Temperature control agent, heat-generating composition using the same, and heating material

Abstract

The present invention aims to provide a means for realizing temperature control of a thermal material (particularly control of the maximum heat generation temperature) at lower cost and more simply, which can be used instead of or in combination with conventional temperature control, and which prevents or reduces the decrease in heat generation temperature due to deterioration of the thermal material over time and the effects of storage at high temperatures, and a thermal material using the same. Another object of the present invention is to provide a more advanced temperature control means that can be used for thermal materials for medical use, and to provide an improved thermal material for medical use that is safer and more effective. One aspect of the present invention is a temperature control agent for controlling the maximum temperature of a thermal material containing a heat-generating composition that reacts with oxygen to generate heat, characterized in that the temperature control agent is in a particulate form that does not pass through a 60-mesh standard sieve, has a melting point of 35°C or higher and 65°C or lower, and contains one or more aliphatic compounds whose water solubility (g / 100mL) at 20°C is 5 or less.

Description

Technical Field

[0001] The present invention relates to a temperature controller used for manufacturing heat generating materials such as a chemical hand warmer (kairo) that generates heat by reacting with oxygen, a warm compress structure, a heat generating composition and a packaging material using the same, and a heat generating material using these.

Background Art

[0002] Heat generating materials using a heat generating composition that generates heat upon contact with oxygen or air are generally widely used as medical devices such as warm compresses for reducing pain by heat and heat generating devices for meridian stimulation, or as daily necessities such as kairos and other heating devices for cold protection.

[0003] The heat generating composition used in such heat generating materials most commonly contains metal powders such as iron powder, salts such as salt, water, and water retention agents such as activated carbon as constituent components, and generates heat by the heat of oxidation generated when the metal reacts with oxygen. Therefore, conventionally, by controlling the amount of oxygen inflow depending on the air permeability, moisture permeability, material, etc. of the air-permeable packaging material, particularly an air-permeable (porous) film, for the bag body that houses the heat generating composition, the heat generating characteristics have been adjusted so as to be within a desired range according to the purpose of the heat generating material.

[0004] What can be adjusted by such a method are the maximum temperature of heat generation, rise time, duration, etc., and the product is designed so that they are optimized when used under certain conditions. However, strictly managing the performance of the packaging material places a burden in terms of manufacturing cost. Furthermore, even if an air-permeable packaging material with high performance is used, if the actual air permeability during use is not as designed due to the usage mode or pinholes in the bag body, the originally planned performance may not be exhibited, or safety problems may occur.

[0005] For example, general disposable warmers are affected by changes in environmental temperature and the amount of air supplied to the warmer due to factors such as moving indoors and outdoors or putting on and taking off coats, and the heat generation temperature may vary. Such warmers are often prohibited from being used at bedtime. This is because covering with a futon or the like reduces heat dissipation and causes a temperature rise, resulting in a risk of low-temperature burns. In addition, disposable warmers for shoes are intended to be used in an environment where air inflow is restricted and are manufactured using a packaging material with relatively high breathability. However, during actual use, temperature variations may occur because the amount of air supplied varies depending on the type of shoes, or there may be a sudden temperature rise when the shoes are removed.

[0006] Similar problems also exist in heat materials for medical applications that require more accurate temperature control. For example, a transdermal absorption type medical poultice that combines a heating element and a drug is touted for merits such as increased efficacy and reduced drug dosage through enhanced transdermal absorption by heat. However, as described above, in conventional temperature regulation, the stability of the heat generation temperature is incomplete, so in reality, there is a problem that the drug dosage is not stable due to unstable temperature. Furthermore, as an alternative to moxibustion that does not use fire, there is a need for a heating element for short-term use. However, since moxibustion uses a high-temperature zone, the risk is high with disposable warmer technology lacking in temperature stability, and it has not been widely spread.

[0007] Therefore, the present inventors have found that by mixing a specific temperature control agent into a heat generating composition or the packaging material of a bag containing the same, the temperature stability of the heat material can be enhanced (Patent Document 3).

[0008] In addition, the heat material is composed of relatively stable components and can be stored at room temperature for a certain period while blocking oxygen. However, when exposed to temperature changes during storage, especially in a high-temperature environment, the storage stability decreases and the maximum temperature may drop. This aspect has not been studied for heat materials using a temperature control agent.

Prior Art Documents

Patent Documents

[0009] Patent Document 1 International Publication Gazette WO1999 / 000078 Patent Document 2 Japanese Unexamined Patent Application Publication No. 2001-170099 Patent Document 3 International Publication Gazette WO2016 / 063815 Summary of the Invention Problems to be Solved by the Invention

[0010] The present invention aims to provide a means for realizing temperature control of a heating material (particularly control of the maximum heat generation temperature) at a lower cost and simply, which can be used instead of or in combination with conventional temperature control by controlling the supply amount of oxygen or air with a breathable film or the like, and preventing or reducing a decrease in the heat generation temperature due to the aging deterioration of the heating material and the influence of storage at high temperatures, and a heating material using the same. Further, the present invention aims to provide a more advanced temperature control means that can be used for a heating material for medical use, and an improved heating material for medical use with higher safety and effectiveness. Means for Solving the Problems

[0011] According to the present invention, (1) A temperature control agent for controlling the maximum temperature of a heating material containing an exothermic composition that generates heat by reacting with oxygen, which is in a particulate form that does not pass through a 60-mesh standard sieve (reference dimension according to JIS Z8801-1: 250 μm), has a melting point of 35°C or higher and 65°C or lower, and contains one or more aliphatic compounds having a water solubility (g / 100 mL) of 5 or less at 20°C; (2) The temperature control agent according to (1) above, wherein the aliphatic compound is in a particulate form that passes through a 16-mesh standard sieve (reference dimension according to JIS Z8801-1: 1000 μm); 〔3〕The temperature control agent according to the above-mentioned 〔1〕 or 〔2〕, which contains one or more compounds selected from the group consisting of higher α-olefin polymers, paraffin waxes, myristyl myristate, polyester polyols, and polyoxyethylene fatty acid diesters; 〔4〕An exothermic composition containing metal powder, salts, water, and activated carbon and reacting with oxygen to generate heat, further characterized by containing the temperature control agent according to any one of the above-mentioned 〔1〕 to 〔3〕; 〔5〕The exothermic composition according to the above-mentioned 〔3〕, wherein the exothermic composition is in a solid form; 〔6〕A warming material including at least a bag or a container at least partially containing the exothermic composition according to the above-mentioned 〔4〕 or 〔5〕 and having air permeability; 〔7〕The warming material according to the above-mentioned 〔6〕, wherein at least the bag or the container is housed in an airtight outer bag that substantially blocks oxygen; 〔8〕The warming material according to the above-mentioned 〔6〕 or 〔7〕, which is used as either a disposable warmer or a medical device; 〔9〕The warming material according to the above-mentioned 〔8〕, wherein the medical device is either a warm compress or a warming device for meridian stimulation; is provided.

Advantages of the Invention

[0012] According to the present invention, in the warming material, a simple, low-cost, and reliable temperature control means that can be used instead of or in addition to temperature control by a breathable film is provided. The maximum exothermic temperature is stable even after long-term storage, and a highly safe warming material with better temperature stability can be realized. In particular, the present invention is suitable for, for example, emergency long-term storage, etc., and provides a warming material with a low risk of low-temperature burns even when used during sleep. Specifically, for example, - A warming material that can be safely used even at bedtime, with a reduced risk of low-temperature burns due to covering with a futon; - A highly safe disposable warmer for shoes that can obtain stable heat generation regardless of the type of shoes and does not cause a rapid temperature rise when the shoes are taken off; - A transdermal absorption type medical warm compress with high temperature stability, high safety, and high effectiveness; - A heating material as a heat-generating tool for meridian stimulation such as moxibustion that can be safely used by controlling the maximum temperature even in a high-temperature zone and the like are provided.

Brief Description of the Drawings

[0013]

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Figure 7

Embodiments for Carrying Out the Invention

[0014] Temperature control agent The temperature control agent of the present invention is characterized by containing one or more aliphatic compounds having a melting point of 35°C or higher and 65°C or lower and a water solubility (g / 100 mL) of 5 or less at 20°C. The above solubility is preferably 3 or less, more preferably 1 or less. The preferred melting point varies depending on the use of the heat-generating material, but generally is preferably 38°C or higher and 60°C or lower. In the present specification, the "aliphatic compound" means an organic compound in which all carbon atoms in the molecule are connected in a linear chain, or an organic compound having a branched structure in the carbon atom chain and not containing a cyclic structure, and includes those having a cyclic structure containing oxygen or nitrogen, such as anhydrides of chain dicarboxylic acids, imides, lactones of oxyacids, and cyclic ethers, which have a close relationship with the parent chain compound and can easily open the ring to become a chain compound.

[0015] Examples of aliphatic compounds having such properties include higher α-olefin polymers, various paraffin waxes such as vegetable, animal, or petroleum-based paraffin waxes, myristyl myristate, polyester polyols, polyoxyethylene fatty acid diesters, etc., and they can be selected from these. In this specification, the higher α-olefin polymer refers to a copolymer of two or more α-olefins having 10 to 35 carbon atoms, or a copolymer of one or more α-olefins having 10 to 35 carbon atoms and one or more other olefins. That is, the higher α-olefin polymer is a copolymer of two or more α-olefins having 10 to 35 carbon atoms, or a copolymer of one or more α-olefins having 10 to 35 carbon atoms and one or more other olefins.

[0016] The higher α-olefin polymer used in the present invention may be a main-chain crystalline polyolefin in which the main chain is folded and crystallized, but a side-chain crystalline polyolefin having a certain long-chain α-olefin in the side chain is preferred. The side-chain crystalline polyolefin has a sharp melting behavior. When not melted, it is not sticky, which is convenient. Such side-chain crystalline polyolefins are manufactured and sold under trade names such as "HS Crystal" (Toyokoku Oil Co., Ltd.) and are commercially available. Similarly, paraffin wax (e.g., Nippon Seiro Co., Ltd.), myristyl myristate (e.g., Croda Japan), polyester polyol (e.g., DIC, Toyokoku Oil Co., Ltd.), polyoxyethylene fatty acid diester (e.g., Sanyo Chemical Industries), and higher α-olefin polymers are also commercially available respectively.

[0017] The melting point is measured as follows using a differential scanning calorimeter. 5 mg to 15 mg of the sample is placed into an aluminum (Al) container, covered with an Al crimp cover on top, and sealed by applying a certain pressure. Using the Al container + crimp cover as the reference, the temperature is raised from -50 °C below the estimated melting point to +30 °C above the estimated melting point at a heating rate of 5 °C / min. After holding for 5 minutes, it is cooled at the same rate and held at the estimated melting point -50 °C for 5 minutes. This is repeated twice, and the DSC curve of the second cycle (2nd-run) is measured. The melting point is read from the main endothermic peak that appears in the DSC curve due to the endotherm accompanying the melting of the sample.

[0018] The water solubility at 20 °C can be measured by dissolving the sample in 100 g (100 ml) of water at 20 °C and reading the mass of the limiting amount (the maximum amount dissolved) at which it no longer dissolves.

[0019] The aliphatic compound contained in the temperature control agent of the present invention can be in the form of pellets, powder, blocks, etc. at normal temperature. However, those in the form of pellets, blocks, etc. are used after being pulverized (for example, cryogenic pulverization) before mixing. After pulverization, it is controlled so that the particle size falls within a predetermined range. In this specification, the size of the particles of the aliphatic compound is indicated by classification using a standard sieve (Tyler sieve). The size of the mesh of the sieve is generally indicated by "mesh" or "μm" (the reference dimension (μm) of the mesh opening of a metal sieve in JIS Z8801-1 (2006), also called the nominal size), and their corresponding relationships are well-known. For the temperature control agent of the present invention, commercially available aliphatic compounds can be appropriately selected and used as they are, or they can be sieved (classified) into particles that pass through various standard sieves and particles that do not pass through, and appropriately selected and blended so as to exhibit a desired heat generation pattern. The aliphatic compound contained in the temperature control agent of the present invention needs to be in a particulate form that does not pass through a 60-mesh standard sieve (mesh opening 250 μm). It is desirable for the aliphatic compound to further contain a particulate form that passes through a 16-mesh standard sieve (mesh opening 1000 μm). As long as the particle size is within this range, it can be completely uniform, and there are no particular restrictions on the distribution. Also, the shape of the particles is not limited.

[0020] In this specification, "not passing through" a sieve with a certain mesh size means that 60% or more of the whole does not pass through the sieve, preferably 80% or more, more preferably 90% or more, and most preferably 100%. Similarly, "passing through" a sieve with a certain mesh size means that 60% or more of the whole passes through the sieve, preferably 80% or more, more preferably 90% or more, and most preferably 100%.

[0021] The mechanism by which the stability of the heat generation characteristics occurs by using the temperature control agent of the present invention is not restricted by a specific theory, but is generally considered as follows. When the temperature control agent is added to the heat generating composition, when the heat generation temperature reaches near the melting point of the temperature control agent, the temperature control agent melts and covers the periphery of the iron powder, thereby inhibiting the oxidation reaction and suppressing the temperature rise. Also, when using particles that do not pass through a 60-mesh standard sieve (aperture 250 μm), compared with the case of using finer particles, it is considered that they are less affected by changes in the ambient temperature during storage, and accidental melting of the temperature control agent (and decrease in the maximum heat generation temperature) is less likely to occur. On the other hand, particles that do not pass through a 16-mesh standard sieve (aperture 1000 μm) take a long time to dissolve and tend to delay the reaction stop, so it is considered that the maximum temperature will be high. In particular, when used in a heat generating composition in the form of a tablet, it is likely to be biased in the dispersed state, and therefore, it is likely that there will be variations in the time to reach the maximum temperature.

[0022] Note that the maximum temperature and heat generation pattern to be achieved vary depending on the use of the heating material. Therefore, the type and content of the temperature control agent are selected so as to achieve the required heat generation performance.

[0023] For example, a warm compress type of kairo that is directly applied to the skin preferably has a heat generation temperature around 40°C. However, if it exceeds 43°C, protein denaturation is said to occur and the risk of low-temperature burns increases. Therefore, it is designed not to exceed 43°C. If the heat generation temperature may reach 43°C or higher, it is desirable to promptly suppress the temperature rise to around the suitable 40°C. On the other hand, it is not desirable for the temperature to continue to drop after suppression because the thermal effect is reduced. Also, in the case of a warm compress type of kairo that is directly applied to the skin and is to be applied to the delicate abdomen of women for the purpose of relieving menstrual pain, a mild heat generation of 40°C or lower is preferred.

[0024] On the other hand, a disposable type of kairo that is attached to clothing is used at around a maximum temperature of 55°C because the skin is protected by the clothing. In the case of a disposable kairo for replacing moxibustion, although it is used at a relatively high temperature for a short time, since it directly touches the skin, a design not exceeding around 55°C is desirable. And in the case of a moxibustion substitute, it is desirable for the temperature to drop promptly after suppressing the temperature rise.

[0025] Thus, since there are maximum temperatures and heat generation patterns suitable for each of various heat generating materials, in order to achieve them, as a temperature control agent, one or more aliphatic compounds having a melting point close to the desired maximum temperature (for example, a melting point of - about 20°C to + about 10°C of the maximum temperature (that is, the maximum temperature is within + about 20°C to - 10°C from the melting point), preferably a melting point with a difference of ± about 8°C or less from the maximum temperature, more preferably a melting point with a difference of ± about 5°C or less from the maximum temperature) can be appropriately selected, and the addition amount, addition method, addition of optional components, etc. can be designed. For example, in order to control the maximum temperature to about 55°C, α-olefin with a melting point of 58°C can be selected.

[0026] Heat generating composition The heat generating composition of the present invention contains at least metal powder, salts, water, and activated carbon, and further contains the temperature control agent of the present invention. The temperature control agent is as described above.

[0027] As the metal powder, iron powder is generally used, but any other powder that generates heat upon oxidation may also be used. As the salts, inorganic salts such as sodium chloride, potassium chloride, and magnesium chloride are generally used. The exothermic composition of the present invention contains activated carbon, but may further contain water retention agents other than activated carbon (such as water-absorbing polymers, vermiculite, sawdust, silica-based substances, etc.). Further, various other conventionally known components can be added as necessary.

[0028] Examples of the compounding ratios of these components include, for example, those composed of 35 to 80% by weight of iron, 1 to 20% by weight of activated carbon, 1 to 10% by weight of salts, 5 to 45% by weight of water, and 0 to 45% by weight of water retention agents other than activated carbon, with the weight of the exothermic composition being 100%. In the exothermic composition of the present invention, 30 to 70% by weight of iron, 1 to 15% by weight of activated carbon, 1 to 5% by weight of salts, 20 to 30% by weight of water, 1 to 25% by weight of water retention agents other than activated carbon, and 5 to 30 parts by weight, preferably 10 to 30 parts by weight of a shaping agent are preferred. The compounding amount of the temperature control agent can be appropriately selected according to the purpose of use of the heating material and the maximum temperature to be achieved as described above. For example, 3 to 40 parts by weight, preferably 3 to 30 parts by weight of the temperature control agent of the present invention is added to and mixed with 100 parts by weight of the exothermic composition having such a composition.

[0029] The heat-generating composition can be produced by mixing the above essential components and optional components selected as needed by a known method, under low-oxygen or oxygen-free conditions when adding salts and water in advance. The heat-generating composition may be in powder form, and it may be further processed by a known method, for example, formed into a cube shape by tableting, a sheet shape by rolling, etc. When forming the heat-generating composition into a solid form, binders such as cellulose (for example, crystalline cellulose), lactose, starch, dextrin, sucrose ester, Teflon (registered trademark), polyethylene glycol, carboxymethyl cellulose, etc. may be added. For example, to form a tablet-shaped solid by tableting, by adding a binder such as crystalline cellulose in an amount of 10 parts by weight or more, preferably in the range of 10 to 30 parts by weight, based on 100 parts by weight of the heat-generating composition, a tablet having a desired appropriate hardness can be obtained. Such a solid heat-generating composition is preferable for preventing sealing failure due to powder adhesion to the sealing portion of the bag or container during enclosure and eliminating variations in the heat generation temperature. Regarding the heat-generating composition, salts may be mixed simultaneously at the time of mixing the powder raw materials, or may be added as salt water.

[0030] For the heat-generating composition of the present invention containing such a temperature control agent, by the JIS S4100 heat generation test, the temperature change when reacting with oxygen in the air through a breathable packaging material (for example, 17,000 to 18,000 seconds / 100 cc (JIS P8117 method (Gurley method))) used for the bag for containing the heat-generating composition can be measured over time to confirm whether the desired maximum temperature is achieved. In addition, the heat generation test conducted for this purpose may be carried out by appropriately modifying the experimental conditions so as to reflect the assumed actual use state.

[0031] Packaging material The heat-generating composition is filled into a bag for containing the heat-generating composition. The bag filled with this heat-generating composition can also be used as it is as a heating material (for example, a so-called non-sticking type kairo, etc.). Generally, the bag for containing the heat-generating composition is formed so that at least a part thereof has air permeability.

[0032] Since the air-permeable packaging material that constitutes the bag for containing the heat-generating composition can change the heat-generating characteristics of the heat-generating material (such as the heat-up rate of heat generation, the duration of heat generation, and the heat transfer property to the object to be heated such as the human body and clothing) depending on its selection, known ones can be appropriately selected and used so that they are within the desired range according to the purpose of use.

[0033] For general warmers for the human body, etc., an air-permeable packaging material with an air permeability of 10,000 - 40,000 seconds / 100 cc (JIS P8117) is used. Also, for example, for warmers for shoes, 2,000 - 7,000 seconds / 100 cc is used. Therefore, generally, as the air-permeable packaging material for the bag for containing the heat-generating composition, a packaging material with an air permeability of 2,000 - 40,000 seconds / 100 cc is used. In the case of a heat-generating material designed to be used at a high temperature and / or for a short time like a heat-generating device for meridian stimulation, a packaging material with an air permeability of 0 - 10,000 seconds / 100 cc can be used. By using the temperature control agent of the present invention, precise air permeability management becomes unnecessary depending on the use of the heat-generating material, and the allowable range of the air-permeable packaging material that can be used is widened.

[0034] In the present invention, the air-permeable packaging material used for the bag body may be a film or sheet that has air permeability entirely or partially. Generally, as the air-permeable packaging material, a single-layer or laminated porous film or sheet is used alone, or in combination with a woven fabric or non-woven fabric, etc., or a single-layer or laminated non-porous film or sheet is used alone, or a combination with a woven fabric or non-woven fabric, etc. with pinholes opened is used. In the present invention, "film" mainly refers to a single body (including single-layer and laminated; the same applies hereinafter) or a relatively thin one, and "sheet" mainly refers to a single body or a laminate of two or more single bodies or a relatively thick one, but they are not strictly distinguished.

[0035] As the resin constituting the film, generally, thermoplastic synthetic resins and the like are used. Specifically, polyethylene, polypropylene, polyester, polyamide, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, ethylene-vinyl acetate copolymer, polycarbonate, etc. are preferably used alone or in combination. It can be appropriately selected according to the purpose and also in accordance with the appropriate required calorific value, temperature, heat-generating composition to be used, etc.

[0036] In the present invention, as the breathable film or sheet, a stretched film, preferably a stretched porous film or a sheet containing the same is preferably used. The stretched porous film generally contains an inorganic filler, and air permeability is exhibited by forming continuous pores by stretching, and the air permeability can be controlled by controlling the pore diameter and the like.

[0037] When laminating, it is usually carried out by a laminating method but is not limited thereto. Any conventionally known method can be applied for lamination. For example, a method of laminating with heat bonding or an adhesive such as a hot melt adhesive or an acrylic or urethane adhesive may be used, and it may be a full surface bonding or a partial bonding to maintain flexibility. Preferably, the curtain spray method or the dry lamination method is used.

[0038] The non-woven fabric is used in the breathable packaging material from the viewpoints of reinforcing the packaging material strength, improving the mechanical properties, etc. As the non-woven fabric that may be laminated with the above film, those conventionally used in technical fields such as heating elements and medical warming appliances can be preferably used. Examples include those containing artificial fibers such as nylon, vinylon, polyester, rayon, acetate, acrylic, polyethylene, polypropylene, polyvinyl chloride, and natural fibers such as cotton, hemp, and silk, and non-woven fabrics in the form of spunbond, thermal bond, spunlace, etc. The basis weight of the non-woven fabric varies depending on the bulkiness due to the specific gravity of the non-woven fabric material and the difference in the entanglement method, but generally about 10 g / m 2 ~ about 200 g / m 2 is suitable, especially about 20 g / m2 ~about 100 g / m 2 is preferred.

[0039] In particular, a breathable sheet in which a non-woven fabric such as nylon or polyester fiber is laminated on a stretched porous film of a thermoplastic synthetic resin is generally widely used.

[0040] A part of the bag body, for example, the back packaging material of a flat bag body, may be the above-mentioned breathable packaging material or a non-breathable packaging material. The non-breathable packaging material can be a single-layer or laminated film or sheet of the above-mentioned resin, and there is no particular limitation regarding the material, thickness, configuration, etc., as long as it is suitable for forming the heat-generating composition-containing bag body.

[0041] The bag body for containing the heat-generating composition can be manufactured by adhering the peripheral portion by a method usually used in this technical field using the above-mentioned packaging material. The heating material can be basically manufactured by enclosing the heat-generating composition of the present invention in this bag body. Generally, the manufacture of the bag body and the manufacture of the heating material are continuous. First, the peripheral portion of the stacked packaging material is adhered with a heat seal or an adhesive leaving a part, the heat-generating composition is put in from the open part, and then this opening is also adhered to enclose the heat-generating composition.

[0042] Also, for those with a narrow application area and / or a short usage time like moxibustion devices, instead of a flat bag body, they may be housed and used in a container having a thickness of about several mm to several cm. Also in this case, for the manufacture of the lid (top material) and the container body, various packaging materials of the above-mentioned types can be appropriately used. For example, the top material (Fig. 7) can optionally contain layers such as a sealant material (3a), a non-woven fabric (3b), an adhesive (3c), and a release paper (3d). As a specific example, in order from 3a, LLDPE (30 μm) / PET spunlace non-woven fabric (30 g / m 2)It can be a / SIS-based hot melt adhesive / PET separator (38 μm). As described above, in the case of using high temperature and / or short-time heat generation such as in moxibustion devices, a packaging material with very high air permeability can be used, so a non-woven fabric can be used alone for the top material and / or the container body.

[0043] Thermal material The heating material can be only the bag body filled with the heat-generating composition of the present invention as described above (for example, a disposable warmer that is not pasted) or only the container (for example, a moxibustion device), but additional elements can be added as necessary. These various elements are known and may be integrated into the bag body, or may be provided as separate members to be combined during use. Examples of additional elements include various fixing means and various parts to be combined during use (for example, containers containing fragrances or drugs, sheets containing water or cosmetics, etc., used according to the application of the heating material). Examples of fixing means include, for example, an adhesive layer or a poultice layer formed on a part of the surface of the bag body or container for accommodating the heat-generating composition so that the heating material can be attached, a band-shaped member for winding around the object to be heated and fixing it, a mask, a supporter, a wristband, etc. provided with a pocket for accommodating the heat-generating material. Also, for the purpose of temperature adjustment, etc., a pedestal may be provided between the container and the adhesive layer to adjust the distance and / or space between the application site and the heating material. Note that the heating material of the present invention may be used in combination with various drugs or fragrances such as camphor and menthol in the adhesive layer, the poultice layer, other components, or the heat-generating composition, and / or the packaging material or container. For example, as heat receptors, capsicum tincture, capsicum extract, capsicum powder, ginger tincture, ginger extract, ginger powder, wild ginger tincture, wild ginger extract, wild ginger powder, capsaicin, capsaicin derivatives, vanillyl butyl ether, vanillyl alkyl ether, nonyl vanillylamide, etc. can be added to the adhesive. As cold receptors, l-menthol, mint, dl-camphor, peppermint oil, thymol, menthyl ethylamide oxalate, etc. can be added to the adhesive.

[0044] A bag or container containing at least a heat - generating composition of a heat - generating material is stored until use while being sealed in an outer bag that blocks oxygen. Such outer bags are also known. As an outer bag for long - term storage, those containing an aluminum layer with low oxygen permeability to reduce the oxidation reaction of iron during storage and low water - vapor permeability to reduce the release of water vapor from the outer bag are particularly preferred.

Examples

[0045] <Manufacture of Moxibustion Devices> A moxibustion device composed of a container body (2) containing a heat - generating composition tablet (1) and a top material (3), similar to the example shown in Fig. 7, was manufactured as follows. As raw materials for the heat - generating composition, iron powder (Powdertech Co., Ltd., reduced iron powder "RDH - 3M"), activated carbon (Osaka Gas Chemical Co., Ltd., wood powder activated carbon "Shirasagi S5"), water - absorbent polymer (Sanyo Chemical Industries, Ltd., polyacrylic acid - based resin "ST - 500D"), crystalline cellulose (Asahi Kasei Chemicals Corporation, crystalline cellulose "Ceolus TG - 101"), salt (Nippon Seikai Co., Ltd., powder salt "EF - 300") and aliphatic compounds (α - olefin: Toyokuni Oil Co., Ltd., "HS Crystal - 6100", paraffin wax: Nippon Seiro Co., Ltd., "SP - 0145") described below were used. The composition of the heat - generating composition was 45 parts of iron powder, 3.5 parts of activated carbon, 5 parts of water - absorbent polymer, 20 parts of crystalline cellulose, 3.5 parts of salt, and 25 parts of aliphatic compound as a temperature - controlling agent ("parts" are all parts by weight).

[0046] The pulverization and sieving of the aliphatic compound were carried out as follows. Each aliphatic compound melted at 100°C in a low - temperature dryer of Isuzu Motors, Ltd. was poured onto a PET film in a plate shape with a thickness of about 2 mm and cooled to room temperature. The completely solidified plate was manually roughly pulverized into about 10 - mm squares. This roughly pulverized material was pulverized with a stainless - steel coffee mill (product number HG6063, sold by Unox Co., Ltd.). The pulverized product was manually sieved with a JIS - standard stainless - steel sieve (Tokyo Screen Co., Ltd., frame size diameter 200×60 mm, specification JIS Z8801 - 1:2000) to obtain a test sample of the temperature - controlling agent.

[0047] First, considering the bulk specific gravity and particle size, cellulose, aliphatic compounds, water-absorbing polymers, activated carbon, salts, and iron were weighed and added to a beaker in this order. Stir thoroughly with a medicine spoon to eliminate uneven distribution of each raw material. 2 g of this mixed raw material was weighed and tableted using the "Tablet Press Quick Mini FY-TQM-30" of Fuji Pharmaceutical Machinery Co., Ltd. (tableting pressure: 15 KN). A pushing die with a diameter of 16.9 mm and a receiving die with an inner diameter of 17 mm were used to produce cylindrical tablets with a diameter of 17 mm and a thickness of 7 mm.

[0048] The container for accommodating the heat-generating composition tablets was manufactured as follows. First, a wooden prototype mold (upper: cylindrical rod, lower: receiving wooden mold with holes) was prepared, and the pushing surface of the cylindrical rod was heated to 200 °C using a laboratory hot stirrer or hot plate. The formable non-woven fabric (Asahi Kasei Corporation, thermoformable non-woven fabric Smash "Y15200 200 g / m 2 ") placed in the receiving wooden mold was pressed with the heated rod to produce a cup-shaped molded product.

[0049] The tablets were placed in the formed non-woven fabric container body, and a top material (OPP 20 μm / LLDPE 30 μm (Toho Kako Co., Ltd.)) was attached to the upper part of the container using a household iron. 0.8 g of water was added to 2 g of the tablets using a syringe from the top material. It was sealed in an airtight outer bag (PET 12 μm / aluminum foil 7 μm / LLDPE 50 μm (Toho Kako Co., Ltd.)).

[0050] However, when paraffin wax was used, a pushing die with a diameter of 13.9 mm and a receiving die with an inner diameter of 14 mm were used to produce cylindrical tablets with a diameter of 14 mm and a thickness of 4 mm (1 g tablets). 0.3 g of water was added to 1 g of the tablets.

[0051] <Measurement of Melting Point and Solubility> The melting points of the respective aliphatic compounds were measured using a differential scanning calorimeter. As the measuring apparatus, a differential scanning calorimeter (DSC6220, all of the above measuring instruments are manufactured by Seiko Instruments Inc.) connected to a fully automatic cooling unit and an analysis system (EXSTAR6000 Thermal Analysis Rheology System, software is DSC Muse measurement software and DSC Muse standard analysis software) was used. As the sample containers, an open-type sample container made of Al, φ5.2 H2.5 (50 μl), and an open-type sample container made of Al (crimp cover) were used.

[0052] 5 mg to 15 mg of the sample was put into the Al container, covered with an Al-made crimp cover thereon, and sealed by applying a certain pressure. Using the Al container + crimp cover as a reference, the temperature was raised from -50°C of the estimated melting point to +30°C of the estimated melting point at a heating rate of 5°C / min. After holding for 5 minutes, it was cooled at the same rate and held at the estimated melting point of -50°C for 5 minutes. This was repeated twice, and the DSC curve of the second cycle (2nd-run) was measured. The melting point was determined from the endothermic peak that appeared in the DSC curve due to the endotherm accompanying the melting of the sample as described above.

[0053] The solubility in water of the powder of each aliphatic compound was measured by dissolving it in 100 g (100 ml) of water at 20°C and reading the mass of the limiting amount at which it no longer dissolved.

[0054] The melting points were 57°C for α-olefin (melting point 58°C), 59.5°C for α-olefin (melting point 62°C), and 62.3°C for paraffin wax. The solubility was less than 1 g / 100 ml in all cases.

[0055] The storage test was carried out at 50°C and a humidity of 35% using Advantec Toyo Co., Ltd.'s low-temperature constant temperature and humidity chamber THE051FA. Storage at 50°C for 2 weeks is equivalent to storage at room temperature for 1 year. Similarly, storage at 50°C for 4 weeks is considered equivalent to 2 years at room temperature, and 6 weeks is equivalent to 3 years. The temperature setting of 50°C was considered in view of the conversion with room temperature in the Arrhenius plot, warehouse storage, and sea container transportation.

[0056] <Heat generation test of moxibustion device> The heat generation test was conducted in accordance with the method of JIS S4100 "Disposable boilers". Under the conditions of an ambient temperature of 20 ± 1°C, a wind speed of 0.5 m / s or less (calm state), an ambient humidity of 55 - 70%, and a temperature of 30 ± 1°C in the heating section of a heating device consisting of a heater and a circulation type constant temperature water tank. Since the moxibustion device is directly attached to the skin during use, it was directly attached to the surface of the heater and measured.

[0057] The heat generation test was carried out in a constant temperature chamber at room temperature of 20°C and humidity of 65%. A tank-shaped heater of W615 × D410 × H60 mm (using an 8 mm thick vinyl chloride plate) installed in the chamber and a circulation type constant temperature water tank installed together were used to circulate hot water at 8 L / min. After controlling the surface temperature of the heater (vinyl chloride plate) to 30°C, the moxibustion device sample was attached to the vinyl chloride plate on the surface of the heater with the container body facing down and a temperature measuring sensor attached to the center of the bottom surface with double-sided tape. (The temperature measuring instrument was the Chino Graphic Recorder KR2S00 of Chino Corporation, and the sensor was Anritsu Corporation, "ST-22E-005").

[0058] The results are shown in Figs. 1 - 6.

[0059] From the above results, it was clarified that the heating material using the heat generating composition containing the temperature control agent of the present invention is hardly affected by long-term storage with respect to the maximum heat generation temperature. Therefore, the heating material using the heat generating composition containing the temperature control material of the present invention has high temperature stability and high safety, and can maintain the designed heat generation performance for a long time.

[0060] This application is based on the Japanese patent application filed on February 5, 2018, Japanese Patent Application No. 2018-018047, and all the contents described in the specification and claims of Japanese Patent Application No. 2018-018047 are incorporated herein.

Explanation of reference numerals

[0061] 1 Heat generating composition 2 Container (body) 3 Top material 3a Sealing material 3b Non-woven fabric 3c Adhesive 3d Release paper

Claims

1. An exothermic composition that reacts with oxygen to generate heat, containing metal powder, salts, water, activated carbon, and a binder, and further containing a temperature controller for controlling the maximum temperature of a heating material containing the exothermic composition, which does not pass through a 60-mesh standard sieve (reference dimension according to JIS Z8801-1: 250 μm) and passes through a 16-mesh standard sieve (reference dimension according to JIS Z8801-1: 1000 μm), has a melting point of 35°C or higher and 65°C or lower, and a water solubility (g / 100 mL) of 5 or less at 20°C, and contains one or more aliphatic compounds selected from the group consisting of higher α-olefin polymers, paraffin waxes, myristyl myristate, polyester polyols, and polyoxyethylene fatty acid diesters, and the exothermic composition is obtained by adding water or brine to a molded article containing powder raw materials characterizes the exothermic composition (wherein the metal powder, the salts, the activated carbon, the binder, and the temperature controller are different components from each other).

2. The exothermic composition according to Claim 1, wherein the temperature controller is a higher α-olefin polymer or paraffin wax.

3. The exothermic composition according to Claim 1 or 2, wherein the molded article is a molded article by tableting or rolling.

4. A heating material including a bag or container at least a part of which is breathable and contains the exothermic composition according to any one of Claims 1 to 3.

5. The heating material according to Claim 4, wherein at least the bag or container is housed in an airtight outer bag that substantially blocks oxygen.

6. The heating material according to Claim 4 or 5, which is used as either a disposable warmer or a medical device.

7. The heating material according to Claim 6, wherein the medical device is either a warm compress or a heat applicator for meridian stimulation.

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