer's skin and a second bag body second sheet 110B located on the side far from the wearer's skin. Yes.
- the second bag body first sheet 110A has a basis weight of 20 to 200 g / m 2 and has a basis weight of 20 to 200 g / m 2 from the viewpoint of preventing the inside from being seen through and from the viewpoint of heat retention, flexibility and thickness. It is preferably 120 g / m 2 .
- the second bag second sheet 110B also has a basis weight of 20 to 200 g / m 2 for the same reason as the second bag first sheet 110A. From the viewpoints of flexibility and thickness, the basis weight is particularly preferably 20 to 120 g / m 2 . From the viewpoint of releasing steam and supplying oxygen to the heat generating layer, the air permeability of the second bag body first sheet 110A and the second bag body second sheet 110B are both 6,000 seconds / 100 ml or less. More preferably, it is 1,000 seconds or less.
- the water vapor evaporated from the water retaining sheet 121C passes through the first sheet 122A and the first bag sheet 110A and reaches the skin.
- the second bag body first sheet 110A and the second bag body second sheet 110B have the same shape and are substantially oval.
- the outer shapes of the second bag body first sheet 110 ⁇ / b> A and the second bag body second sheet 110 ⁇ / b> B form the outer shape of the main body 101.
- the second bag body first sheet 110A and the second bag body second sheet 110B are overlapped with each other, joined at the periphery thereof, and joined at the center in the X direction along the Y direction.
- the bag body 110 has two spaces.
- the heat generating body 120 is accommodated in each space, respectively.
- a hot melt adhesive can be used in order to join the second bag body first sheet 110A and the second bag body second sheet 110B.
- a hot melt adhesive can be used in order to join the second bag body first sheet 110A and the second bag body second sheet 110B.
- the heat generating body 120 is being fixed to the bag body 110 by the adhesive agent, the heat seal, etc. (not shown).
- the second bag body first sheet 110A and the second bag body second sheet 110B for example, a fiber sheet including a nonwoven fabric can be used.
- the bag body 110 is formed with substantially V-shaped notches 113A and 113B cut inwardly along the Y direction from the long side at the position of the center of the two long sides extending in the X direction. .
- Notch portions 113A and 113B have different degrees of notches.
- the notch portion 113A is located between or near the wearer's eyebrows when the steam heating device 100 is attached.
- the notch portion 113B is located on the wearer's nasal bridge when the steam heating device 100 is attached. Therefore, the notch portion 113B is more severely cut than the notch portion 113A.
- at least one of the notch portions 113A and 113B shown in FIG. 2 may be a slit.
- the ear hooking portion 102 in the steam heating device 100 is arranged on the first bag sheet 110A in the main body portion 101 as shown in FIGS.
- the ear hooking portion 102 is reversed outward in the X direction to be in an open state.
- the contour formed by the left and right ear hooks 102 is substantially the same as the contour of the main body 101.
- the ear hook 102 can be made of the same material as the bag 110.
- the steam heating device 100 of the present embodiment is entirely packaged by a packaging material (not shown) having an oxygen barrier property before use, so that the heat generating part 121 does not come into contact with oxygen in the air. Yes.
- the amount of water contained in the heating tool 100 is 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. Since the amount of water contained in the whole heating tool 100 is 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the oxidizable metal, the heat capacity of the heating element with respect to the obtained calorific value can be kept small. An exothermic temperature rise becomes large, a desired temperature rise is obtained, favorable exothermic property is ensured, and a decrease in exothermic temperature can be suppressed. Especially, 50 mass parts or more and 72 mass parts or less are preferable.
- the present invention is not limited to the above-described embodiment, and modifications, configurations, arrangement changes, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
- abutted and used for a wearer's eyes was illustrated as a vapor
- the steam heating tool may be used while being in contact with the shoulder, knee, elbow or the like of the wearer.
- the heat generating part 121 had the sheet
- the present invention further discloses the following compositions and uses for the above-described embodiments.
- a heat generating part formed by laminating a heat generating layer made of a heat generating composition containing an oxidizable metal, water, and a water retention agent, and a water retaining sheet containing a polymer,
- a steam heating tool having air permeability at least in part, and a bag body containing the heat generating part,
- the amount of water contained in the steam heating tool is 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the content of the water retention agent is 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- the amount of water contained in the heat generating layer is 8 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- ⁇ 2> The steam heating apparatus according to ⁇ 1>, wherein the water retention agent contains activated carbon, and the content of the activated carbon in the water retention agent is 90 to 100% by mass.
- ⁇ 3> The steam heating device according to ⁇ 1> or ⁇ 2>, wherein the heat generating portion is disposed so that the water retaining sheet side faces a skin surface of the wearer.
- ⁇ 4> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 3>, wherein a sheet having an air permeability of 50,000 seconds / 100 ml or more is attached to the opposite side of the heat generating layer to the water retaining sheet.
- ⁇ 8> The steam heating tool according to any one of ⁇ 1> to ⁇ 7>, wherein the water content contained in the water retaining sheet is 50 to 350 g / m 2 in terms of basis weight.
- the water retention sheet includes a fiber base material and a water-absorbing polymer.
- the exothermic layer further includes a polysaccharide thickener having a molecular weight of 1 million to 50 million.
- ⁇ 12> The steam heating device according to any one of ⁇ 1> to ⁇ 11>, wherein the average particle diameter of the oxidizable metal is 10 to 200 ⁇ m.
- ⁇ 14> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 13>, wherein the content of the water retention agent is 3 to 13 parts by mass with respect to 100 parts by mass of the oxidizable metal.
- ⁇ 15> The steam heating tool according to any one of ⁇ 1> to ⁇ 14>, wherein an average particle diameter of the carbon component is 10 to 200 ⁇ m.
- ⁇ 16> The steam heating device according to any one of ⁇ 1> to ⁇ 15>, wherein the content of the water retention agent is 4 to 290 g / m 2 .
- ⁇ 17> The steam heating tool according to any one of ⁇ 1> to ⁇ 16>, wherein the content of the carbon component is 98% by mass or more based on the mass of the water retention agent.
- ⁇ 18> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 17>, wherein the content of the water-absorbing polymer and / or cellulose fiber in the water retention agent is 10% by mass or less.
- the exothermic layer further contains a reaction accelerator, and the content of the reaction accelerator is 2 to 15 parts by mass with respect to 100 parts by mass of the oxidizable metal. Steam heating equipment.
- ⁇ 21> The steam heating tool according to any one of ⁇ 1> to ⁇ 20>, wherein the water content contained in the water retention sheet is 20 to 25% by mass of the maximum water absorption amount of the water retention sheet.
- ⁇ 22> The steam heating tool according to any one of ⁇ 1> to ⁇ 21>, wherein the water content in the water retaining sheet is 180 to 260 g / m 2 .
- ⁇ 23> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 22>, wherein the water retention sheet has an air permeability of 50 seconds / 100 ml or less in a state containing water.
- ⁇ 24> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 23>, wherein the water retaining sheet contains a water absorbent polymer, and the water absorbent polymer has a particle size of 1 to 1000 ⁇ m.
- ⁇ 25> The steam heating tool according to any one of ⁇ 1> to ⁇ 24>, wherein the ratio of the water-absorbing polymer to the water retaining sheet is 10 to 70% by mass in a dry state.
- ⁇ 26> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 25>, wherein a sheet having an air permeability of 80,000 seconds / 100 ml or more is attached to the opposite side of the heat-generating layer to the water retaining sheet.
- the heating part is housed in a bag, and the air permeability of a sheet located on the side far from the skin of the wearer of the bag is 80,000 seconds / 100 ml or more.
- Any one of ⁇ 1> to ⁇ 26> Steam heating device according to crab.
- ⁇ 28> The steam heating apparatus according to any one of ⁇ 1> to ⁇ 27>, wherein the heat generating portion is accommodated in a bag, and the bag is further accommodated in a second bag having air permeability.
- ⁇ 30> The steam heating tool according to any one of ⁇ 1> to ⁇ 29>, wherein the amount of water contained in the steam heating tool is 50 parts by mass or more and 72 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
- Example 1 A steam heating tool having the structure shown in FIG. 1 was produced as follows.
- Oxidizable metal Iron powder (Iron powder RKH, average particle size 45 ⁇ m, DOWA IP Creation Co., Ltd.)
- Water retention agent Activated carbon (Carborafamine, average particle size 40 ⁇ m, manufactured by Nippon Enviro Chemicals Co., Ltd.)
- Thickener Xanthan gum (molecular weight 2,000,000, Echo Gum BT, DSP Gokyo Food & Chemical Co., Ltd.)
- Example 1 At the composition ratio shown in Table 1, Example 1 to adjust the heating powder aqueous dispersion in the same manner as, 25cm 2 (5cm ⁇ 5cm) of water retaining sheet 121C on the heating powder aqueous dispersion of 25 cm 2 ( 5 cm ⁇ 5 cm) (see Table 1 for the coating amount). Thereafter, 5% salt water was further added before coating with the sheet 121B, and finally, a heat generating layer of 63.8 parts by mass of water was manufactured with respect to 100 parts by mass of the iron powder.
- an exterior bag made of air-through nonwoven fabric (skin side, air permeability 1 sec / 100 ml, basis weight 30 g / m 2 ) and needle punched nonwoven fabric (opposite side of skin, air permeability 1 sec / 100 ml, basis weight 80 g / m 2 )
- the heat generation part contained in the bag body was put, and the peripheral part was hermetically sealed to make a steam heating device.
- the steam heating tool was put in an oxygen-blocking bag until the evaluation described later was carried out. The series of operations was performed under a nitrogen stream.
- ⁇ 2 Moisture content of water retention sheet ( W121C )
- the water content of the water retaining sheet was calculated by the following formula.
- ⁇ Moisture content of water retention sheet ( W121C ) Coating amount x moisture content in exothermic composition (composition ratio of water / total value of composition ratio)-( ⁇ 1 >> moisture amount W 121 of exothermic layer) (Equation 3)
- Water retention sheet 121C wood pulp paper (20 g / m 2 ), water-absorbing polymer (50 g / m 2 ), and wood pulp paper (30 g / m 2 )) before applying the exothermic composition: wood pulp A water-absorbing polymer is uniformly sprayed on the upper surface of a paper made from paper (20 g / m 2 ), water is sprayed from the top at 200 g / m 2 , and then paper made from wood pulp (30 g / m 2 ) is laminated to 100.
- the apparatus 30 shown in FIG. 7 includes an aluminum measurement chamber (volume 2.1 L) 31, and an inflow path 32 through which dehumidified air (humidity less than 2%, flow rate 2.1 L / min) flows into the lower portion of the measurement chamber 31. And an outflow passage 33 through which air flows out from the upper part of the measurement chamber 31.
- An inlet temperature / humidity meter 34 and an inlet flow meter 35 are attached to the inflow path 32.
- an outlet temperature / humidity meter 36 and an outlet flow meter 37 are attached to the outflow passage 33.
- a thermometer (thermistor) 38 is attached in the measurement chamber 31.
- thermometer having a temperature resolution of about 0.01 ° C. is used.
- the steam heating tool is taken out from the oxygen shielding bag and placed in the measurement chamber 31 with its water vapor discharge surface (the surface on the first bag sheet side) facing up.
- a thermometer 38 with a metal ball (4.5 g) is placed on it. In this state, dehumidified air is flowed from the lower part of the measurement chamber 31.
- a difference in absolute humidity before and after the air flows into the measurement chamber 31 is obtained from the temperature and humidity measured by the inlet temperature and humidity meter 34 and the outlet temperature and humidity meter 36.
- the amount of water vapor released by the steam heating tool is calculated from the flow rates measured by the inlet flow meter 35 and the outlet flow meter 37. Details of this apparatus are described in Japanese Patent Application Laid-Open No. 2004-73688, which is related to the earlier application of the present applicant. Using this device 30, the amount of steam in 10 minutes after opening and the amount of steam in 20 minutes after opening were measured.
- Example 1 In each of Examples 1 to 4, the maximum temperature was high, the temperature rising time was short, and the amount of steam generated during 10 minutes and 20 minutes was large. Further, as apparent from the coating amount, the thickness of the heat generating layer could be reduced. On the other hand, in Comparative Example 1, since the water content in the water retention sheet was 38% by mass of the maximum water absorption amount of the water retention sheet, the rate of temperature increase was slow, and in 20 minutes The amount of steam generated has decreased. Furthermore, the thickness of the heat generating layer has also increased.
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Abstract
Description
被酸化性金属、水、保水剤を含有する発熱組成物からなる発熱層と、ポリマーを含有する保水シートと、が積層されてなる発熱部と、
少なくとも一部に通気性を有し、前記発熱部を収容する袋体と、を有する蒸気温熱具であって、
(A)蒸気温熱具に含まれる水分量が、前記被酸化性金属100質量部に対し、40質量部以上80質量部以下、
(B)前記保水剤の含量が前記被酸化性金属100質量部に対し、0.3質量部以上20質量部以下、
(C)前記発熱層に含まれる水分量が、前記被酸化性金属100質量部に対し、8質量部以上45質量部以下、
(D)前記保水シートに含まれる水分量が、保水シートの最大吸水量の15~30質量%である蒸気温熱具が提供される。
特許文献1に記載の温熱具では、蒸気温熱発生部と保水シート間で水分のやり取りを行い、蒸気温熱発生部内の水分量(具体的には発熱体内の水分量)を発熱に適した水分に調整している。このような特許文献1では、蒸気発生の立ち上がりと蒸気発生の持続性に依然検討の余地があった。
そこで、本発明者らは、以下の蒸気温熱具100を発案した。
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。
図1から図4を参照して、本実施形態の蒸気温熱具100について説明する。
はじめに、図1を参照して、蒸気温熱具100の概要について説明する。
蒸気温熱具100は、被酸化性金属、水、保水剤を含有する発熱組成物からなる発熱層121Aと保水シート121Cとが積層されてなる発熱部121を有する蒸気温熱具である。
この蒸気温熱具100は、
(A)蒸気温熱具100に含まれる水分量が、被酸化性金属100質量部に対し、40質量部以上80質量部以下、
(B)発熱層121A中に含まれる前記保水剤の含量が前記被酸化性金属100質量部に対し、0.3質量部以上20質量部以下、
(C)発熱層121Aに含まれる水分量が、前記被酸化性金属100質量部に対し、8質量部以上45質量部以下、
(D)保水シート121Cに含まれる水分量が、保水シートの最大吸水量の15~30質量%である。
蒸気温熱具100は、被酸化性金属の酸化反応によって発熱して十分な温熱効果を付与するものであり、JIS規格S4100に準拠した測定において、発熱温度38~70℃の性能を有することができる。この蒸気温熱具100から発生する水蒸気量は、0.01mg/(cm2・min)以上であることが好ましく、中でも、0.03mg/(cm2・min)以上であることが好ましい。また、水蒸気発生量の上限値は、たとえば、0.8mg/(cm2・min)以下であることが好ましく、0.4mg/(cm2・min)以下であることがより好ましい。なかでも、0.01mg/(cm2・min)以上0.8mg/(cm2・min)以下であることが好ましく、0.03mg/(cm2・min)以上0.4mg/(cm2・min)以下であることが好ましい。
蒸気温熱具100は、図1に示す発熱体120を有する。
発熱体120は、発熱部121と、発熱部121を内包する第1袋体122とを備える。
発熱部121は、発熱層121Aと、保水シート121Cと、シート121Bとを備える。
発熱層121Aは、被酸化性金属、水、保水剤を含有する発熱組成物からなる。
同様の観点から、被酸化性金属が粉末である場合、その平均粒径が10μm以上であることが好ましく、さらには、20μm以上であることが好ましい。また、その平均粒径が、200μm以下であることが好ましく、さらには、150μm以下、中でも、100μm以下であることが好ましい。
同様の観点から、発熱層121Aを構成する発熱組成物中の被酸化性金属の含有量は、坪量で表して、100g/m2以上が好ましく、200g/m2以上であることが好ましい。また、3,000g/m2以下であることが好ましく、さらには、1500g/m2以下であることが好ましい。
同様の観点から、炭素成分は、平均粒径が10μm以上であることが好ましく、12μm以上であることがさらに好ましい。また、炭素成分は、平均粒径が200μm以下であることが好ましく、さらには、100μm以下であることが好ましい。
なお、保水剤の含有量は、被酸化性金属100質量部に対して、1質量部以上であることが好ましく、さらには、3質量部以上であることが好ましい。また、保水剤の含有量は、被酸化性金属100質量部に対して、15質量部以下であることが好ましく、さらには13質量部以下であることが好ましい。
なお、保水剤の含有量は、坪量で表して、4g/m2以上であることが好ましく、さらには、7g/m2以上であることが好ましい。また、保水剤の含有量は、坪量で表して、290g/m2以下であることが好ましく、殊更160g/m2以下であることが好ましい。
更に、保水剤中、吸水性ポリマー及びセルロース繊維の含有量は合計で、保水剤全量に対して好ましくは10質量%以下、さらに好ましくは5質量%以下である。吸水性ポリマー及びセルロース繊維の含有量は合計で、保水剤全量に対して更に好ましくは2質量%以下である。さらには、発熱層121A中に吸水性ポリマー及びセルロース繊維の双方を含まないことが好ましい。
このように、発熱層121Aの水分量を被酸化性金属100質量部に対し、8質量部以上、45質量部以下とすることで、良好な発熱状態の発熱層121Aとすることができる。すなわち、発熱層121Aの水分量は発熱速度を左右する。被酸化性金属100質量部に対し、水分量を8質量部以上、45質量部以下とすることで良好に発熱し、発熱温度の立ち上がりが速く、発熱温度が持続する。
反応促進剤は、被酸化性金属の酸化反応を持続させる目的で用いられる。また、反応促進剤を用いることにより、被酸化性金属の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、アルカリ土類金属の硫酸塩、及び塩化物から選ばれる1種又は2種以上が挙げられる。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、第1塩化鉄、第2塩化鉄等の各種塩化物、及び硫酸ナトリウムから選ばれる1種又は2種以上を用いることが好ましい。
同様の観点から、反応促進剤の含有量は、被酸化性金属100質量部に対して2質量部以上であることが好ましく、さらには3質量部以上であることが好ましく、15質量部以下であることが好ましく、さらには、12質量部以下であることが好ましい。
増粘剤には主として、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、アルギン酸ソーダ等のアルギン酸塩、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、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、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又は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;ポリビニルアルコール(PVA)などの増粘剤;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た1種又は2種以上の混合物を用いることができる。
増粘剤の含有量は、被酸化性金属100質量部に対して、0.05質量部以上であることが好ましく、さらに0.1質量部以上であることが好ましい。また、増粘剤の含有量は、被酸化性金属100質量部に対して5質量部以下であることが好ましく、さらに3質量部以下であることが好ましい。
更に、多糖類系増粘剤は、分子量1,000,000以上であることが好ましく、さらには分子量2,000,000以上であることが好ましい。また、多糖類系増粘剤は、分子量50,000,000以下であることが好ましく、40,000,000以下であることが好ましい。
分子量1,000,000以上50,000,000以下の多糖類系増粘剤を、被酸化性金属100質量部に対して0.05質量部以上、5質量部以下で含むことが好ましい。
構成要件(A)、(C)の条件下で、水の含有量を保水シート121Cの最大吸水量の15質量%以上とすることで短時間に発生する蒸気量を増やす効果がある。
一方で、保水シート121Cの水の含有量を保水シート121Cの最大吸水量の30質量%以下とすることで、保水シート121Cの通気性を確保することができ、且つ、保水シート121Cから蒸気も放出しやすくすることができる。保水シート121Cから蒸気を放出することができるので、発熱層121A中の水分を主として発熱に利用し、保水シート121C中の水分を蒸気に利用できる。これにより、発熱層121Aの発熱状態を良好な状態のまま、所望の蒸気量の蒸気温熱具100とすることができる。
なかでも、短時間に発生する蒸気量を増やす観点から、水の含有量は、当該保水シート121Cの最大吸水量の20質量%以上25質量%以下であることがより好ましい。
これに加え、構成要件(A)、(C)の条件下で、水の含有量を保水シート121Cの最大吸水量の30質量%以下とすることで、保水シート121Cの熱容量が過剰に大きくなり、昇温速度が低下してしまうことを抑制できる。
保水シート121Cを25cm2のサイズにカットした質量(W0)を測定した後、5質量%塩化ナトリウム水溶液に5分間浸漬した。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を算出した。
Wmax=W1-W0
また、保水シート121Cに含まれる水分量は、坪量で表して、50g/m2以上であることが好ましく、さらには、180g/m2以上であることが好ましい。また、保水シート121Cに含まれる水分量は、坪量で表して、350g/m2以下であることが好ましく、さらには、260g/m2以下であることが好ましい。
なお、水分を含んだ状態(すなわち、水分量が当該保水シート121Cの最大吸水量の15質量%以上30質量%以下)の通気度下限値は、たとえば、1秒/100mlである。
通気度はJIS P8117(1998年)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6.42cm2の面積を通過する時間で定義される。したがって、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。通気度は、王研式通気度計で計測することができる。
図5には、保水シート121Cと、発熱層121Aとを示した。成分(A)は、被酸化性金属、成分(B)は、保水剤である。
図5中では、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シート121Cとした例が示されている。保水シート121Cに成分(b)を含む場合、保水シート121C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121A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シート121Cに含まれる水の含有量を保水シート121Cの最大吸水量の15~30質量%にすることが容易にでき、好ましいものは、(ii)の形態のものである。なお、(ii)の形態の保水シート121Cは、例えば、成分(a)を含むシート上に成分(b)吸水性ポリマーを均一に散布し、その上から200g/m2の量の水を噴霧した後、更にその上に成分(a)を含む同一の又は異なるシートを積層し、100±0.5℃、5kg/cm2の圧力にてプレス乾燥して含水率が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。
吸水性ポリマーの粒子の粒径は、1μm以上であることが好ましく、さらには10μm以上であることが好ましい。また、吸水性ポリマーの粒子の粒径は、1000μm以下であることが好ましく、さらには500μm以下であることが好ましい。
保水シート121Cに占める成分(b)吸水性ポリマーの粒子の割合は、乾燥状態で10質量%以上であることが好ましく、さらには、20質量%以上であることが好ましい。また、保水シート121Cに占める成分(b)吸水性ポリマーの粒子の割合は、乾燥状態で70質量%以下であることが好ましく、さらには、65質量%以下であることが好ましい。
シート121Bとしては、たとえば合成樹脂フィルムがあげられ、ポリエチレンフィルム、ポリエチレンテレフタレートフィルム等があげられる。
第1袋体122は、第1シート122Aと第2シート122Bとを含んで構成されており、これらのシート122A、122Bの周縁部を好ましくは密閉接合することで袋体122が構成されている。シート122A、122B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部121が配置される。
このような通気度を有第1シート122A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。かかる多孔性シートを用いる場合には、多孔性シートの外面にニードルパンチ不織布、エアスルー不織布、及び、スパンボンド不織布から選択される1種又は2種以上の不織布を始めとする各種の繊維シートをラミネートして、第1シート122Aの風合いを高めてもよい。第1シート122Aは、その一部又は全部が通気性を有する通気性シートであってもよいし、通気性を有しない非通気性シートであってもよいが、第2シート122Bよりも通気性の高いシート(即ち通気度の低いシート)であることが好ましい。
なお、第1シート122Aを着用者の肌に近い側に位置するもの(肌側の面)とし、第2シート122Bを着用者の肌から遠い側に位置するものとした場合、第1シート122Aの通気度は、通気度(JIS P8117)は、7,000秒/100ml以下であることが好ましく、さらには、6,000秒/100ml以下であることが好ましく、殊更5,000秒/100ml以下であることが好ましい。また、第1の袋体シート20aの通気度(JIS P8117)は、1,000秒/100ml以上であることが好ましく、さらには、1500秒/100ml以上であることが好ましく、殊更、1800秒/100ml以上であることが好ましい。
蒸気温熱具100は、被酸化性金属の酸化反応によって発熱して十分な温熱効果を付与するものであり、JIS規格S4100に準拠した測定において、発熱温度40~70℃の性能を有することができる。蒸気温熱具100は、水蒸気の発生を伴う蒸気発熱具である。
蒸気温熱具100は、本実施形態では、いわゆるアイマスクタイプのものであり、ヒトの目及びその周囲に当接させて、所定温度に加熱された水蒸気(以下、「蒸気温熱」とも言う。)を目及びその周囲に付与するために用いられるものである。
本体部101は、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。本体部101は略長円形をしている。耳掛け部102は一対で用いられ、各耳掛け部102は本体部101の長手方向(X方向)の各端部にそれぞれ取り付けられている。蒸気温熱具100は、各耳掛け部102を着用者の耳に掛けて、本体部101を着用者の両目を覆うように装着される。この着用状態下、蒸気温熱具100から発生した蒸気温熱が着用者の目に施され、目の疲れや充血、眼精疲労が緩和され、またリラックス感が得られる。更に入眠感も誘発される。
なお、蒸気を放出するとともに発熱層に酸素を供給するという観点から、第2袋体第1シート110A、第2袋体第2シート110Bの通気度は、いずれも、6,000秒/100ml以下であり、1,000秒以下であることがより好ましい。保水シート121Cから蒸発した水蒸気は、第1シート122A、第1袋体シート110Aを通過して、肌に到達する。
以上のような、温熱具100において、温熱具100に含まれる水分量は、被酸化性金属100質量部に対し、40質量部以上80質量部以下である。
温熱具100全体に含まれる水分量を被酸化性金属100質量部に対し、40質量部以上80質量部以下とすることで、得られる発熱量に対する発熱体の熱容量を小さく抑えることができるため、発熱温度上昇が大きくなり、所望の温度上昇が得られ、良好な発熱性を確保するとともに、発熱温度の低下も抑制できる。なかでも、50質量部以上、72質量部以下がこのましい。
たとえば、前記実施形態では、蒸気温熱具として、着用者の目に当接させて使用するアイマスク型のものを例示したが、これに限られるものではない。
たとえば、蒸気温熱具は、着用者の肩、膝、肘等に当接させて使用するものであってもよい。この場合には、耳掛け部102にかえて粘着剤等の固定手段を設けることが好ましい。
さらに、前記実施形態では、発熱部121は、シート121Bを有するものであったが、これに限らず、発熱部121は、シート121Bを含まないものであってもよい。
少なくとも一部に通気性を有し、前記発熱部を収容する袋体と、を有する蒸気温熱具であって、
(A)蒸気温熱具に含まれる水分量が、前記被酸化性金属100質量部に対し、40質量部以上80質量部以下、
(B)前記保水剤の含量が前記被酸化性金属100質量部に対し、0.3質量部以上20質量部以下、
(C)前記発熱層に含まれる水分量が、前記被酸化性金属100質量部に対し、8質量部以上45質量部以下、
(D)前記保水シートに含まれる水分量が、保水シートの最大吸水量の15~30質量%である蒸気温熱具。
<3>前記発熱部は、前記保水シート側が着用者の肌面に対向するように配置される、<1>又は<2>に記載の蒸気温熱具。
<4>前記発熱層の保水シートと反対側には、通気度が50,000秒/100ml以上のシートが付着されている<1>ないし<3>のいずれかに記載の蒸気温熱具。
<5>(E)前記保水シートの通気度が500秒/100ml以下である<1>ないし<4>のいずれかに記載の蒸気温熱具。
<6>前記発熱部が袋体に内包されており、前記袋体の少なくとも一方の面の通気度が1,000~7,000秒/100mlである<1>ないし<5>のいずれかに記載の蒸気温熱具。
<7>前記発熱部が袋体に内包されており、前記袋体の着用者の肌から遠い側の位置するシートの通気度が50,000秒/100ml以上である<1>ないし<6>のいずれかに記載の蒸気温熱具。
<8>前記保水シートに含まれる水分量が、坪量で表して、50~350g/m2である<1>ないし<7>のいずれかに記載の蒸気温熱具。
<9>前記保水シートは、繊維基材と吸水性のポリマーとを有するものである<1>ないし<8>のいずれかに記載の蒸気温熱具。
<10>前記発熱層が更に分子量100万以上5000万以下の多糖類系増粘剤を含む、<1>ないし<9>のいずれかに記載の蒸気温熱具。
<11>分子量100万以上5000万以下の多糖類系増粘剤の含有量が被酸化性金属100質量部に対して0.05~5質量部である<1>ないし<10>のいずれかに記載の蒸気温熱具。
<12>被酸化性金属の平均粒径が10~200μmである<1>ないし<11>のいずれかに記載の蒸気温熱具。
<13>被酸化性金属の含有量が100~3000g/m2である<1>ないし<12>のいずれかに記載の蒸気温熱具。
<14>保水剤の含有量が被酸化性金属100質量部に対して3~13質量部である<1>ないし<13>のいずれかに記載の蒸気温熱具。
<15>炭素成分の平均粒径が10~200μmである<1>ないし<14>のいずれかに記載の蒸気温熱具。
<16>保水剤の含有量が4~290g/m2である<1>ないし<15>のいずれかに記載の蒸気温熱具。
<17>炭素成分の含有量が保水剤の質量に対して98質量%以上である<1>ないし<16>のいずれかに記載の蒸気温熱具。
<18>保水剤中、吸水性ポリマー及び/又はセルロース繊維の含有量は10質量%以下である<1>ないし<17>のいずれかに記載の蒸気温熱具。
<19>発熱層に含まれる水分量が、被酸化性金属100質量部に対し15質量部以上40質量部以下である<1>ないし<18>のいずれかに記載の蒸気温熱具。
<20>発熱層はさらに反応促進剤を含み、該反応促進剤の含有量は被酸化性金属100質量部に対して2~15質量部である<1>ないし<19>のいずれかに記載の蒸気温熱具。
<21>保水シートに含まれる水分量が保水シートの最大吸水量の20~25質量%である<1>ないし<20>のいずれかに記載の蒸気温熱具。
<22>保水シートに含まれる水分量が180~260g/m2である<1>ないし<21>のいずれかに記載の蒸気温熱具。
<23>保水シートの通気度が水を含んだ状態で50秒/100ml以下である<1>ないし<22>のいずれかに記載の蒸気温熱具。
<24>保水シートが吸水性ポリマーを含有し、吸水性ポリマーの粒径が1~1000μmである<1>ないし<23>のいずれかに記載の蒸気温熱具。
<25>保水シートに占める吸水性ポリマーの割合は、乾燥状態で10~70質量%である<1>ないし<24>のいずれかに記載の蒸気温熱具。
<26>発熱層の保水シートと反対側には、通気度が80000秒/100ml以上のシートが付着されている<1>ないし<25>のいずれかに記載の蒸気温熱具。
<27>前記発熱部は、袋体に収容されており、袋体の着用者の肌から遠い側に位置するシートの通気度が80,000秒/100ml以上である<1>ないし<26>のいずれかに記載の蒸気温熱具。
<28>前記発熱部は、袋体に収容されており、袋体がさらに通気性を有する第2袋体に収容されている<1>ないし<27>のいずれかに記載の蒸気温熱具。
<29>本体部と耳掛け部とを有している<1>ないし<28>のいずれかに記載の蒸気温熱具。
<30>蒸気温熱具に含まれる水分量が、被酸化性金属100質量部に対し50質量部以上72質量部以下である <1>ないし<29>のいずれかに記載の蒸気温熱具。
(実施例1~4)
図1で示す構造の蒸気温熱具を以下のように作製した。
表1で示す組成比で、被酸化性金属、保水剤、水、反応促進剤、増粘剤、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た。一方で被酸化性金属、保水剤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。
なお、被酸化性金属、保水剤、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。なお、後述する比較例1においても同様である。
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)製)
保水剤: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)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)製)
増粘剤:キサンタンガム(分子量2,000,000、エコーガムBT、DSP五協フード&ケミカル(株)製)
木材パルプ製の紙(20g/m2、伊野紙(株)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、30g/m250g/m2、アクアリックCA、(株)日本触媒製)と木材パルプ製の紙(30g/m2、伊野紙(株)製)を積層して一体化したポリマーシートを保水シート121Cとして使用した。
25cm2(5cm×5cm)の保水シート121C上に上記発熱粉体水分散物を25cm2(5cm×5cm)の範囲に塗布した(塗工量は表1参照)。その後、シート121Bで被覆した。シート121Bは、非通気性のシート(50,000秒/100ml以上)であり、ポリエチレンフィルムである。
表1で示す組成比で、実施例1と同様の手順で発熱粉体水分散物を調整し、25cm2(5cm×5cm)の保水シート121C上に上記発熱粉体水分散物を25cm2(5cm×5cm)の範囲に塗布した(塗工量は表1参照)。その後、シート121Bで被覆する前に、更に5%塩水を添加し、最終的に、鉄粉100質量部に対し、水63.8質量部の発熱層を製造した。
通気性を有する袋体(肌側に第1袋体シートの通気度2,500秒/ml、肌と反対側に非通気性の第1袋体シート、6.5cm×6.5cm)に実施例1~4、比較例1の発熱体をそれぞれ入れて、周縁部を密閉シールした。このとき、実施例1~4、比較例1では、保水シート側が、第1袋体シート側に位置するように、発熱部を配置した。
さらにエアスルー不織布(肌側、通気度1秒/100ml、坪量30g/m2)とニードルパンチ不織布(肌と反対側、通気度1秒/100ml、坪量80g/m2)で作った外装袋(第2袋体、7.5cm×7.5cm)の中に、発熱部を袋体に収容されたもの(発熱体)を入れて、周縁部を密閉シールしたものを蒸気温熱具とした。蒸気温熱具は、後述する評価を実施するまで、酸素遮断袋に入れた。なお、一連の作業は窒素気流下でおこなった。
実施例1~4及び比較例1の発熱体、及び、これを備えた蒸気温熱具について、以下のように評価した。評価結果は、表1に示した。
1.水分量測定
《1》発熱層の水分率(RH2O)及び水分量(W121)
保水シート上に形成された発熱層を2g採取して、水分計(ケット水分計 FD-240、(株)ケット科学研究所製)を用い、120℃、15分加熱乾燥したとき、放出された水分量を測定して、発熱層の水分率RH2Oを測定した。
・発熱層の水分率(RH2O)=放出された水分量/検体量(2g)・・・(式1)
・発熱層の水分量(W121)=塗工量×発熱組成物中の固形分率(水を除く組成比の合計値/組成比の合計値)×測定した水分率RH2O/(1-測定した水分率RH2O)・・・(式2)
下記式(式3)で示すとおり、保水シートの水分量は、下記式にて算出した。
・保水シートの水分量(W121C)
=塗工量×発熱組成物中の水分率(水の組成比/組成比の合計値)-(《1》発熱層の水分量W121)・・・(式3)
発熱組成物を塗工する前の保水シート121C(木材パルプ製の紙(20g/m2)と吸水性ポリマー(50g/m2)と木材パルプ製の紙(30g/m2)作り方:木材パルプ製の紙(20g/m2)上面に吸水性ポリマーを均一に散布し、その上から200g/m2で水を吹きかけた後、木材パルプ製の紙(30g/m2)を積層して100℃(±5℃)でプレス乾燥したもの、厚み0.5mm。乾燥時の水分量5%以下)を25cm2のサイズにカットした質量(W0)を測定した後、5質量%塩化ナトリウム水溶液に5分間浸漬した。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を算出した。
Wmax=W1-W0
酸素遮断袋から蒸気温熱具を取り出し、保水シート121C上の発熱層121Aを削り取り、除去した。
その後、JIS P 8117(1998年)に準じて王研式通気度計にて測定した。
(最高温度、昇温時間)
JIS S4100に準拠した測定機を用いて、蒸気温熱具100の外袋の肌側の面側を外側にし、肌側と反対側の面に、温度センサーを設置して固定した。温度センサーは、メッシュ材(ポリエステル製、厚み8ミリのダブルラッセル生地)で測定面に固定されている。開封後、10秒間隔で温度を測定して40分間測定を行い、その最高温度を測定した。具体的には、温度の立ち上がり(発熱温度が35℃から45℃に到達した時間(分))、酸素遮断袋から開封後の最高温度(℃)について評価した。
図7に示す装置30を用いて次のように測定した。図7に示す装置30は、アルミニウム製の測定室(容積2.1L)31と、測定室31の下部に除湿空気(湿度2%未満、流量2.1L/分)を流入させる流入路32と、測定室31の上部から空気を流出させる流出路33とを備えている。流入路32には、入口温湿度計34と入口流量計35とが取り付けられている。一方、流出路33には、出口温湿度計36と出口流量計37とが取り付けられている。測定室31内には温度計(サーミスタ)38が取り付けられている。温度計38としては、温度分解能が0.01℃程度のものを使用する。測定環境温度30℃(30±1℃)において蒸気温熱具を酸素遮断袋から取り出し、その水蒸気放出面(第1袋体シート側の面)を上にして測定室31に載置する。金属球(4.5g)をつけた温度計38をその上に載せる。この状態で測定室31の下部から除湿空気を流す。入口温湿度計34と出口温湿度計36で計測される温度及び湿度から測定室31に空気が流入する前後の絶対湿度の差を求める。さらに入口流量計35と出口流量計37で計測される流量から蒸気温熱具が放出した水蒸気量を算出する。この装置の詳細は、本出願人の先の出願に係る特開2004-73688号公報に記載されている。
この装置30を使用して、開封後から10分間での蒸気量、開封後から20分間での蒸気量を測定した。
これに対し、比較例1では、保水シート中の水分量が、保水シートに含まれる水分量が、保水シートの最大吸水量の38質量%であったため、昇温速度が遅く、しかも20分間での蒸気発生量が少なくなってしまった。さらに、発熱層の厚みも厚くなってしまった。
Claims (11)
- 被酸化性金属、水、保水剤を含有する発熱組成物からなる発熱層と、ポリマーを含有する保水シートと、が積層されてなる発熱部と、
少なくとも一部に通気性を有し、前記発熱部を収容する袋体と、を有する蒸気温熱具であって、
(A)蒸気温熱具に含まれる水分量が、前記被酸化性金属100質量部に対し、40質量部以上80質量部以下、
(B)前記保水剤の含量が前記被酸化性金属100質量部に対し、0.3質量部以上20質量部以下、
(C)前記発熱層に含まれる水分量が、前記被酸化性金属100質量部に対し、8質量部以上45質量部以下、
(D)前記保水シートに含まれる水分量が、保水シートの最大吸水量の15~30質量%である蒸気温熱具。 - 前記保水剤が活性炭を含有し、前記保水剤における前記活性炭の含有量が90~100質量%である請求項1に記載の蒸気温熱具。
- 前記発熱部は、前記保水シート側が着用者の肌面に対向するように配置される、請求項1又は2に記載の蒸気温熱具。
- 前記発熱層の保水シートと反対側には、通気度が50,000秒/100ml以上のシートが付着されている請求項1ないし3のいずれかに記載の蒸気温熱具。
- (E)前記保水シートの通気度が500秒/100ml以下である請求項1ないし4のいずれかに記載の蒸気温熱具。
- 前記発熱部が袋体に内包されており、前記袋体の少なくとも一方の面の通気度が1,000~7,000秒/100mlである請求項1ないし5のいずれかに記載の蒸気温熱具。
- 前記発熱部が袋体に内包されており、前記袋体の着用者の肌から遠い側に位置するシートの通気度が50,000秒/100ml以上である請求項1ないし6のいずれかに記載の蒸気温熱具。
- 前記保水シートに含まれる水分量が、坪量で表して、50~350g/m2である請求項1ないし7のいずれかに記載の蒸気温熱具。
- 前記保水シートは、繊維基材と吸水性のポリマーとを有するものである請求項1ないし8のいずれかに記載の蒸気温熱具。
- 前記発熱層が更に分子量100万以上5000万以下の多糖類系増粘剤を含む、請求項1ないし9のいずれかに記載の蒸気温熱具。
- 分子量100万以上5000万以下の多糖類系増粘剤の含有量が被酸化性金属100質量部に対して0.05~5質量部である請求項1ないし10のいずれかに記載の蒸気温熱具。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019037775A (ja) * | 2017-08-23 | 2019-03-14 | 花王株式会社 | 温熱具 |
Families Citing this family (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10105259B2 (en) | 2000-09-15 | 2018-10-23 | Bruder Healthcare Company, Llc | Wound and therapy compress and dressing |
AU2001292683A1 (en) | 2000-09-15 | 2002-03-26 | Bruder Healthcare Company | Wound and therapy compress and dressing |
US9925087B2 (en) | 2000-09-15 | 2018-03-27 | Bruder Healthcare Company, Llc | Wound and therapy compress and dressing |
CN104334130B (zh) | 2012-06-07 | 2016-10-12 | 花王株式会社 | 发热体及具备其的温热用具 |
WO2014143139A1 (en) | 2013-03-15 | 2014-09-18 | Bruder Healthcare Company | Wound and therapy compress and dressing |
JP6377421B2 (ja) | 2013-06-10 | 2018-08-22 | 花王株式会社 | 温熱具 |
JP6162599B2 (ja) * | 2013-12-27 | 2017-07-12 | 花王株式会社 | 温熱具 |
JP6711816B2 (ja) * | 2014-08-06 | 2020-06-17 | 珠海漢盈科技有限公司Handy Technology (Zhuhai) Ltd. | 自己発熱保温型フィルム並びにそれにより製造されたフェイスマスク及びアイシート |
JP2016116806A (ja) * | 2014-12-24 | 2016-06-30 | 花王株式会社 | 発熱体 |
US20160286994A1 (en) * | 2015-04-01 | 2016-10-06 | Preston Keith Felty | Disposable sleeve for a container |
RU2695621C2 (ru) | 2015-06-10 | 2019-07-24 | Као Корпорейшн | Маска с паровым обогревом |
WO2017014271A1 (ja) * | 2015-07-21 | 2017-01-26 | 花王株式会社 | 温熱具 |
JP6721300B2 (ja) * | 2015-07-21 | 2020-07-15 | 花王株式会社 | 発熱具及びその製造方法 |
JP6715104B2 (ja) * | 2015-07-21 | 2020-07-01 | 花王株式会社 | 温熱具 |
US12011388B2 (en) | 2016-03-01 | 2024-06-18 | The Hilsinger Company Parent, Llc | Therapeutic thermal compress with phase-change material |
US11998480B2 (en) * | 2016-03-01 | 2024-06-04 | The Hilsinger Company Parent, Llc | Self-heating compress for moist heat delivery |
EP3473215A4 (en) * | 2016-06-17 | 2020-01-22 | Kao Corporation | HOT STEAM TOOL AND METHOD OF USING THE SAME |
CN106551783B (zh) * | 2016-11-18 | 2019-03-01 | 珠海汉盈科技有限公司 | 一种双面使用蒸汽眼罩或面罩 |
USD844795S1 (en) | 2016-11-30 | 2019-04-02 | Bruder Healthcare Company, Llc | Therapeutic eye mask |
USD871598S1 (en) | 2016-11-30 | 2019-12-31 | Bruder Healthcare Company, Llc | Therapeutic eye mask |
CN107057657A (zh) * | 2017-04-05 | 2017-08-18 | 北京建筑大学 | 一种保水发热剂 |
WO2018235879A1 (ja) * | 2017-06-22 | 2018-12-27 | 花王株式会社 | 温熱具 |
CN107499725B (zh) * | 2017-09-20 | 2020-05-15 | 俞明富 | 一种用于食品的无火焰自动加热剂及其应用方法 |
CN107693206B (zh) * | 2017-11-14 | 2023-12-15 | 尤社互动创新科技(大连)有限公司 | 一种利用蒸汽介质加热热敷眼罩的装置 |
JP7181025B2 (ja) * | 2018-03-08 | 2022-11-30 | 花王株式会社 | 温熱具 |
KR20200116982A (ko) * | 2018-03-14 | 2020-10-13 | 카오카부시키가이샤 | 온열구 |
CN108714074B (zh) * | 2018-04-04 | 2020-09-22 | 广州市兴世机械制造有限公司 | 发热眼罩成型方法及发热眼罩 |
JP2020192309A (ja) * | 2019-05-24 | 2020-12-03 | 花王株式会社 | 水蒸気発生体及び温熱具 |
CN112451201B (zh) * | 2020-11-26 | 2021-06-08 | 王兴伟 | 一种儿科用自发热贴剂及其制备方法 |
KR102665906B1 (ko) * | 2021-06-08 | 2024-05-16 | 카오카부시키가이샤 | 온열구 |
US11825891B1 (en) * | 2021-09-14 | 2023-11-28 | Robert Dean Wilson | Gloves with finger-warming insert pockets |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0975388A (ja) * | 1995-07-08 | 1997-03-25 | Akio Usui | インキ状ないしクリーム状の発熱組成物及びこれを用いた発熱体並びにこの発熱体の製造方法 |
JP2003129041A (ja) * | 2001-10-25 | 2003-05-08 | Maikooru Kk | 発熱組成物及びこれを用いた発熱体並びにこの発熱体の製造方法 |
JP2004026904A (ja) * | 2002-06-21 | 2004-01-29 | Sanyo Chem Ind Ltd | 発熱体用保水剤及び発熱体 |
JP2004073688A (ja) | 2002-08-21 | 2004-03-11 | Kao Corp | 目用水蒸気発生温熱シート |
JP2004208978A (ja) * | 2002-12-27 | 2004-07-29 | Mycoal Products Corp | 発熱組成物及び発熱体 |
JP2009039370A (ja) | 2007-08-10 | 2009-02-26 | Kao Corp | 蒸気温熱具 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2303208B (en) | 1995-07-08 | 1998-01-21 | Akio Usui | Viscous liquid exothermic composition,exothermic device made thereof and manufacturing method of exothermic device |
JP3049707B2 (ja) * | 1998-04-03 | 2000-06-05 | 花王株式会社 | 水蒸気発生体 |
EP1147752B1 (en) | 2000-04-18 | 2005-02-16 | Kao Corporation | Steam generating unit, mask and eye pillow respectively containing the same, and use thereof |
US8197526B2 (en) * | 2003-05-09 | 2012-06-12 | Kao Corporation | Warming tool |
JP4638199B2 (ja) * | 2004-10-05 | 2011-02-23 | ユニ・チャーム株式会社 | マスク |
JP4460484B2 (ja) * | 2005-04-25 | 2010-05-12 | 株式会社タクマ | 化学カイロの製造方法 |
US8137392B2 (en) | 2005-12-15 | 2012-03-20 | Kimberly-Clark Worldwide, Inc. | Conformable thermal device |
JP5284700B2 (ja) * | 2007-11-09 | 2013-09-11 | 花王株式会社 | 発熱具 |
CN102227198B (zh) | 2008-12-10 | 2015-10-14 | 花王株式会社 | 发热器具 |
RU2388973C1 (ru) * | 2009-02-18 | 2010-05-10 | Общество с ограниченной ответственностью "БАРГАН ПРОДАКШН ГРУПП" (BARGAN PRODUCTION GROUP) | Экзотермический нагреватель |
JP2011062336A (ja) * | 2009-09-17 | 2011-03-31 | Maikooru Kk | 発熱体 |
US9709260B2 (en) | 2010-06-18 | 2017-07-18 | Kao Corporation | Heat generating device |
-
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- 2012-12-21 TW TW101149221A patent/TWI504388B/zh active
- 2012-12-21 CN CN201280063336.1A patent/CN104010599B/zh active Active
- 2012-12-21 EP EP12860486.5A patent/EP2796117B1/en active Active
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0975388A (ja) * | 1995-07-08 | 1997-03-25 | Akio Usui | インキ状ないしクリーム状の発熱組成物及びこれを用いた発熱体並びにこの発熱体の製造方法 |
JP2003129041A (ja) * | 2001-10-25 | 2003-05-08 | Maikooru Kk | 発熱組成物及びこれを用いた発熱体並びにこの発熱体の製造方法 |
JP2004026904A (ja) * | 2002-06-21 | 2004-01-29 | Sanyo Chem Ind Ltd | 発熱体用保水剤及び発熱体 |
JP2004073688A (ja) | 2002-08-21 | 2004-03-11 | Kao Corp | 目用水蒸気発生温熱シート |
JP2004208978A (ja) * | 2002-12-27 | 2004-07-29 | Mycoal Products Corp | 発熱組成物及び発熱体 |
JP2009039370A (ja) | 2007-08-10 | 2009-02-26 | Kao Corp | 蒸気温熱具 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2796117A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019037775A (ja) * | 2017-08-23 | 2019-03-14 | 花王株式会社 | 温熱具 |
Also Published As
Publication number | Publication date |
---|---|
TWI504388B (zh) | 2015-10-21 |
KR101649806B1 (ko) | 2016-08-19 |
TW201336485A (zh) | 2013-09-16 |
EP2796117B1 (en) | 2016-11-09 |
JP5296256B2 (ja) | 2013-09-25 |
JP2013146554A (ja) | 2013-08-01 |
KR20140105835A (ko) | 2014-09-02 |
US9671134B2 (en) | 2017-06-06 |
EP2796117A1 (en) | 2014-10-29 |
US20140345543A1 (en) | 2014-11-27 |
RU2014129895A (ru) | 2016-02-10 |
EP2796117A4 (en) | 2015-08-12 |
RU2581250C2 (ru) | 2016-04-20 |
CN104010599B (zh) | 2015-09-30 |
HK1199810A1 (zh) | 2015-07-24 |
CN104010599A (zh) | 2014-08-27 |
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