WO2023182487A1 - Heat-generating body and heat-generating composition - Google Patents

Heat-generating body and heat-generating composition Download PDF

Info

Publication number
WO2023182487A1
WO2023182487A1 PCT/JP2023/011760 JP2023011760W WO2023182487A1 WO 2023182487 A1 WO2023182487 A1 WO 2023182487A1 JP 2023011760 W JP2023011760 W JP 2023011760W WO 2023182487 A1 WO2023182487 A1 WO 2023182487A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
heating element
heat
iron powder
generating composition
Prior art date
Application number
PCT/JP2023/011760
Other languages
French (fr)
Japanese (ja)
Inventor
美喜雄 高岩
光浩 坂本
Original Assignee
エステー株式会社
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.)
Filing date
Publication date
Application filed by エステー株式会社 filed Critical エステー株式会社
Publication of WO2023182487A1 publication Critical patent/WO2023182487A1/en

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • C09K5/18—Non-reversible chemical reactions

Definitions

  • the present invention relates to a heat generating element and a heat generating composition, and more particularly to a heat generating element and a heat generating composition that do not impair the heat generating performance of the heat generating element even when stored for a long period of time.
  • heating elements have been known that utilize the reaction heat obtained by reacting a heat generating composition mainly composed of metal powder such as iron powder with oxygen in the air.
  • a method of supplying heat to the human body is used.
  • the heating material is sealed in an inner bag, and this inner bag is further sealed in an outer bag, but the heating element deteriorates during storage, and as a result, In many cases, the desired performance cannot be guaranteed, such as the duration of heat generation being reduced.
  • the outer bag is made of a material made by laminating aluminum onto a polyester film base material, cracks may occur in the laminated aluminum, and the bag is particularly susceptible to this effect when stored for a long period of time.
  • the outer bag is made of a polyethylene terephthalate film base material coated with a metal oxide such as aluminum oxide (for example, Patent Document 1), it will be difficult to use in industries where inexpensive products are required, and the versatility will be lost. There's a problem.
  • Heating elements that utilize the oxidation reaction between metal powder and oxygen are required to quickly raise the temperature after opening and maintain a specified temperature for a specified period of time. There is a need for a heating element that maintains the heat generation performance of the device without degrading it.
  • the present invention has been made to solve the above problems, and the present invention provides a heating element that can maintain heat generation time equivalent to that before storage even after long-term storage. And, it is an object of the present invention to provide a heating element composition.
  • the heating element of the present invention is a heating element for supplying heat, and has at least an outer bag and a breathable inner bag, and a heat generating composition is sealed inside the inner bag,
  • the initial heat generating composition sealed in the inner bag of the heating element contains at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water, and the content of the iron powder is in the heat generating composition. , 15% to 45% by weight, and the water content of the initial exothermic composition is 35% to 60% by weight in the exothermic composition, and the total initial exothermic composition is 100% by weight. It is characterized by
  • the heating element is (A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture, (B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%; It is preferable that the ratio is (B)/(A) ⁇ 80%.
  • the heating element is (A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture, (B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%; It is preferable that the absolute value of the difference is within 1 hour.
  • the carbon component is preferably activated carbon, and the activated carbon preferably has an average particle size of 1 to 150 ⁇ m. Further, it is preferable that the heating element maintains a heat generation state of 40° C. or higher for a duration of 0.1 to 12 hours.
  • a method for preventing deterioration over time of a heating element of the present invention is a method for preventing deterioration over time of a heating element for supplying heat, wherein the heating element has at least an outer bag and a breathable inner bag.
  • a heat-generating composition is sealed inside the inner bag, and the heat-generating composition initially sealed in the inner bag of the heating element includes at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water, the content of the iron powder is 15% to 45% by weight in the exothermic composition, and the initial water content of the exothermic composition is 35% to 60% by weight in the exothermic composition. %, and the entire initial exothermic composition is 100% by weight.
  • 3 is a graph showing the temperature characteristics of the heating element of Example 1.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 2.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 3.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 4.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 5.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 6.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 7.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 8.
  • 7 is a graph showing the temperature characteristics of the heating element of Example 9.
  • 3 is a graph showing the temperature characteristics of a heating element of Comparative Example 1.
  • 7 is a graph showing the temperature characteristics of a heating element of Comparative Example 2.
  • 7 is a graph showing the temperature characteristics of a heating element of Comparative Example 3.
  • the heating element of the present invention has at least an outer bag and a breathable inner bag, and a heat generating composition is sealed inside the inner bag.
  • the exothermic composition initially contains at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water when enclosed in the inner bag.
  • the water content of the exothermic composition when sealed in the inner bag (initial stage) is preferably 35% by weight or more and 60% by weight or less, and preferably 39% by weight or more and 55% by weight or less. It is particularly preferable that Regarding the water content in the heat generating composition, it is generally said that problems will occur if the water content is too high or too low, so it is necessary to prevent excess water from being present in the heat generating element.
  • the formulation of exothermic compositions has been devised. However, according to the present invention, even if a large amount of water is blended, sufficient heat generation properties are maintained.
  • iron powder used in the present invention examples include cast iron powder, atomized iron powder, electrolytic iron powder, reduced iron powder, sponge iron powder, and iron alloy powder thereof. Furthermore, these iron powders may contain carbon and oxygen, and may contain other metals with iron containing 50% or more of iron.
  • the type of metal included in the alloy etc. is not particularly limited as long as the iron component acts as a component of the exothermic composition, but examples include metals such as aluminum, manganese, copper, and silicon, and semiconductors.
  • the metals used in the present invention also include semiconductors.
  • the content of metals other than iron is usually 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the entire iron powder.
  • two or more types of iron powders may be used as a mixture, or two or more types of iron powders of the same type may be used as a mixture.
  • Commercially available cast iron powders include CIP (manufactured by Daitetsu Kogyo Co., Ltd.), and reduced iron powders include InSIP (manufactured by Powder Tech Co., Ltd.) and DKP3 (DOWA IP Creation Co., Ltd.).
  • the heat-generating composition (initial heat-generating composition) at the time of being sealed in the inner bag of the initial heat-generating element preferably has an iron powder content of 15% by weight or more and 45% by weight or less in the heat-generating composition. , 20% by weight or more and 40% by weight or less is particularly preferable.
  • Examples of the carbon component used in the present invention include carbon black, graphite, activated carbon, etc., but it is preferable to use activated carbon.
  • Examples of the activated carbon include activated carbon with a water absorption rate of 4.2, and activated carbon with a water absorption rate of 2.2.
  • the average particle size of the activated carbon is preferably 1 to 150 ⁇ m, particularly preferably 10 to 100 ⁇ m.
  • the content of the carbon component in the heat generating composition encapsulated in the initial heating element is preferably 5% by weight or more and 16% by weight or less, and preferably 7% by weight or more and 13% by weight. The following is particularly preferable.
  • two or more types of activated carbon may be used as a mixture, or two or more of the same type of activated carbon may be used as a mixture.
  • the reaction promoter used in the present invention is not particularly limited as long as it can accelerate the exothermic reaction, but examples include metal halides such as sodium chloride and potassium chloride, metal sulfates such as potassium sulfate, Examples include inorganic electrolytes such as nitrates such as sodium nitrate, acetates such as sodium acetate, and carbonates such as ferrous carbonate. Further, in the present invention, electrolytes used in known disposable body warmers and heating elements can also be used. These reaction accelerators are usually used in the form of an aqueous solution, but they can also be used in the form of powder.
  • the heat-generating composition of the present invention includes a water-retaining agent such as wood flour and vermiculite, a water-absorbing polymer such as a cross-linked poly(meth)acrylic acid, a hydrogen generation inhibitor such as sodium sulfite and sodium thiosulfate, pH adjusters such as slaked lime, aggregates, functional substances, nonionic, amphoteric, anionic, and cationic surfactants such as polyoxyethylene alkyl ether, hydrophobic polymer compounds such as polyethylene and polypropylene, dimethyl silicone oil, etc.
  • a water-retaining agent such as wood flour and vermiculite
  • a water-absorbing polymer such as a cross-linked poly(meth)acrylic acid
  • a hydrogen generation inhibitor such as sodium sulfite and sodium thiosulfate
  • pH adjusters such as slaked lime
  • aggregates aggregates
  • functional substances such as polyoxyethylene alkyl ether, hydrophobic polymer compounds such as polyethylene and polypropy
  • Heating aids such as FeCl2
  • metals other than iron such as silicon and aluminum
  • materials other than iron oxide such as manganese dioxide
  • Additional additives consisting of metal oxides, acidic substances such as hydrochloric acid, maleic acid, and acetic acid, fibrous materials such as pulp, fertilizer components such as urea, humectants such as glycerin and D-sorbitol, mold release agents, or mixtures thereof. It may contain at least one selected from the components.
  • the heat generating composition of the present invention may be any of the components of heat generating compositions conventionally disclosed, commercially available, or known and used in disposable hand warmers and heating elements, selected as appropriate. be able to.
  • the initial exothermic composition is 100% by weight in total, and the total of the above-mentioned iron powder, carbon component, reaction accelerator, water retention agent, water, and other components contained in the exothermic composition is 100% by weight. It becomes. It is preferable that the blending ratio of each component is appropriately selected depending on the use, purpose, etc. In addition, two or more types of each component (for example, iron powder, etc.) may be blended, and it is preferable that they are appropriately selected depending on the use, purpose, etc.
  • the amount of the heat-generating composition sealed in the inner bag is preferably 1 to 60 g. , 10 to 40 g is particularly preferred.
  • the moisture residual rate of the initial heat generating composition is 100%, and the ratio of residual moisture to the amount of iron powder after storage for a predetermined period, for example, after storage for 4 years (the weight of iron powder is taken as 100).
  • the weight ratio of the residual moisture content is preferably 45% or more, more preferably 50% or more. If the ratio of residual moisture to the amount of iron powder after storage for 4 years is 45% or more, the heating element can still perform its original heat generation performance even after storage for 4 years.
  • measuring the residual moisture content after storage for 4 years it is possible to measure samples that have been stored for 4 years since the heating element was manufactured, but instead, measurements should be taken of samples that have been subjected to a forced deterioration test of the heating element. It's okay.
  • a forced deterioration test of a heating element involves accelerating the deterioration of the heating element by leaving it in an environment with a room temperature of 50°C and a humidity of 40%. This is an accelerated test that corresponds to the deterioration of Similarly, a sample left for 2 weeks corresponds to a 2-year deterioration test, a sample left for 3 weeks corresponds to a 3-year deterioration test, and a sample left for 4 weeks corresponds to a 4-year deterioration test.
  • the ratio of residual moisture to the amount of iron powder is 45% or more after being left in an environment with a room temperature of 50°C and a humidity of 40% for 4 weeks, the original heat generating performance of the heating element will not be maintained even after being stored for 4 years. This means that it can be performed without deterioration.
  • the state of the heating element after storage for 4 years will be evaluated using the 4-year deterioration test.
  • the heating element of the present invention has sufficiently satisfactory heating characteristics, with an initial rise time of the heating element within 20 minutes and a duration of heating of 0.1 to 12 hours. Moreover, even after long-term storage, for example, 4 years, the heating element has a rising time of less than 20 minutes and a duration of 0.1 to 12 hours, with almost no deterioration of its good heating properties. It's something that doesn't exist.
  • the heating element of the present invention is (A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture, (B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%;
  • the ratio is (B)/(A) ⁇ 80%, and the good heat generation properties are hardly deteriorated.
  • it is further preferable that the ratio is 85% or more.
  • the heating element of the present invention is (A) Based on the duration that the heating element maintains a heat generation state of 40°C or more immediately after manufacture, (B) The difference in the duration of time that a heating element maintains a heat generation state of 40°C or higher after being left in an environment with a room temperature of 50°C and a humidity of 40% for 4 weeks after manufacture, that is, from (B) to (A) It is preferable that the absolute value of the subtracted value is 1 hour or less, particularly preferably 0.8 hour or less.
  • the heating element of the present invention preferably has an initial duration of heat generation of 0.1 to 12 hours.
  • the heat generation duration is the time during which a temperature of 40° C. or higher is maintained, and can be defined based on JIS S4100.
  • the term "initial" refers to the state immediately after the heating element is manufactured, and in the present invention, it may also be expressed as, for example, 0 years.
  • the heating element of the present invention is a heating element that can maintain a stable heating state for a predetermined period of time, and for example, has a storage period of 0 to 4 years and maintains the initial heating duration without significantly reducing it. It is possible to do so without impairing the original heat generation performance.
  • the heating element of the present invention has an inner bag enclosing a heat generating composition and an outer bag enclosing the inner bag.
  • At least a part of the inner bag is breathable, for example, it is composed of at least one breathable layer, and the breathable layer may be a breathable film, a nonwoven fabric of the breathable film, or a woven fabric. Examples include, but are not limited to, materials laminated with cloth, paper, etc. Further, a non-breathable film may be used for a part of the inner bag.
  • breathable films preferably used in the present invention include nonwoven fabrics, uniaxially or biaxially stretched porous films, and nonporous films with through holes.
  • the porous film preferably has through-holes with an average pore diameter of 0.5 to 1000 ⁇ m.
  • porous film one obtained by uniaxially or biaxially stretching a film is preferably used.
  • Synthetic resins are used as materials for the film, such as polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, saponified ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer.
  • Polymers, polyethylene terephthalate, etc. may be used, and one type or a mixture of two or more of these resins may be used.
  • the heating element of the present invention can have an adhesive layer on at least a portion of the inner bag.
  • the adhesive used in this adhesive layer is not particularly limited, but examples include vinyl acetate adhesive, polyvinyl acetal adhesive, vinyl chloride adhesive, acrylic adhesive, polyamide adhesive, Examples include polyethylene adhesives, cellulose adhesives, chloroprene (neoprene) adhesives, nitrile rubber adhesives, butyl rubber adhesives, and silicone rubber adhesives.
  • the heating element of the present invention has excellent versatility because ordinary materials can be used for the inner bag.
  • a non-breathable film or sheet is used, such as a conventionally disclosed non-breathable film or sheet, a commercially available non-breathable film or sheet, or a well-known non-breathable film or sheet.
  • non-breathable films or sheets used in disposable body warmers and heating elements.
  • non-breathable films or sheets include polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polystyrene, saponified ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, and polyethylene terephthalate. It will be done.
  • the heating element of the present invention has excellent versatility since ordinary materials can be used for the outer bag.
  • Example 1 15.000% by weight of iron powder (9.000% by weight of cast iron powder and 6.000% by weight of reduced iron powder), 11.415% by weight of activated carbon (water absorption rate 4.2, activated carbon with an average particle size of 75 ⁇ m or less) and water absorption.
  • each heating element contained 15.00 g of the heat generating composition in an inner bag (one side was a breathable film made of biaxially stretched polyethylene with through holes, and the other side was a non-breathable film made of biaxially stretched polyethylene).
  • a heat-sealed inner bag was placed inside an airtight biaxially oriented polypropylene (OPP) film coated with polyvinylidene chloride (PVDC).
  • OPP airtight biaxially oriented polypropylene
  • PVDC polyvinylidene chloride
  • a JIS temperature characteristic graph and table were created using the average values.
  • the heating element after one week of the forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created.
  • the heating element after 2 weeks of the forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created.
  • the heating element after 3 weeks of forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created.
  • the heating element after 4 weeks of forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created.
  • a sample left for one week (7 days) at a room temperature of 50°C and a humidity of 40% corresponds to a one-year deterioration test
  • a sample left in the same manner for two weeks corresponds to a two-year deterioration test
  • a sample left for 3 weeks corresponds to a 3-year deterioration test
  • a sample left for 4 weeks corresponds to a 4-year deterioration test.
  • Example 2 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 20.000% by weight of iron powder (12.000% by weight of cast iron powder and 8.000% by weight of reduced iron powder), 10.500% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) and 12.950% by weight of activated carbon (2.450% by weight with water absorption rate of 2.6 and average particle size of 75 ⁇ m or less) and 9.540% by weight of fillers (2.080% by weight of wood flour and 7.460% by weight of vermiculite).
  • iron powder 12.000% by weight of cast iron powder and 8.000% by weight of reduced iron powder
  • activated carbon water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less
  • 12.950% by weight of activated carbon (2.450% by weight with water absorption rate of 2.6 and average particle size of 75 ⁇ m or less
  • Example 1 %, 2.340% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 55.000% of 8% salt water (50.600% by weight of water and 4.400% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 1 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 3 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 25.000% by weight of iron powder (15.000% by weight of cast iron powder and 10.000% by weight of reduced iron powder), 9.585% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) 11.760% by weight of activated carbon (2.175% by weight of activated carbon with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less) and 8.810% by weight of fillers (1.870% by weight of wood flour and 6.940% by weight of vermiculite).
  • activated carbon water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less
  • 11.760% by weight of activated carbon (2.175% by weight of activated carbon with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less
  • 8.810% by weight of fillers (1.870% by
  • Example 1 %, 2.260% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 52.000% of 8% salt water (47.840% by weight of water and 4.160% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 1 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 4 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 30.000% by weight of iron powder (18.000% by weight of cast iron powder and 12.000% by weight of reduced iron powder), 8.670% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) and 10.570% by weight of activated carbon (1.900% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less) and 8.080% by weight of fillers (1.660% by weight of wood flour and 6.420% by weight of vermiculite).
  • iron powder 18.000% by weight of cast iron powder and 12.000% by weight of reduced iron powder
  • activated carbon water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less
  • 10.570% by weight of activated carbon (1.900% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or
  • Example 1 %, 2.180% by weight of super absorbent resin as water retaining materials, 0.170% by weight of sodium tripolyphosphate, and 49.000% of 8% salt water (45.080% by weight of water and 3.920% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 1 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 5 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 35.000% by weight of iron powder (21.000% by weight of cast iron powder and 14.000% by weight of reduced iron powder), 7.500% by weight of activated carbon (activated carbon with a water absorption rate of 4.2 and an average particle size of 75 ⁇ m or less). and 9.430% by weight of activated carbon (1.930% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less) and 6.700% by weight of fillers (1.600% by weight of wood flour and 5.100% by weight of vermiculite).
  • activated carbon activated carbon with a water absorption rate of 4.2 and an average particle size of 75 ⁇ m or less
  • 9.430% by weight of activated carbon (1.930% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less
  • 6.700% by weight of fillers (1.600% by weight
  • Example 1 %, 2.200% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 46.500% by weight of 8% salt water (42.780% by weight of water and 3.720% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 2 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 6 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 40.000% by weight of iron powder (24.000% by weight of cast iron powder and 16.000% by weight of reduced iron powder), 6.840% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) and 8.190% by weight of activated carbon (1.350% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less) and 6.620% by weight of fillers (1.240% by weight of wood flour and 5.380% by weight of vermiculite).
  • iron powder 24.000% by weight of cast iron powder and 16.000% by weight of reduced iron powder
  • activated carbon water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less
  • 8.190% by weight of activated carbon (1.350% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or
  • Example 1 %, 2.020% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 43.000% of 8% salt water (39.560% by weight of water and 3.440% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 2 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 7 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 45.000% by weight of iron powder (27.000% by weight of cast iron powder and 18.000% by weight of reduced iron powder), 5.925% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) 7.000% by weight of activated carbon with a water absorption rate of 2.6 and 1.075% by weight of average particle size of 75 ⁇ m or less), and 5.890% by weight of fillers (1.030% by weight of wood flour and 4.860% by weight of vermiculite).
  • Example 1 %, 1.940% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 40.000% of 8% salt water (36.800% by weight of water and 3.200% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 2 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 8 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 40.000% by weight of iron powder (24.000% by weight of cast iron powder and 16.000% by weight of reduced iron powder), 6.840% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) and 8.190% by weight of activated carbon (1.350% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less) and 6.620% by weight of fillers (1.240% by weight of wood flour and 5.380% by weight of vermiculite).
  • iron powder 24.000% by weight of cast iron powder and 16.000% by weight of reduced iron powder
  • activated carbon water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less
  • 8.190% by weight of activated carbon (1.350% by weight with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or
  • a heat generating composition 2.020% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 43.000% of 8% salt water (39.560% by weight of water and 3.440% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heat generating elements were produced in the same manner as in Example 1, except that 30.50 g of the obtained heat generating composition was sealed in the inner bag.
  • the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 2 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 9 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 45.000% by weight of iron powder (27.000% by weight of cast iron powder and 18.000% by weight of reduced iron powder), 5.925% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) 7.000% by weight of activated carbon with a water absorption rate of 2.6 and 1.075% by weight of average particle size of 75 ⁇ m or less), and 5.890% by weight of fillers (1.030% by weight of wood flour and 4.860% by weight of vermiculite).
  • % 1.940% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 40.000% of 8% salt water (36.800% by weight of water and 3.200% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heat generating elements were produced in the same manner as in Example 1, except that 30.5 g of the obtained heat generating composition was sealed in the inner bag.
  • the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 3 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • a heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 57.725% by weight of iron powder (17.773% by weight of cast iron powder and 39.952% by weight of reduced iron powder), 2.413% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) and activated carbon with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less (2.033% by weight) and 4.446% by weight of fillers (2.593% by weight of wood flour and 3.124% by weight of vermiculite) and 5.717% by weight of fillers (wood flour 2.593% and vermiculite 3.124% by weight).
  • Example 1 %, 1.302% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 8% salt water (28.189% by weight of water and 2.451% by weight of salt) 30.640% by weight % to prepare an exothermic composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used.
  • the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 3 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 2 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 57.725% by weight of iron powder (17.773% by weight of cast iron powder and 39.952% by weight of reduced iron powder), 2.413% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 ⁇ m or less) and activated carbon with a water absorption rate of 2.6 and an average particle size of 75 ⁇ m or less (2.033% by weight) and 4.446% by weight of fillers (2.593% by weight of wood flour and 3.124% by weight of vermiculite) and 5.717% by weight of fillers (wood flour 2.593% and vermiculite 3.124% by weight).
  • Example 1 %, 1.302% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 8% salt water (28.189% by weight of water and 2.451% by weight of salt) 30.640% by weight % to prepare an exothermic composition.
  • Five heating elements were produced in the same manner as in Example 1, except that 30.5 g of the obtained heat generating composition was sealed in the inner bag.
  • the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 3 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
  • Example 3 A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 50.000% by weight of iron powder (30.000% by weight of cast iron powder and 20.000% by weight of reduced iron powder), 5.000% by weight of activated carbon (activated carbon with water absorption rate of 4.2 and average particle size of 75 ⁇ m or less). and 5.800% by weight of activated carbon (0.800% by weight with water absorption rate of 2.6 and average particle size of 75 ⁇ m or less) and 5.160% by weight of fillers (0.800% by weight of wood flour and 4.360% by weight of vermiculite).
  • activated carbon activated carbon with water absorption rate of 4.2 and average particle size of 75 ⁇ m or less
  • 5.800% by weight of activated carbon (0.800% by weight with water absorption rate of 2.6 and average particle size of 75 ⁇ m or less
  • 5.160% by weight of fillers (0.800% by weight of wood flour and 4.360% by weight of vermic
  • Example 1 %, 1.870% by weight of super absorbent resin as water retaining materials, 0.170% by weight of sodium tripolyphosphate, and 37.000% of 8% salt water (34.040% by weight of water and 2.960% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
  • Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table.
  • Example 3 the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.

Abstract

[Problem] To provide a heat-generating body for heat supplying use, which, when stored for a long period, can keep the heat generation time thereof at the same level as that before the storage. [Solution] Provided is a heat-generating body for heat supplying use, comprising at least an outer bag and an air-permeable inner bag, in which a heat-generating composition is enclosed in the inner bag, the heat-generating composition comprises at least an iron powder, a carbon component, a reaction accelerator, a water-retaining agent and water at the time point of being enclosed in the inner bag of the heat-generating body, and the content of the iron powder in the heat-generating composition is 15% by weight to 45% by weight and the content of the water in the heat-generating composition at the initial stage is 35% by weight to 55% by weight in which the whole weight of the heat-generating composition at the initial stage is 100% by weight.

Description

発熱体、および、発熱組成物Heating element and exothermic composition
　本発明は発熱体及び発熱組成物に関し、長期間保存しても発熱体の発熱性能を損なわない発熱体および発熱組成物に関する。 The present invention relates to a heat generating element and a heat generating composition, and more particularly to a heat generating element and a heat generating composition that do not impair the heat generating performance of the heat generating element even when stored for a long period of time.
　従来から、鉄粉等の金属粉を主成分とする発熱組成物と空気中の酸素とを反応させて得られる反応熱を利用した発熱体が知られており、かかる発熱体を人体と接触させて人体に熱を供給する方法が利用されている。 Conventionally, heating elements have been known that utilize the reaction heat obtained by reacting a heat generating composition mainly composed of metal powder such as iron powder with oxygen in the air. A method of supplying heat to the human body is used.
　一般の貼る人体用カイロでは、発熱原料を内袋に封入し、この内袋をさらに外袋に封入する態様が通常とられているが、保存期間中に発熱体に劣化が生じ、その結果、発熱の持続時間が減少するなど、所望の性能を担保できないことが多い。 In general pasted body warmers, the heating material is sealed in an inner bag, and this inner bag is further sealed in an outer bag, but the heating element deteriorates during storage, and as a result, In many cases, the desired performance cannot be guaranteed, such as the duration of heat generation being reduced.
　例えば、外袋を、ポリエステルフィルム基材にアルミニウムを積層してなる材料で構成すると、積層したアルミニウムにクラックが発生する場合があり、特に長期に保存する場合にはこの影響を受け易い。また、外袋を、ポリエチレンテレフタレートフィルム基材に酸化アルミニウム等の金属酸化物を被覆した材料で構成する（例えば、特許文献１）と、安価品が求められる業界では使用しづらく汎用性がなくなるという問題がある。 For example, if the outer bag is made of a material made by laminating aluminum onto a polyester film base material, cracks may occur in the laminated aluminum, and the bag is particularly susceptible to this effect when stored for a long period of time. Additionally, if the outer bag is made of a polyethylene terephthalate film base material coated with a metal oxide such as aluminum oxide (for example, Patent Document 1), it will be difficult to use in industries where inexpensive products are required, and the versatility will be lost. There's a problem.
　したがって、長期間の保存後でも所定の温度を所定時間持続できるなどの所定の性能を保持できることが要求されるが、未だ、このような発熱体は知られていないのが現状である。 Therefore, it is required to be able to maintain a predetermined performance such as being able to maintain a predetermined temperature for a predetermined time even after long-term storage, but at present, such a heating element is not yet known.
特開平１１－２３９５８４号公報Japanese Patent Application Publication No. 11-239584
　このような金属粉と酸素との酸化反応を利用した発熱体は、開封後すみやかに昇温し、所定温度を所定時間持続することが求められており、特に、長期間保存した後でも、当初の発熱性能を低下させずに保持している発熱体が求められている。 Heating elements that utilize the oxidation reaction between metal powder and oxygen are required to quickly raise the temperature after opening and maintain a specified temperature for a specified period of time. There is a need for a heating element that maintains the heat generation performance of the device without degrading it.
　本発明は上記問題点を解決するためになされたものであり、本発明は熱を供給する発熱体が、長期間保存した後でも保存前と同等の発熱時間を持続することができる発熱体、および、発熱体組成物を提供することを目的とする。 The present invention has been made to solve the above problems, and the present invention provides a heating element that can maintain heat generation time equivalent to that before storage even after long-term storage. And, it is an object of the present invention to provide a heating element composition.
本発明の発熱体は、熱を供給するための発熱体であって、少なくとも外袋と、通気性の内袋とを有し、該内袋の内部には発熱組成物が封入されており、該発熱体の内袋内に封入された当初の発熱組成物が、少なくとも、鉄粉末、炭素成分、反応促進剤、保水剤、および水を含有し、該鉄粉末の含有量が発熱組成物中、１５重量％～４５重量％であり、当初の発熱組成物の水の含有量が、発熱組成物中、３５重量％～６０重量％であり、当初の発熱組成物全体で１００重量％とすることを特徴とする。 The heating element of the present invention is a heating element for supplying heat, and has at least an outer bag and a breathable inner bag, and a heat generating composition is sealed inside the inner bag, The initial heat generating composition sealed in the inner bag of the heating element contains at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water, and the content of the iron powder is in the heat generating composition. , 15% to 45% by weight, and the water content of the initial exothermic composition is 35% to 60% by weight in the exothermic composition, and the total initial exothermic composition is 100% by weight. It is characterized by
　本発明において、前記発熱体は、
（Ａ）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間、
に対する
（B）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間、
の比率が、（B）／（A）≧８０％であることが好ましい。
　また、前記発熱体は、
（Ａ）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間、
に対する
（B）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間、
との差の絶対値が１時間以内であることが好ましい。
　また、本発明において、前記炭素成分は活性炭であり、該活性炭の平均粒径が１～１５０μｍであることが好ましい。
　また、前記発熱体は、４０℃以上の発熱状態を保持する持続時間が、０．１～１２時間であることが好ましい。 In the present invention, the heating element is
(A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
(B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%;
It is preferable that the ratio is (B)/(A)≧80%.
Further, the heating element is
(A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
(B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%;
It is preferable that the absolute value of the difference is within 1 hour.
Further, in the present invention, the carbon component is preferably activated carbon, and the activated carbon preferably has an average particle size of 1 to 150 μm.
Further, it is preferable that the heating element maintains a heat generation state of 40° C. or higher for a duration of 0.1 to 12 hours.
　本発明の発熱体の経時劣化を防ぐ方法は、熱を供給するための発熱体の経時劣化を防ぐ方法であって、前記発熱体は、少なくとも外袋と、通気性の内袋とを有し、該内袋の内部には発熱組成物が封入されており、該発熱体の内袋内に封入された当初の発熱組成物が、少なくとも、鉄粉末、炭素成分、反応促進剤、保水剤、および水を含有し、該鉄粉末の含有量を発熱組成物中、１５重量％～４５重量％とし、当初の発熱組成物の水の含有量を、発熱組成物中、３５重量％～６０重量％とし、当初の発熱組成物全体で１００重量％とすることを特徴とする。 A method for preventing deterioration over time of a heating element of the present invention is a method for preventing deterioration over time of a heating element for supplying heat, wherein the heating element has at least an outer bag and a breathable inner bag. A heat-generating composition is sealed inside the inner bag, and the heat-generating composition initially sealed in the inner bag of the heating element includes at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water, the content of the iron powder is 15% to 45% by weight in the exothermic composition, and the initial water content of the exothermic composition is 35% to 60% by weight in the exothermic composition. %, and the entire initial exothermic composition is 100% by weight.
　本発明によれば、長期間保存しても保存前と同等の発熱時間を持続する発熱体を得ることができる。　 According to the present invention, it is possible to obtain a heating element that maintains the same heat generation time as before storage even after long-term storage.　
実施例１の発熱体の温度特性を示すグラフである。3 is a graph showing the temperature characteristics of the heating element of Example 1. 実施例２の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 2. 実施例３の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 3. 実施例４の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 4. 実施例５の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 5. 実施例６の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 6. 実施例７の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 7. 実施例８の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 8. 実施例９の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of the heating element of Example 9. 比較例１の発熱体の温度特性を示すグラフである。3 is a graph showing the temperature characteristics of a heating element of Comparative Example 1. 比較例２の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of a heating element of Comparative Example 2. 比較例３の発熱体の温度特性を示すグラフである。7 is a graph showing the temperature characteristics of a heating element of Comparative Example 3.
　以下、本発明について詳細に説明する。
　本発明の発熱体は、少なくとも外袋と、通気性の内袋とを有し、内袋の内部には発熱組成物が封入されている。発熱組成物は、内袋に封入された当初、少なくとも、鉄粉末、炭素成分、反応促進剤、保水剤、および水を含有する。 The present invention will be explained in detail below.
The heating element of the present invention has at least an outer bag and a breathable inner bag, and a heat generating composition is sealed inside the inner bag. The exothermic composition initially contains at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water when enclosed in the inner bag.
　内袋に封入された時点（当初）の発熱組成物は、水の含有量が発熱組成物中、３５重量％以上、６０重量％以下であることが好ましく、３９重量％以上、５５重量％以下であることが特に好ましい。
　発熱組成物中の水の含有量について、一般的には、水の含有量は多すぎても少なすぎても問題が生じると言われており、余分な水が発熱体中に存在しないように発熱組成物の配合が工夫されてきた。しかしながら、本発明によれば、多量の水を配合しても、十分な発熱特性を有するのである。 The water content of the exothermic composition when sealed in the inner bag (initial stage) is preferably 35% by weight or more and 60% by weight or less, and preferably 39% by weight or more and 55% by weight or less. It is particularly preferable that
Regarding the water content in the heat generating composition, it is generally said that problems will occur if the water content is too high or too low, so it is necessary to prevent excess water from being present in the heat generating element. The formulation of exothermic compositions has been devised. However, according to the present invention, even if a large amount of water is blended, sufficient heat generation properties are maintained.
　本発明に使用される鉄粉末としては、例えば、鋳鉄鉄粉、アトマイズ鉄粉、電解鉄粉、還元鉄粉、スポンジ鉄粉及びそれらの鉄合金粉等が挙げられる。更に、これらの鉄粉末が炭素や酸素を含有していてもよく、また、鉄を５０％以上含む鉄で、他の金属を含んでいてもよい。合金等として含まれる金属の種類は鉄成分が発熱組成物の成分として働けば特に制限されるものではないが、アルミニウム、マンガン、銅、ケイ素等の金属、半導体が挙げられる。本発明に用いられる金属には半導体も含まれる。本発明において、鉄以外の金属の含有量は、鉄粉末全体に対して、通常０．０１～５０重量％であり、好ましくは０．１～１０重量％である。本発明においては、２種類以上の鉄粉末を混合して使用してもよく、また、同種類の鉄粉末を２以上混合して使用してもよい。市販品の鋳鉄鉄粉としては、ＣＩＰ（ダイテツ工業株式会社製）等が挙げられ、還元鉄粉としては、ＩｎＳＩＰ（パウダーテック株式会社製）、ＤＫＰ３（ＤＯＷＡ　ＩＰクリエイション株式会社製）等が挙げられる。 Examples of the iron powder used in the present invention include cast iron powder, atomized iron powder, electrolytic iron powder, reduced iron powder, sponge iron powder, and iron alloy powder thereof. Furthermore, these iron powders may contain carbon and oxygen, and may contain other metals with iron containing 50% or more of iron. The type of metal included in the alloy etc. is not particularly limited as long as the iron component acts as a component of the exothermic composition, but examples include metals such as aluminum, manganese, copper, and silicon, and semiconductors. The metals used in the present invention also include semiconductors. In the present invention, the content of metals other than iron is usually 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the entire iron powder. In the present invention, two or more types of iron powders may be used as a mixture, or two or more types of iron powders of the same type may be used as a mixture. Commercially available cast iron powders include CIP (manufactured by Daitetsu Kogyo Co., Ltd.), and reduced iron powders include InSIP (manufactured by Powder Tech Co., Ltd.) and DKP3 (DOWA IP Creation Co., Ltd.). .
　当初の発熱体の内袋に封入された時点の発熱組成物（当初の発熱組成物）は、鉄粉末の含有量が発熱組成物中、１５重量％以上、４５重量％以下であることが好ましく、２０重量％以上、４０重量％以下であることが特に好ましい。 The heat-generating composition (initial heat-generating composition) at the time of being sealed in the inner bag of the initial heat-generating element preferably has an iron powder content of 15% by weight or more and 45% by weight or less in the heat-generating composition. , 20% by weight or more and 40% by weight or less is particularly preferable.
　本発明に用いられる炭素成分としては、カーボンブラック、黒鉛、活性炭等が挙げられるが、活性炭を用いることが好ましく、活性炭としては、例えば、吸水率が４．２の活性炭や、吸水率が２．６の活性炭等がある。また、活性炭の平均粒径は、１～１５０μｍであることが好ましく、１０～１００μｍであることが特に好ましい。炭素成分としては、用途や目的等に応じて適宜種類を選択して使用することが好ましい。
また、当初の発熱体に封入されている発熱組成物は、炭素成分の含有量が発熱組成物中、５重量％以上、１６重量％以下であることが好ましく、７重量％以上、１３重量％以下であることが特に好ましい。本発明においては、２種類以上の活性炭を混合して使用してもよく、また、同種類の活性炭を２以上混合して使用してもよい。 Examples of the carbon component used in the present invention include carbon black, graphite, activated carbon, etc., but it is preferable to use activated carbon. Examples of the activated carbon include activated carbon with a water absorption rate of 4.2, and activated carbon with a water absorption rate of 2.2. There are 6 types of activated carbon. Furthermore, the average particle size of the activated carbon is preferably 1 to 150 μm, particularly preferably 10 to 100 μm. As the carbon component, it is preferable to select and use an appropriate type depending on the use, purpose, etc.
Further, the content of the carbon component in the heat generating composition encapsulated in the initial heating element is preferably 5% by weight or more and 16% by weight or less, and preferably 7% by weight or more and 13% by weight. The following is particularly preferable. In the present invention, two or more types of activated carbon may be used as a mixture, or two or more of the same type of activated carbon may be used as a mixture.
　本発明に用いられる反応促進剤としては、発熱の反応促進ができるものであれば特に制限はないが、例えば、塩化ナトリウム、塩化カリウム等の金属ハロゲン化物や、硫酸カリウム等の金属硫酸塩類や、硝酸ナトリウム等の硝酸塩や、酢酸ナトリウム等の酢酸塩や、炭酸第一鉄等の炭酸塩等の無機電解質が一例として挙げられる。また、本発明においては、公知の使い捨てカイロや発熱体に使用されている電解質も用いることもできる。これらの反応促進剤は、通常は水溶液として用いられるが、粉体のままで用いることもできる。 The reaction promoter used in the present invention is not particularly limited as long as it can accelerate the exothermic reaction, but examples include metal halides such as sodium chloride and potassium chloride, metal sulfates such as potassium sulfate, Examples include inorganic electrolytes such as nitrates such as sodium nitrate, acetates such as sodium acetate, and carbonates such as ferrous carbonate. Further, in the present invention, electrolytes used in known disposable body warmers and heating elements can also be used. These reaction accelerators are usually used in the form of an aqueous solution, but they can also be used in the form of powder.
　本発明の発熱組成物は、上記成分の他に、木粉、バーミキュライト等の保水剤、ポリ（メタ）アクリル酸架橋体等の吸水性ポリマー、亜硫酸ナトリウム、チオ硫酸ナトリウム等の水素発生抑制剤、消石灰等のｐＨ調整剤、骨材、機能性物質、ポリオキシエチレンアルキルエーテル等のノニオン、両性イオン、アニオン、カチオンの界面活性剤、ポリエチレンやポリプロピレン等の疎水性高分子化合物、ジメチルシリコーンオイル等の有機ケイ素化合物、焦電物質、セラミック等の遠赤外線放射性物質、トルマリン等のマイナスイオン発生剤、ＦｅＣｌ２等の発熱助剤、ケイ素やアルミニウム等の鉄以外の金属、二酸化マンガン等の酸化鉄以外の金属酸化物、塩酸やマレイン酸や酢酸等の酸性物質、パルプ等の繊維状物、尿素等の肥料成分、グリセリンやＤ－ソルビトール等の保湿剤、離型剤又はこれらの混合物からなる付加的な成分から選ばれた少なくとも一種を含有してもよい。また、本発明の発熱組成物は、従来より開示されている、または市販されている、または公知の、使い捨てカイロや発熱体に使用される発熱組成物の如何なる成分をも適宜選択して使用することができる。 In addition to the above-mentioned components, the heat-generating composition of the present invention includes a water-retaining agent such as wood flour and vermiculite, a water-absorbing polymer such as a cross-linked poly(meth)acrylic acid, a hydrogen generation inhibitor such as sodium sulfite and sodium thiosulfate, pH adjusters such as slaked lime, aggregates, functional substances, nonionic, amphoteric, anionic, and cationic surfactants such as polyoxyethylene alkyl ether, hydrophobic polymer compounds such as polyethylene and polypropylene, dimethyl silicone oil, etc. Organosilicon compounds, pyroelectric substances, far-infrared emitting substances such as ceramics, negative ion generators such as tourmaline, heating aids such as FeCl2 , metals other than iron such as silicon and aluminum, and materials other than iron oxide such as manganese dioxide Additional additives consisting of metal oxides, acidic substances such as hydrochloric acid, maleic acid, and acetic acid, fibrous materials such as pulp, fertilizer components such as urea, humectants such as glycerin and D-sorbitol, mold release agents, or mixtures thereof. It may contain at least one selected from the components. Furthermore, the heat generating composition of the present invention may be any of the components of heat generating compositions conventionally disclosed, commercially available, or known and used in disposable hand warmers and heating elements, selected as appropriate. be able to.
　本発明において、当初の発熱組成物は全体で１００重量％であり、上記した鉄粉末、炭素成分、反応促進剤、保水剤、水、および、その他の発熱組成物含有成分の合計が１００重量％となっている。各成分の配合割合は、用途、目的等に応じて、適宜選択されることが好ましい。また、それぞれの成分（例えば、鉄粉末など）は、２種類以上を配合しても良く、用途、目的等に応じて適宜選択されることが好ましい。 In the present invention, the initial exothermic composition is 100% by weight in total, and the total of the above-mentioned iron powder, carbon component, reaction accelerator, water retention agent, water, and other components contained in the exothermic composition is 100% by weight. It becomes. It is preferable that the blending ratio of each component is appropriately selected depending on the use, purpose, etc. In addition, two or more types of each component (for example, iron powder, etc.) may be blended, and it is preferable that they are appropriately selected depending on the use, purpose, etc.
　本発明の発熱体は、内袋に封入される発熱組成物の充填量を用途等に応じて適宜選択することが好ましく、例えば、発熱組成物の充填量は、１～６０ｇであることが好ましく、１０～４０ｇであることが特に好ましい。 In the heating element of the present invention, it is preferable to appropriately select the amount of the heat-generating composition sealed in the inner bag depending on the application, etc. For example, the amount of the heat-generating composition filled is preferably 1 to 60 g. , 10 to 40 g is particularly preferred.
　本発明の発熱体において、当初の発熱組成物の水分残存率は１００％であり、所定期間保存後の、例えば4年間保存後の鉄粉量に対する水分残存の割合（鉄粉重量を１００としたときの、残存水分量の重量比）は４５％以上であることが好ましく、更に好ましくは、５０％以上である。　
　４年間保存後の鉄粉量に対する水分残存の割合が４５％以上であれば、４年間保存した後でも当初の発熱体の発熱性能を低下させることなく発揮することができる。４年間保存後の残存水分量の測定にあたっては、発熱体の製造から４年間保存した試料の測定をしてもよいが、これに代えて発熱体の強制劣化試験を行った試料の測定をしてもよい。 In the heating element of the present invention, the moisture residual rate of the initial heat generating composition is 100%, and the ratio of residual moisture to the amount of iron powder after storage for a predetermined period, for example, after storage for 4 years (the weight of iron powder is taken as 100). The weight ratio of the residual moisture content is preferably 45% or more, more preferably 50% or more.
If the ratio of residual moisture to the amount of iron powder after storage for 4 years is 45% or more, the heating element can still perform its original heat generation performance even after storage for 4 years. When measuring the residual moisture content after storage for 4 years, it is possible to measure samples that have been stored for 4 years since the heating element was manufactured, but instead, measurements should be taken of samples that have been subjected to a forced deterioration test of the heating element. It's okay.
　発熱体の強制劣化試験とは、作製した発熱体を室温５０℃、湿度４０％の環境下に放置することによって発熱体の劣化を促進し、１週間（７日間）放置した試料が１年分の劣化に相当する加速試験である。同様にして２週間放置した試料が２年劣化試験、３週間放置した試料が３年劣化試験、４週間放置した試料が４年劣化試験に相当する。従って、室温５０℃、湿度４０％の環境下で４週間放置後の鉄粉量に対する水分残存の割合が４５％以上である場合には、４年間保存した後でも当初の発熱体の発熱性能を低下させることなく発揮することができることを意味する。以下、本発明の説明においては４年間保存後の発熱体の状態について、前記４年劣化試験を用いて評価することとする。 A forced deterioration test of a heating element involves accelerating the deterioration of the heating element by leaving it in an environment with a room temperature of 50°C and a humidity of 40%. This is an accelerated test that corresponds to the deterioration of Similarly, a sample left for 2 weeks corresponds to a 2-year deterioration test, a sample left for 3 weeks corresponds to a 3-year deterioration test, and a sample left for 4 weeks corresponds to a 4-year deterioration test. Therefore, if the ratio of residual moisture to the amount of iron powder is 45% or more after being left in an environment with a room temperature of 50°C and a humidity of 40% for 4 weeks, the original heat generating performance of the heating element will not be maintained even after being stored for 4 years. This means that it can be performed without deterioration. In the following description of the present invention, the state of the heating element after storage for 4 years will be evaluated using the 4-year deterioration test.
　本発明の発熱体は、当初の発熱体の立ち上がり時間が２０分以内であり、発熱持続時間が０．１～１２時間であり、十分満足のいく発熱特性を有するものである。しかも、長期間、例えば、４年間保存した後でも、その発熱体は、立ち上がり時間は２０分以内であり、持続時間も０．１～１２時間であり、良好な発熱特性を殆ど低下させることがないものである。
　例えば、本発明の発熱体は、
（Ａ）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間、
に対する
（B）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間、
の比率が、（B）／（A）≧８０％であり、良好な発熱特性を殆ど低下させることがないものである。本発明においては、該比率が、８５％以上であることが更に好ましい。 The heating element of the present invention has sufficiently satisfactory heating characteristics, with an initial rise time of the heating element within 20 minutes and a duration of heating of 0.1 to 12 hours. Moreover, even after long-term storage, for example, 4 years, the heating element has a rising time of less than 20 minutes and a duration of 0.1 to 12 hours, with almost no deterioration of its good heating properties. It's something that doesn't exist.
For example, the heating element of the present invention is
(A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
(B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%;
The ratio is (B)/(A)≧80%, and the good heat generation properties are hardly deteriorated. In the present invention, it is further preferable that the ratio is 85% or more.
　また、本発明の発熱体は、
（A）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間を基準とした時に、
（B）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間、の差が、すなわち、（B）から（A）を減じた値の絶対値が１時間以下であることが好ましく、０．８時間以下であることが特に好ましい。 Moreover, the heating element of the present invention is
(A) Based on the duration that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
(B) The difference in the duration of time that a heating element maintains a heat generation state of 40°C or higher after being left in an environment with a room temperature of 50°C and a humidity of 40% for 4 weeks after manufacture, that is, from (B) to (A) It is preferable that the absolute value of the subtracted value is 1 hour or less, particularly preferably 0.8 hour or less.
本発明の発熱体は、当初の発熱持続時間が０．１～１２時間であることが好ましい。
　ここで発熱持続時間とは、４０℃以上を保持し、持続する時間であり、ＪＩＳ　Ｓ４１００に基づいて規定することができる。
　また、本発明において当初とは、発熱体を製造した後すぐの状態を意味し、本発明においては、例えば経過年数０年相当などと表現されることもある。 The heating element of the present invention preferably has an initial duration of heat generation of 0.1 to 12 hours.
Here, the heat generation duration is the time during which a temperature of 40° C. or higher is maintained, and can be defined based on JIS S4100.
Furthermore, in the present invention, the term "initial" refers to the state immediately after the heating element is manufactured, and in the present invention, it may also be expressed as, for example, 0 years.
本発明の発熱体は、上記したように、安定した発熱状態を所定期間保持できる発熱体であり、例えば、保存期間が０～４年間で、当初の発熱持続時間を殆ど低下させることなく保持することができ、当初の発熱性能を損なわないものである。 As described above, the heating element of the present invention is a heating element that can maintain a stable heating state for a predetermined period of time, and for example, has a storage period of 0 to 4 years and maintains the initial heating duration without significantly reducing it. It is possible to do so without impairing the original heat generation performance.
　本発明の発熱体は、発熱組成物を封入した内袋と、該内袋を内包した外袋とを有する。内袋の少なくとも一部は通気性になっており、例えば、少なくとも１層以上の通気性を有する層からなり、通気性を有する層としては、通気性フィルムや、その通気性フィルムの不織布、織布、紙等を積層したものなどが挙げられるが、これらに限定されるものではない。また、内袋の一部には非通気性フィルムを用いてもよい。 The heating element of the present invention has an inner bag enclosing a heat generating composition and an outer bag enclosing the inner bag. At least a part of the inner bag is breathable, for example, it is composed of at least one breathable layer, and the breathable layer may be a breathable film, a nonwoven fabric of the breathable film, or a woven fabric. Examples include, but are not limited to, materials laminated with cloth, paper, etc. Further, a non-breathable film may be used for a part of the inner bag.
　本発明に好ましく用いられる通気性フィルムとしては、不織布、一軸または二軸延伸された多孔質フィルム、無孔フィルムに貫通孔をもうけたものなどが挙げられる。その多孔質フィルムは、その平均孔径が０．５～１０００μｍの貫通孔を有することが好ましい。 Examples of breathable films preferably used in the present invention include nonwoven fabrics, uniaxially or biaxially stretched porous films, and nonporous films with through holes. The porous film preferably has through-holes with an average pore diameter of 0.5 to 1000 μm.
　多孔質フィルムとしては、フィルムを一軸または二軸延伸することによって得られたものなどが好ましく使用される。そのフィルムの材料としては、合成樹脂等が用いられ、例えば、ポリエチレン、ポリプロピレン、ポリアミド、ポリエステル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリウレタン、ポリスチレン、エチレン－酢酸ビニル共重合ケン化物、エチレン－酢酸ビニル共重合体、ポリエチレンテレフタレートなどが挙げられ、これらの１種または２種以上混合した樹脂でもよい。 As the porous film, one obtained by uniaxially or biaxially stretching a film is preferably used. Synthetic resins are used as materials for the film, such as polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, saponified ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer. Polymers, polyethylene terephthalate, etc. may be used, and one type or a mixture of two or more of these resins may be used.
本発明の発熱体は、内袋の少なくとも一部に粘着層を有することができる。この粘着層に用いられる粘着剤としては、特に限定されるものではないが、例えば、酢酸ビニル系粘着剤、ポリビニルアセタール系粘着剤、塩化ビニル系粘着剤、アクリル系粘着剤、ポリアミド系粘着剤、ポリエチレン系粘着剤、セルロース系粘着剤、クロロプレン（ネオプレン）系粘着剤、ニトリルゴム系粘着剤、ブチルゴム系粘着剤、シリコーンゴム系粘着剤などが挙げられる。
　本発明の発熱体は、内袋として通常の材料を使用できるので汎用性にも優れている。 The heating element of the present invention can have an adhesive layer on at least a portion of the inner bag. The adhesive used in this adhesive layer is not particularly limited, but examples include vinyl acetate adhesive, polyvinyl acetal adhesive, vinyl chloride adhesive, acrylic adhesive, polyamide adhesive, Examples include polyethylene adhesives, cellulose adhesives, chloroprene (neoprene) adhesives, nitrile rubber adhesives, butyl rubber adhesives, and silicone rubber adhesives.
The heating element of the present invention has excellent versatility because ordinary materials can be used for the inner bag.
　本発明の発熱体を構成する外袋としては、例えば、非通気性フィルムまたはシートが使用され、従来より開示されている非通気性フィルムまたはシート、市販されている非通気性フィルムまたはシート、公知の使い捨てカイロや発熱体に使用されている非通気性のフィルムまたはシートなどが挙げられる。非通気性フィルムまたはシートとしては、ポリエチレン、ポリプロピレン、ポリアミド、ポリエステル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、エチレン－酢酸ビニル共重合ケン化物、、エチレン－酢酸ビニル共重合体、ポリエチレンテレフタレートなどが挙げられる。
　本発明の発熱体は、外袋として通常の材料を使用できるので汎用性にも優れている。
  As the outer bag constituting the heating element of the present invention, for example, a non-breathable film or sheet is used, such as a conventionally disclosed non-breathable film or sheet, a commercially available non-breathable film or sheet, or a well-known non-breathable film or sheet. Examples include non-breathable films or sheets used in disposable body warmers and heating elements. Examples of non-breathable films or sheets include polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polystyrene, saponified ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, and polyethylene terephthalate. It will be done.
The heating element of the present invention has excellent versatility since ordinary materials can be used for the outer bag.
　以下に、実施例を用いて本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.
（実施例１）
　鉄粉（鋳造鉄粉９．０００重量％および還元鉄粉６．０００重量％）を１５．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭１１．４１５重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭２．７２５重量％）を１４．１４０重量％、充填剤（木粉２．２９０重量％およびバーミキュライト７．９８０重量％）を１０．２７０重量％、保水剤として高吸水性樹脂を２．４２０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水５３．３６０重量％および食塩４．６４０重量％）を５８．０００重量％混合し、発熱組成物を作製した。 (Example 1)
15.000% by weight of iron powder (9.000% by weight of cast iron powder and 6.000% by weight of reduced iron powder), 11.415% by weight of activated carbon (water absorption rate 4.2, activated carbon with an average particle size of 75 μm or less) and water absorption. 14.140% by weight of activated carbon (2.725% by weight of activated carbon with a ratio of 2.6 and an average particle size of 75 μm or less), 10.270% by weight of fillers (2.290% by weight of wood flour and 7.980% by weight of vermiculite), As water retention agents, 2.420% by weight of super absorbent resin, 0.170% by weight of sodium tripolyphosphate, and 58.000% by weight of 8% salt water (53.360% by weight of water and 4.640% by weight of salt) The mixture was mixed to prepare an exothermic composition.
　得られた発熱組成物を用いて、５個の発熱体を作製した。すなわち、発熱体は、それぞれ、発熱組成物１５．００ｇを内袋（一方の面を２軸延伸ポリエチレンに貫通孔を設けた通気性フィルム、他方の面を２軸延伸ポリエチレンからなる非通気性フィルムで形成）の内部に封入し、ヒートシールした内袋を、気密性のある２軸延伸ポリプロピレン（ＯＰＰ）フィルムにポリ塩化ビニリデン（ＰＶＤＣ）をコートした外袋に収納して作製された。得られた発熱体について、以下に記す強制劣化試験を行った。
　まず、発熱体作製直後（０週）の各発熱体について、ＪＩＳ　Ｓ４１００に基づいて、立上がり時間、最高温度、水分残存量、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。次に、強制劣化試験１週間後の発熱体について、同様に、ＪＩＳ　Ｓ４１００に基づいて前記測定を行い、ＪＩＳ温度特性グラフ及び表を作成した。次いで、強制劣化試験２週間後の発熱体についても、同様に、ＪＩＳ　Ｓ４１００に基づいて前記測定を行い、ＪＩＳ温度特性グラフ及び表を作成した。次いで、強制劣化試験３週間後の発熱体についても、同様に、ＪＩＳ Ｓ４１００に基づいて前記測定を行い、ＪＩＳ温度特性グラフ及び表を作成した。次いで、強制劣化試験４週間後の発熱体についても、同様に、ＪＩＳ　Ｓ４１００に基づいて前記測定を行い、ＪＩＳ温度特性グラフ及び表を作成した。
　なお、前述のとおり、強制劣化試験は、室温５０℃、湿度４０％の環境下に１週間（７日間）放置した試料が１年劣化試験に相当し、同様にして２週間放置した試料が２年劣化試験、３週間放置した試料が３年劣化試験、４週間放置した試料が４年劣化試験に相当する。この強制劣化試験において、各劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表１に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図１に示す。 Using the obtained exothermic composition, five heating elements were produced. That is, each heating element contained 15.00 g of the heat generating composition in an inner bag (one side was a breathable film made of biaxially stretched polyethylene with through holes, and the other side was a non-breathable film made of biaxially stretched polyethylene). A heat-sealed inner bag was placed inside an airtight biaxially oriented polypropylene (OPP) film coated with polyvinylidene chloride (PVDC). A forced deterioration test described below was conducted on the obtained heating element.
First, for each heating element immediately after the heating element was produced (0 weeks), the rise time, maximum temperature, residual moisture content, and duration of maintaining the temperature at 40°C or higher were measured based on JIS S4100. A JIS temperature characteristic graph and table were created using the average values. Next, the heating element after one week of the forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created. Next, the heating element after 2 weeks of the forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created. Next, the heating element after 3 weeks of forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created. Next, the heating element after 4 weeks of forced deterioration test was similarly subjected to the above measurements based on JIS S4100, and a JIS temperature characteristic graph and table were created.
As mentioned above, in the forced deterioration test, a sample left for one week (7 days) at a room temperature of 50°C and a humidity of 40% corresponds to a one-year deterioration test, and a sample left in the same manner for two weeks corresponds to a two-year deterioration test. A sample left for 3 weeks corresponds to a 3-year deterioration test, and a sample left for 4 weeks corresponds to a 4-year deterioration test. In this forced deterioration test, the amount of moisture loss was measured for each sample of the deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例２）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉１２．０００重量％および還元鉄粉８．０００重量％）を２０．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭１０．５００重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭２．４５０重量％）を１２．９５０重量％、充填剤（木粉２．０８０重量％およびバーミキュライト７．４６０重量％）を９．５４０重量％、保水材として高吸水性樹脂を２．３４０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水５０．６００重量％および食塩４．４００重量％）を５５．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表１に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図２に示す。 (Example 2)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 20.000% by weight of iron powder (12.000% by weight of cast iron powder and 8.000% by weight of reduced iron powder), 10.500% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) and 12.950% by weight of activated carbon (2.450% by weight with water absorption rate of 2.6 and average particle size of 75 μm or less) and 9.540% by weight of fillers (2.080% by weight of wood flour and 7.460% by weight of vermiculite). %, 2.340% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 55.000% of 8% salt water (50.600% by weight of water and 4.400% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例３）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉（鋳造鉄粉１５．０００重量％および還元鉄粉１０．０００重量％）を２５．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭９．５８５重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭２．１７５重量％）を１１．７６０重量％、充填剤（木粉１．８７０重量％およびバーミキュライト６．９４０重量％）を８．８１０重量％、保水材として高吸水性樹脂を２．２６０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水４７．８４０重量％および食塩４．１６０重量％）を５２．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表１に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図３に示す。 (Example 3)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 25.000% by weight of iron powder (15.000% by weight of cast iron powder and 10.000% by weight of reduced iron powder), 9.585% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) 11.760% by weight of activated carbon (2.175% by weight of activated carbon with a water absorption rate of 2.6 and an average particle size of 75 μm or less) and 8.810% by weight of fillers (1.870% by weight of wood flour and 6.940% by weight of vermiculite). %, 2.260% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 52.000% of 8% salt water (47.840% by weight of water and 4.160% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例４）
発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉１８．０００重量％および還元鉄粉１２．０００重量％）を３０．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭８．６７０重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭１．９００重量％）を１０．５７０重量％、充填剤（木粉１．６６０重量％およびバーミキュライト６．４２０重量％）を８．０８０重量％、保水材として高吸水性樹脂を２．１８０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水４５．０８０重量％および食塩３．９２０重量％）を４９．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表１に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図４に示す。 (Example 4)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 30.000% by weight of iron powder (18.000% by weight of cast iron powder and 12.000% by weight of reduced iron powder), 8.670% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) and 10.570% by weight of activated carbon (1.900% by weight with a water absorption rate of 2.6 and an average particle size of 75 μm or less) and 8.080% by weight of fillers (1.660% by weight of wood flour and 6.420% by weight of vermiculite). %, 2.180% by weight of super absorbent resin as water retaining materials, 0.170% by weight of sodium tripolyphosphate, and 49.000% of 8% salt water (45.080% by weight of water and 3.920% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 1. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例５）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉２１．０００重量％および還元鉄粉１４．０００重量％）を３５．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭７．５００重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭１．９３０重量％）を９．４３０重量％、充填剤（木粉１．６００重量％およびバーミキュライト５．１００重量％）を６．７００重量％、保水材として高吸水性樹脂を２．２００重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水４２．７８０重量％および食塩３．７２０重量％）を４６．５００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表２に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図５に示す。 (Example 5)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 35.000% by weight of iron powder (21.000% by weight of cast iron powder and 14.000% by weight of reduced iron powder), 7.500% by weight of activated carbon (activated carbon with a water absorption rate of 4.2 and an average particle size of 75 μm or less). and 9.430% by weight of activated carbon (1.930% by weight with a water absorption rate of 2.6 and an average particle size of 75 μm or less) and 6.700% by weight of fillers (1.600% by weight of wood flour and 5.100% by weight of vermiculite). %, 2.200% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 46.500% by weight of 8% salt water (42.780% by weight of water and 3.720% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例６）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉２４．０００重量％および還元鉄粉１６．０００重量％）を４０．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭６．８４０重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭１．３５０重量％）を８．１９０重量％、充填剤（木粉１．２４０重量％およびバーミキュライト５．３８０重量％）を６．６２０重量％、保水材として高吸水性樹脂を２．０２０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水３９．５６０重量％および食塩３．４４０重量％）を４３．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表２に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図６に示す。 (Example 6)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 40.000% by weight of iron powder (24.000% by weight of cast iron powder and 16.000% by weight of reduced iron powder), 6.840% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) and 8.190% by weight of activated carbon (1.350% by weight with a water absorption rate of 2.6 and an average particle size of 75 μm or less) and 6.620% by weight of fillers (1.240% by weight of wood flour and 5.380% by weight of vermiculite). %, 2.020% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 43.000% of 8% salt water (39.560% by weight of water and 3.440% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例７）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉２７．０００重量％および還元鉄粉１８．０００重量％）を４５．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭５．９２５重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭１．０７５重量％）を７．０００重量％、充填剤（木粉１．０３０重量％およびバーミキュライト４．８６０重量％）を５．８９０重量％、保水材として高吸水性樹脂を１．９４０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水３６．８００重量％および食塩３．２００重量％）を４０．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表２に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図７に示す。 (Example 7)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 45.000% by weight of iron powder (27.000% by weight of cast iron powder and 18.000% by weight of reduced iron powder), 5.925% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) 7.000% by weight of activated carbon with a water absorption rate of 2.6 and 1.075% by weight of average particle size of 75 μm or less), and 5.890% by weight of fillers (1.030% by weight of wood flour and 4.860% by weight of vermiculite). %, 1.940% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 40.000% of 8% salt water (36.800% by weight of water and 3.200% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例８）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉２４．０００重量％および還元鉄粉１６．０００重量％）を４０．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭６．８４０重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭１．３５０重量％）を８．１９０重量％、充填剤（木粉１．２４０重量％およびバーミキュライト５．３８０重量％）を６．６２０重量％、保水材として高吸水性樹脂を２．０２０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水３９．５６０重量％および食塩３．４４０重量％）を４３．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を内袋に３０．５０ｇ封入した以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表２に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図８に示す。 (Example 8)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 40.000% by weight of iron powder (24.000% by weight of cast iron powder and 16.000% by weight of reduced iron powder), 6.840% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) and 8.190% by weight of activated carbon (1.350% by weight with a water absorption rate of 2.6 and an average particle size of 75 μm or less) and 6.620% by weight of fillers (1.240% by weight of wood flour and 5.380% by weight of vermiculite). %, 2.020% by weight of super absorbent resin as a water-retaining material, 0.170% by weight of sodium tripolyphosphate, and 43.000% of 8% salt water (39.560% by weight of water and 3.440% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heat generating elements were produced in the same manner as in Example 1, except that 30.50 g of the obtained heat generating composition was sealed in the inner bag. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 2. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（実施例９）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉２７．０００重量％および還元鉄粉１８．０００重量％）を４５．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭５．９２５重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭１．０７５重量％）を７．０００重量％、充填剤（木粉１．０３０重量％およびバーミキュライト４．８６０重量％）を５．８９０重量％、保水材として高吸水性樹脂を１．９４０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水３６．８００重量％および食塩３．２００重量％）を４０．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を内袋に３０．５ｇ封入した以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表３に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図９に示す。 (Example 9)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 45.000% by weight of iron powder (27.000% by weight of cast iron powder and 18.000% by weight of reduced iron powder), 5.925% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) 7.000% by weight of activated carbon with a water absorption rate of 2.6 and 1.075% by weight of average particle size of 75 μm or less), and 5.890% by weight of fillers (1.030% by weight of wood flour and 4.860% by weight of vermiculite). %, 1.940% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 40.000% of 8% salt water (36.800% by weight of water and 3.200% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heat generating elements were produced in the same manner as in Example 1, except that 30.5 g of the obtained heat generating composition was sealed in the inner bag. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（比較例１）　
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉（鋳造鉄粉１７．７７３重量％および還元鉄粉３９．９５２重量％）を５７．７２５重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭２．４１３重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭２．０３３重量％）を４．４４６重量％、充填剤（木粉２．５９３重量％およびバーミキュライト３．１２４重量％）を５．７１７重量％、保水材として高吸水性樹脂を１．３０２重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水２８．１８９重量％および食塩２．４５１重量％）３０．６４０重量％を混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表３に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図１０に示す。 (Comparative example 1)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 57.725% by weight of iron powder (17.773% by weight of cast iron powder and 39.952% by weight of reduced iron powder), 2.413% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) and activated carbon with a water absorption rate of 2.6 and an average particle size of 75 μm or less (2.033% by weight) and 4.446% by weight of fillers (2.593% by weight of wood flour and 3.124% by weight of vermiculite) and 5.717% by weight of fillers (wood flour 2.593% and vermiculite 3.124% by weight). %, 1.302% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 8% salt water (28.189% by weight of water and 2.451% by weight of salt) 30.640% by weight % to prepare an exothermic composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（比較例２）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉（鋳造鉄粉１７．７７３重量％および還元鉄粉３９．９５２重量％）を５７．７２５重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭２．４１３重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭２．０３３重量％）を４．４４６重量％、充填剤（木粉２．５９３重量％およびバーミキュライト３．１２４重量％）を５．７１７重量％、保水材として高吸水性樹脂を１．３０２重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水２８．１８９重量％および食塩２．４５１重量％）３０．６４０重量％を混合し、発熱組成物を作製した。
　得られた発熱組成物３０．５ｇを内袋に封入した以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表３に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図１１に示す。 (Comparative example 2)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 57.725% by weight of iron powder (17.773% by weight of cast iron powder and 39.952% by weight of reduced iron powder), 2.413% by weight of activated carbon (water absorption rate of 4.2, activated carbon with average particle size of 75 μm or less) and activated carbon with a water absorption rate of 2.6 and an average particle size of 75 μm or less (2.033% by weight) and 4.446% by weight of fillers (2.593% by weight of wood flour and 3.124% by weight of vermiculite) and 5.717% by weight of fillers (wood flour 2.593% and vermiculite 3.124% by weight). %, 1.302% by weight of super absorbent resin as a water retaining material, 0.170% by weight of sodium tripolyphosphate, and 8% salt water (28.189% by weight of water and 2.451% by weight of salt) 30.640% by weight % to prepare an exothermic composition.
Five heating elements were produced in the same manner as in Example 1, except that 30.5 g of the obtained heat generating composition was sealed in the inner bag. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Further, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
（比較例３）
　発熱組成物の各成分を以下に示すように変更した以外は実施例１と同様にして、発熱組成物を作製した。すなわち、鉄粉末（鋳造鉄粉３０．０００重量％および還元鉄粉２０．０００重量％）を５０．０００重量％、活性炭（吸水率４．２、平均粒径７５μｍ以下の活性炭５．０００重量％および吸水率２．６、平均粒径７５μｍ以下の活性炭０．８００重量％）を５．８００重量％、充填剤（木粉０．８００重量％およびバーミキュライト４．３６０重量％）を５．１６０重量％、保水材として高吸水性樹脂を１．８７０重量％、トリポリリン酸ソーダを０．１７０重量％、および、８％塩水（水３４．０４０重量％および食塩２．９６０重量％）を３７．０００重量％混合し、発熱組成物を作製した。
　得られた発熱組成物を用いた以外は実施例１と同様にして５個の発熱体を作製した。得られた発熱体について、実施例１と同様にして、立上り時間、最高温度、水分残存率、温度４０℃以上を保持する持続時間を測定し、５個のサンプルの平均値によってＪＩＳ温度特性グラフ及び表を作成した。また、実施例１と同様にして、各強制劣化試験の試料について、水分減少量を測定し、水分残存率と鉄粉重量に対する残存水分の割合の平均値を求めた。この結果を表３に示す。また、強制劣化試験におけるＪＩＳ温度特性グラフを図１２に示す。 (Comparative example 3)
A heat generating composition was prepared in the same manner as in Example 1 except that each component of the heat generating composition was changed as shown below. That is, 50.000% by weight of iron powder (30.000% by weight of cast iron powder and 20.000% by weight of reduced iron powder), 5.000% by weight of activated carbon (activated carbon with water absorption rate of 4.2 and average particle size of 75 μm or less). and 5.800% by weight of activated carbon (0.800% by weight with water absorption rate of 2.6 and average particle size of 75 μm or less) and 5.160% by weight of fillers (0.800% by weight of wood flour and 4.360% by weight of vermiculite). %, 1.870% by weight of super absorbent resin as water retaining materials, 0.170% by weight of sodium tripolyphosphate, and 37.000% of 8% salt water (34.040% by weight of water and 2.960% by weight of salt). They were mixed in weight percent to prepare a heat generating composition.
Five heating elements were produced in the same manner as in Example 1 except that the obtained heating composition was used. Regarding the obtained heating element, the rise time, maximum temperature, moisture residual rate, and duration of maintaining the temperature at 40°C or higher were measured in the same manner as in Example 1, and the JIS temperature characteristic graph was calculated based on the average value of 5 samples. and created a table. Further, in the same manner as in Example 1, the amount of moisture loss was measured for each sample of the forced deterioration test, and the average value of the residual moisture rate and the ratio of residual moisture to the weight of iron powder was determined. The results are shown in Table 3. Furthermore, a JIS temperature characteristic graph in the forced deterioration test is shown in FIG.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000003
  
　以上の結果から明らかなように、実施例１～実施例９では、
（Ａ）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間、
と、
（Ｂ）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間（４年間保存後の発熱持続時間に相当）、
との差の絶対値が１時間以下であり、発熱持続時間の低下はほとんど認められなかった。一方、比較例１～比較例３では、（Ａ）と（Ｂ）の差の絶対値が２時間以上であり、経年劣化が認められた。
　また、実施例１～９では、（Ｂ）／（Ａ）が８０％以上であり、発熱持続時間の低下はほとんど認められなかった。一方、比較例１～３では、（Ｂ）／（Ａ）が４４％～７７％であり、経年劣化が認められた。 As is clear from the above results, in Examples 1 to 9,
(A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
and,
(B) Duration of heat generation at 40°C or higher in a heating element left in an environment with a room temperature of 50°C and a humidity of 40% for 4 weeks after manufacture (equivalent to the duration of heat generation after storage for 4 years),
The absolute value of the difference was less than 1 hour, and almost no decrease in fever duration was observed. On the other hand, in Comparative Examples 1 to 3, the absolute value of the difference between (A) and (B) was 2 hours or more, indicating deterioration over time.
Further, in Examples 1 to 9, (B)/(A) was 80% or more, and almost no decrease in heat generation duration was observed. On the other hand, in Comparative Examples 1 to 3, (B)/(A) was 44% to 77%, and deterioration over time was observed.
　実施例１～実施例９および比較例１～３について、粘着剤層（アクリル系粘着剤製）を作製して発熱体を作製したところ、上記結果と同様の結果が得られることが分かった。
  For Examples 1 to 9 and Comparative Examples 1 to 3, when heating elements were produced by producing adhesive layers (made of acrylic adhesive), it was found that results similar to those described above were obtained.

Claims (6)

  1. 　熱を供給するための発熱体であって、
    少なくとも外袋と、通気性の内袋とを有し、
    該内袋の内部には発熱組成物が封入されており、
    該発熱体の内袋内に封入された当初の発熱組成物が、少なくとも、鉄粉末、炭素成分、反応促進剤、保水剤、および水を含有し、
    該鉄粉末の含有量が発熱組成物中、１５重量％～４５重量％であり、
    当初の発熱組成物の水の含有量が、発熱組成物中、３５重量％～６０重量％であり、当初の発熱組成物全体で１００重量％とすることを特徴とする発熱体。     A heating element for supplying heat,
    It has at least an outer bag and a breathable inner bag,
    A heat-generating composition is sealed inside the inner bag,
    The initial heat generating composition sealed in the inner bag of the heating element contains at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water,
    The content of the iron powder is 15% to 45% by weight in the exothermic composition,
    A heat generating element characterized in that the initial water content of the heat generating composition is 35% to 60% by weight in the heat generating composition, and the total amount of water in the initial heat generating composition is 100% by weight.
  2. 　前記発熱体は、
    （Ａ）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間、
    に対する
    （Ｂ）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間、
    の比率が、（Ｂ）／（Ａ）≧８０％であることを特徴とする請求項１に記載の発熱体。     The heating element is
    (A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
    (B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being left for 4 weeks in an environment with a room temperature of 50°C and a humidity of 40%,
    The heating element according to claim 1, wherein the ratio of (B)/(A)≧80%.
  3. 　前記炭素成分が活性炭であり、該活性炭の平均粒径が１～１５０μｍであることを特徴とする請求項１または２に記載の発熱体。 The heating element according to claim 1 or 2, wherein the carbon component is activated carbon, and the activated carbon has an average particle size of 1 to 150 μm.
  4. 　前記発熱体は、
    （Ａ）製造直後の発熱体における、４０℃以上の発熱状態を保持する持続時間、
    と、
    （Ｂ）製造後、室温５０℃、湿度４０％の環境下に４週間放置した発熱体における、４０℃以上の発熱状態を保持する持続時間、
    との差の絶対値が１時間以内であることを特徴とする請求項１から３のいずれか1項に記載の発熱体。     The heating element is
    (A) Duration of time that the heating element maintains a heat generation state of 40°C or more immediately after manufacture,
    and,
    (B) The duration of time the heating element maintains a heat generation state of 40°C or higher after being manufactured for 4 weeks at a room temperature of 50°C and a humidity of 40%;
    4. The heating element according to claim 1, wherein the absolute value of the difference is within 1 hour.
  5. 　前記発熱体は、４０℃以上の発熱状態を保持する持続時間が、０．１～１２時間であることを特徴とする請求項１から４のいずれか1項に記載の発熱体。 The heating element according to any one of claims 1 to 4, wherein the heating element maintains a heat generation state of 40° C. or higher for a duration of 0.1 to 12 hours.
  6. 　熱を供給するための発熱体の経時劣化を防ぐ方法であって、
    　前記発熱体は、少なくとも外袋と、通気性の内袋とを有し、該内袋の内部には発熱組成物が封入されており、
    　該発熱体の内袋内に封入された当初の発熱組成物が、少なくとも、鉄粉末、炭素成分、反応促進剤、保水剤、および水を含有し、
    該鉄粉末の含有量を発熱組成物中、１５重量％～４５重量％とし、
    当初の発熱組成物の水の含有量を、発熱組成物中、３５重量％～６０重量％とし、当初の発熱組成物全体で１００重量％とすることを特徴とする発熱体の経時劣化を防ぐ方法。
    　     A method for preventing deterioration over time of a heating element for supplying heat, the method comprising:
    The heating element has at least an outer bag and a breathable inner bag, and a heat generating composition is sealed inside the inner bag,
    The initial heat generating composition sealed in the inner bag of the heating element contains at least iron powder, a carbon component, a reaction accelerator, a water retention agent, and water,
    The content of the iron powder is 15% to 45% by weight in the exothermic composition,
    Preventing deterioration over time of a heating element characterized by setting the water content of the initial heating composition to 35% to 60% by weight, and 100% by weight in the entire initial heating composition. Method.
PCT/JP2023/011760 2022-03-25 2023-03-24 Heat-generating body and heat-generating composition WO2023182487A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022050106A JP2023142957A (en) 2022-03-25 2022-03-25 Exothermic body and exothermic composition
JP2022-050106 2022-03-25

Publications (1)

Publication Number Publication Date
WO2023182487A1 true WO2023182487A1 (en) 2023-09-28

Family

ID=88101649

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/011760 WO2023182487A1 (en) 2022-03-25 2023-03-24 Heat-generating body and heat-generating composition

Country Status (2)

Country Link
JP (1) JP2023142957A (en)
WO (1) WO2023182487A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04130176A (en) * 1990-09-21 1992-05-01 Powder Tec Kk Packaged heat generating material
JPH10298542A (en) * 1997-04-25 1998-11-10 Kaihatsu Kogyo Kk Food-heating agent
JP2001137275A (en) * 1999-11-11 2001-05-22 Hisamitsu Pharmaceut Co Inc Skin-applicable exothermic sheet
JP2004208921A (en) * 2002-12-27 2004-07-29 Kao Corp Water vapor generator
JP2005319049A (en) * 2004-05-07 2005-11-17 Kao Corp Heating compact
JP2007090057A (en) * 2005-08-31 2007-04-12 Kao Corp Steam heating device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04130176A (en) * 1990-09-21 1992-05-01 Powder Tec Kk Packaged heat generating material
JPH10298542A (en) * 1997-04-25 1998-11-10 Kaihatsu Kogyo Kk Food-heating agent
JP2001137275A (en) * 1999-11-11 2001-05-22 Hisamitsu Pharmaceut Co Inc Skin-applicable exothermic sheet
JP2004208921A (en) * 2002-12-27 2004-07-29 Kao Corp Water vapor generator
JP2005319049A (en) * 2004-05-07 2005-11-17 Kao Corp Heating compact
JP2007090057A (en) * 2005-08-31 2007-04-12 Kao Corp Steam heating device

Also Published As

Publication number Publication date
JP2023142957A (en) 2023-10-06

Similar Documents

Publication Publication Date Title
RU2627152C2 (en) Heating element and warming tool using same
EP2120812B1 (en) A pressure sensitive adhesive composition comprising salt
JPS6220583A (en) Thermogenic agent composition
WO2019058892A1 (en) Method for generating chlorine dioxide gas, liquid composition, gel composition, and chlorine dioxide gas generating kit
WO2017188429A1 (en) Sheet for absorbing moisture
EP2800732A1 (en) Porous oxygen activated heater
JP2001212167A (en) Heating bag
US20050244629A1 (en) Heating element
WO2023182487A1 (en) Heat-generating body and heat-generating composition
EP3721984A1 (en) Moisture absorbent pack for vehicle lamp having improved durability
JPWO2014157726A1 (en) Exothermic composition and disposable body warmer using the same
JP5886398B1 (en) Rust prevention composition and rust prevention material using the same
JPS58132074A (en) Preparation of pyrogenic composition
JP2001089757A (en) Heat-generating composition and heating tool
WO2014157725A1 (en) Heat generating composition, and disposable body warmer using same
JP2007075432A (en) Deodorization sheet and deodorization method
JPH01270867A (en) Hydrous cooling member
JP2604686B2 (en) Method for controlling the amount of dissolved oxygen in water and equipment used therefor
JP2009082281A (en) Exothermic bag
JP2022102592A (en) Oxidizable metal powder for chemical body warmer, and chemical body warmer
JP2001212166A (en) Disposable body warmer
JP3319699B2 (en) Heating structure and method of manufacturing the same
JP2019059648A (en) Chlorine dioxide gas generating agent
JP2576646B2 (en) Oxygen absorbing sheet
WO2022210193A1 (en) Film used for outer bag for chemical body warmer

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23775080

Country of ref document: EP

Kind code of ref document: A1