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

Abstract

To provide a means that realizes a temperature control (especially control of a maximum exothermic temperature) of a warming material at lower cost and conveniently, usable in place of a conventional temperature control, or in combination therewith, and prevents or reduces a decrease of an exothermic temperature due to temporal deterioration and an influence under high temperature storage of the warming material, a warming material therewith, further, a high degree of temperature control means usable for the warming material of a medical usage, and a warming material for improved medical usage having high safety and efficacy.SOLUTION: A method of manufacturing a temperature control agent for controlling a maximum temperature of a warming material containing an exothermic composition that generates heat by reacting with oxygen comprises sieving aliphatic compounds having a melting point of 35°C or more and 65°C or less and a water solubility (g / 100 mL) at 20°C of 5 or less into one passing through a 16-mesh standard sieve (standard size according to JIS Z8801-1: 1000 μm) and the other one not passing through a 60-mesh standard sieve (standard size according to JIS Z8801-1: 250 μm) to obtain powder.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a temperature control agent used in the manufacture of thermal materials such as chemical hand warmers (hand warmers) that generate heat by reacting with oxygen and hot compress structures, a heat-generating composition and packaging material using the same, and thermal materials using these. [Background technology]

[0002] Heat-generating materials using heat-generating compositions that generate heat upon contact with oxygen or air are widely used in medical devices such as hot compresses and meridian-stimulating heating devices for alleviating pain through heat, and in everyday items such as body warmers and other heating devices for protection against the cold.

[0003] The heat-generating compositions used in such heating materials most commonly contain metal powders such as iron powder, salts such as table salt, water, and moisture-retaining agents such as activated carbon as constituent ingredients, and generate heat through the heat of oxidation produced when the metal reacts with oxygen. Therefore, heat-generating properties have traditionally been adjusted to fall within a desired range depending on the purpose of the heating material by controlling the amount of oxygen inflow through the breathable packaging material (particularly the breathable (porous) film) that houses the heat-generating composition.

[0004] These methods can be used to adjust the maximum temperature, rise time, duration, etc. of heat generation, and the product is designed to optimize these when used under certain conditions. However, strict control of packaging performance imposes a burden on manufacturing costs. Furthermore, no matter how high-performance breathable packaging materials are used, if the amount of ventilation in actual use is not as designed due to the manner of use or pinholes in the bag, the intended performance may not be achieved or safety issues may arise.

[0005] For example, the heating temperature of a typical disposable hand warmer can fluctuate due to changes in the ambient temperature and the amount of air supplied to the warmer caused by moving indoors and outdoors, putting on and taking off a coat, etc. Such hand warmers are often prohibited from being used while sleeping. This is because being covered with a bedding or other covering reduces heat dissipation, causing the temperature to rise and posing a risk of low-temperature burns. Furthermore, disposable hand warmers for shoes are designed for use in environments with limited air flow and are manufactured using packaging materials with relatively high breathability. However, in actual use, the amount of air supplied varies depending on the type of shoe, resulting in temperature variations and a sudden rise in temperature when the shoes are taken off.

[0006] Similar problems also exist with medical heating materials, which require more precise temperature control. For example, transdermal medical hot compresses, which combine a heat source with a drug, are touted for their benefits, such as increased effectiveness and reduced drug dosage due to the more efficient transdermal absorption of heat. However, as mentioned above, conventional temperature control methods do not provide sufficient stability for the generated heat, resulting in inconsistent drug dosage. Furthermore, there is a need for short-term heating elements as an alternative to moxibustion, which does not require fire. However, because moxibustion uses high temperatures, disposable body warmer technology, which lacks temperature stability, poses significant risks and has not become widespread.

[0007] Therefore, the inventors discovered that the temperature stability of the heating material can be improved by mixing a specific temperature control agent into the heat-generating composition or the packaging material of the bag that contains it (Patent Document 3).

[0008] Furthermore, while thermal materials are composed of relatively stable components and can be stored at room temperature for a certain period of time while blocking out oxygen, temperature changes during storage, particularly exposure to high-temperature environments, can reduce shelf life and the maximum temperature. This point has not been considered for thermal materials that use temperature control agents. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication WO1999 / 000078 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-170099 [Patent Document 3] International Publication WO2016 / 063815 Summary of the Invention [Problem to be solved by the invention]

[0010] 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 in place of or in conjunction with conventional temperature control methods that use breathable films to control the amount of oxygen or air supplied, and which prevents or reduces the decrease in heat generation temperature caused by deterioration of the thermal material over time and the effects of storage at high temperatures, and a thermal material using such a means. Another aim 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. [Means for solving the problem]

[0011] According to the present invention, [1] A temperature control agent for controlling the maximum temperature of a heating material containing a heat-generating composition that generates heat upon reaction with oxygen, characterized in that the temperature control agent contains one or more aliphatic compounds that are in a particulate form that does not pass through a 60-mesh standard sieve (standard size according to JIS Z8801-1: 250 μm), have a melting point of 35°C or higher and 65°C or lower, and have 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 (standard size according to JIS Z8801-1: 1000 μm); [3] The temperature control agent according to [1] or [2], which contains one or more compounds selected from the group consisting of higher α-olefin polymers, paraffin wax, myristyl myristate, polyester polyols, and polyoxyethylene fatty acid diesters; [4] A heat-generating composition containing metal powder, salts, water, and activated carbon, which generates heat upon reaction with oxygen, and further containing the temperature control agent according to any one of [1] to [3] above; [5] The heat-generating composition according to [3] above, wherein the heat-generating composition is in a solid form; [6] A heating material comprising a bag or container, at least a portion of which is breathable, containing the heat-generating composition according to [4] or [5]; [7] The thermal material according to [6], wherein at least the bag or container is housed in an airtight outer bag that substantially blocks oxygen; [8] The heating material according to [6] or [7] above, which is used as either a disposable body warmer or a medical device; [9] The thermal material according to [8], wherein the medical device is either a hot compress or a thermal device for stimulating meridians. is provided. [Effects of the Invention]

[0012] According to the present invention, a simple, low-cost, and reliable temperature control means is provided for a thermal material that can be used in place of or in addition to temperature control using a breathable film, and the maximum heat generation temperature remains stable even after long-term storage, making it possible to realize a thermal material with excellent temperature stability and high safety. In particular, the present invention provides a thermal material that is suitable for long-term emergency stockpiling, for example, and that has a low risk of low-temperature burns even when used while sleeping. Specifically, for example, - A heating material that can be safely used while sleeping, reducing the risk of low-temperature burns caused by covering the mattress; - Highly safe disposable warmers for shoes that provide stable heat regardless of the type of shoes and do not cause a sudden rise in temperature even when taking off the shoes; - Transdermal medical hot compress with high temperature stability, safety and effectiveness; - A heating material for stimulating meridians such as moxibustion, which can be used safely by controlling the maximum temperature even in high temperature ranges etc. will be provided. [Brief explanation of the drawings]

[0013] [Figure 1] Figure 1 shows the results of a time-dependent deterioration test in which a heating element containing α-olefin (melting point 58°C) as a temperature regulator was stored at 50°C. "60mesh↓" indicates a sample that passed through a 60-mesh standard sieve (JIS Z8801-1 standard dimension: 250 μm), while "16-60mesh" indicates a sample that passed through a 16-mesh standard sieve (JIS Z8801-1 standard dimension: 1000 μm) but not a 60-mesh standard sieve (JIS Z8801-1 standard dimension: 250 μm) (the same applies to the following figures). Panel (A) shows the heat generation pattern immediately after production; (B) after 2 weeks of storage; (C) after 4 weeks of storage; and (D) after 6 weeks of storage. [Figure 2] FIG. 2 shows the change in maximum temperature over time for the results shown in FIG. [Figure 3] Figure 3 shows the results of a time-dependent deterioration test in which a heating element containing an α-olefin (melting point 62°C) as a temperature regulator was stored at 50°C. Panel (A) shows the heat generation pattern immediately after production, (B) after 2 weeks of storage, (C) after 4 weeks of storage, and (D) after 6 weeks of storage. [Figure 4] FIG. 4 is a graph showing the change in maximum temperature over time for the results shown in FIG. [Figure 5] Figure 5 shows the results of a time-dependent deterioration test in which a heating element containing paraffin wax (P) as a temperature regulator was stored at 50°C. Panel (A) shows the heat generation pattern immediately after production, (B) after 2 weeks of storage, (C) after 4 weeks of storage, and (D) after 6 weeks of storage. [Figure 6] FIG. 6 is a graph showing the change in maximum temperature over time for the results shown in FIG. [Figure 7]Figure 7 shows an example of the structure of a thermal device (moxibustion device) for stimulating meridians of the present invention. Panel A is a cross-sectional view of the moxibustion device, Panel B is a perspective view of a heat-generating composition tablet (1), Panel C is a perspective view of the heat-generating composition tablet (1) placed in a container body (2), and Panel D is a perspective view of the container body (2) containing the heat-generating composition tablet (1) together with an adhesive-treated top material (adhesive tape) (3) attached thereto. Note that the heat-generating composition tablet (1) in Figure 7 is shown schematically in its form before water (or salt water) is added (before swelling). DETAILED DESCRIPTION OF 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 to 65°C and a water solubility (g / 100 mL) of 5 or less at 20°C. The solubility is preferably 3 or less, more preferably 1 or less. The preferred melting point varies depending on the application of the heating material, but is generally 38°C to 60°C. In this specification, the term "aliphatic compound" refers to an organic compound in which all carbon atoms in the molecule are connected in a single chain, or a compound that has a branched carbon atom chain but does not contain a cyclic structure. This includes anhydrides of chain dicarboxylic acids, imides, lactones of hydroxy acids, cyclic ethers, and other compounds that have a cyclic structure containing oxygen or nitrogen but are closely related to the chain compound that is their parent, and that easily open the ring to form a chain compound.

[0015] Aliphatic compounds having such properties can be selected from higher α-olefin polymers, various vegetable, animal, or petroleum-based paraffin waxes, myristyl myristate, polyester polyols, polyoxyethylene fatty acid diesters, etc. In this specification, 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 with one or more other olefins. In other words, higher α-olefin polymers are copolymers 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 with 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 crystallizes, but a side-chain crystalline polyolefin having a certain long-chain α-olefin in the side chain is preferred. Side-chain crystalline polyolefins have sharp melting behavior and are conveniently non-sticky when not molten. Such side-chain crystalline polyolefins are commercially available, for example, under the trade name "HS Crystal" (Toyokuni Seiyu). Similarly, paraffin wax (e.g., Nippon Seiro), myristyl myristate (e.g., Croda Japan), polyester polyols (e.g., DIC, Toyokuni Seiyu), polyoxyethylene fatty acid diesters (e.g., Sanyo Chemical), and higher α-olefin polymers are also commercially available.

[0017] Melting point measurements are performed using a differential scanning calorimeter as follows: 5 mg to 15 mg of sample is placed in an aluminum (Al) container, and an Al crimp cover is placed over it, sealing it with a certain amount of pressure. Using the Al container and crimp cover as a reference, the temperature is raised at a rate of 5°C / min from the estimated melting point of -50°C to the estimated melting point of +30°C. After holding for 5 minutes, the sample is cooled at the same rate and held at the estimated melting point of -50°C for 5 minutes. This process is repeated twice, and the DSC curve for the second cycle (2nd run) is measured. The melting point is read from the main endothermic peak that appears on the DSC curve due to the endothermic heat associated with the sample melting.

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

[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 room temperature. However, pellets, blocks, etc. are crushed (e.g., freeze-crushed) before mixing. After crushing, the particle size is controlled to fall within a predetermined range. In this specification, the particle size of the aliphatic compound is indicated by classification using a standard sieve (Tyler sieve). The size of the sieve openings is generally indicated in "mesh" or "μm" (the standard size (μm) of the openings of metal sieves in JIS Z8801-1 (2006), also referred to as nominal size), and the correspondence between them is well known. Commercially available aliphatic compounds can be appropriately selected and used as they are for the temperature control agent of the present invention. Alternatively, they can be sieved (classified) using various standard sieves into particles that pass through and particles that do not, and then appropriately selected and blended to exhibit the desired heat generation pattern. The aliphatic compound contained in the temperature control agent of the present invention must be in a particulate form that does not pass through a 60-mesh standard sieve (opening 250 μm). The aliphatic compound preferably also has a particulate form that passes through a 16 mesh standard sieve (openings 1000 μm). As long as the particle size is within this range, the particle size may be completely uniform, and there is no particular restriction on the particle size distribution.

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

[0021] The mechanism by which the use of the temperature control agent of the present invention stabilizes the heat generation characteristics is not limited to a particular theory, but is generally thought to be as follows: When a temperature control agent is added to a heat generation composition, the temperature control agent melts when the heat generation temperature reaches near the melting point of the temperature control agent, covering the periphery of the iron powder, thereby inhibiting the oxidation reaction and suppressing the temperature rise. Furthermore, when particles that do not pass through a 60-mesh standard sieve (250 μm opening) are used, they are less susceptible to temporary changes in environmental temperature during storage than when finer particles are used, and accidental melting of the temperature control agent (and a decrease in the maximum exothermic temperature) is less likely to occur. On the other hand, particles that do not pass through a 16-mesh standard sieve (1000 μm opening) tend to take longer to dissolve and delay the cessation of the reaction, resulting in a higher maximum temperature. In particular, when used in an exothermic composition in the form of a tablet, uneven dispersion is likely to occur, which is likely to result in variations in the time it takes to reach the maximum temperature.

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

[0023] For example, a hot compress hand warmer that is applied directly to the skin should preferably generate heat at around 40°C, but if it exceeds 43°C, protein denaturation occurs, increasing the risk of low-temperature burns. Therefore, it is desirable to design it so that the temperature does not exceed 43°C, and if there is a possibility that the temperature may rise above 43°C, it is desirable to quickly suppress the temperature rise to the appropriate level of around 40°C. On the other hand, it is undesirable for the temperature to continue to drop after suppression, as this reduces the thermal effect. Furthermore, even for hot compress hand warmers that are applied directly to the skin, a mild heat generation of below 40°C is preferable when they are applied to the delicate abdomen of women to relieve menstrual pain.

[0024] On the other hand, disposable warmers that are attached to clothing are used at a maximum temperature of around 55°C because the skin is protected by the clothing. Disposable warmers that are used as a substitute for moxibustion are used at a relatively high temperature for a short period of time, but because they come into direct contact with the skin, it is desirable that they be designed not to exceed around 55°C. Furthermore, in the case of a substitute for moxibustion, it is desirable that the temperature quickly drops after suppressing the temperature rise.

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

[0026] Heat-generating composition The exothermic composition of the present invention contains at least a metal powder, a salt, 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 other materials that generate heat of oxidation may also be used. As the salt, 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 also contain a water-retaining agent other than activated carbon (e.g., water-absorbent polymer, vermiculite, sawdust, silica-based material, etc.). Furthermore, various other conventionally known components may be added as needed.

[0028] An example of the blending ratio of these components is, based on 100% of the heat-generating composition, 35-80% by weight of iron, 1-20% by weight of activated carbon, 1-10% by weight of salts, 5-45% by weight of water, and 0-45% by weight of a moisture-retaining agent other than activated carbon. The heat-generating composition of the present invention preferably contains 30-70% by weight of iron, 1-15% by weight of activated carbon, 12-5% by weight of salts, 20-30% by weight of water, 1-25% by weight of a moisture-retaining agent other than activated carbon, and 5-30 parts by weight, preferably 10-30 parts by weight, of an excipient. The amount of the temperature-regulating agent can be appropriately selected depending on the intended use of the heating material and the maximum temperature to be achieved, as described above. For example, 3-40 parts by weight, preferably 3-30 parts by weight, of the temperature-regulating agent of the present invention is added to 100 parts by weight of the heat-generating composition and mixed.

[0029] The exothermic composition can be produced by mixing the essential ingredients described above and optional ingredients selected as necessary, using known methods, under low-oxygen or oxygen-free conditions when salt and water are added in advance. The exothermic composition may be in the form of a powder, which may be further processed by known methods, for example, into cubes by tableting or sheets by rolling. When the exothermic composition is formed into a solid form, a binder such as cellulose (e.g., crystalline cellulose), lactose, starch, dextrin, sucrose ester, Teflon (registered trademark), polyethylene glycol, or carboxymethyl cellulose may be added. For example, to form a solid tablet by tableting, a binder such as crystalline cellulose may be added in an amount of 10 parts by weight or more, preferably 10 to 30 parts by weight, per 100 parts by weight of the exothermic composition to produce a tablet of the desired appropriate hardness. Such a solid exothermic composition is preferable because it prevents sealing defects due to powder adhesion to the sealed portion of a bag or container during packaging and eliminates variations in the exothermic temperature. Regarding the exothermic composition, salts may be mixed simultaneously with the powdered raw materials when mixing them, or they may be added as a salt solution.

[0030] The exothermic composition of the present invention containing such a temperature control agent can be tested according to JIS S4100 exothermic test to determine whether it has achieved the desired maximum temperature by reacting it 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 in the exothermic composition storage bag to contain it, and measuring the temperature change over time. Note that the exothermic test conducted for this purpose may be conducted by appropriately modifying the experimental conditions so as to reflect the expected actual usage conditions.

[0031] packaging material The exothermic composition is filled into a pouch for containing the exothermic composition. The pouch filled with the exothermic composition can be used as a heating material (for example, a non-stick type body warmer) as is. Generally, the exothermic composition pouch is formed so that at least a portion thereof is breathable.

[0032] The breathable packaging material that constitutes the bag for containing the heat-generating composition changes the heat-generating characteristics of the heat-generating material (such as the speed at which heat is generated, the duration of heat generation, and heat transfer to the object to be heated, such as the human body or clothing), so any known material can be appropriately selected and used so that these characteristics fall within the desired range depending on the intended use.

[0033] Commonly used human body warmers and the like use breathable packaging materials with an air permeability of 10,000 to 40,000 seconds / 100cc (JIS P8117). Shoe warmers, for example, use 2,000 to 7,000 seconds / 100cc. Therefore, as breathable packaging materials for heat-generating composition storage bags, packaging materials with an air permeability of 2,000 to 40,000 seconds / 100cc are generally used. For heating materials designed for high temperature and / or short-term use, such as meridian-stimulating heating devices, packaging materials with an air permeability of 0 to 10,000 seconds / 100cc can be used. By using the temperature control agent of the present invention, precise air permeability control is not required depending on the application of the heating material, broadening the acceptable range of breathable packaging materials that can be used.

[0034] The breathable packaging material used in the bag of the present invention may be a film or sheet that is breathable entirely or partially. Generally, breathable packaging materials include single-layer or laminated porous films or sheets used alone or in combination with woven or nonwoven fabrics, or single-layer or laminated imperforate films or sheets with pinholes, used alone or in combination with woven or nonwoven fabrics. In the present invention, the term "film" primarily refers to a single material (including single-layer and laminated materials; the same applies hereinafter) or a relatively thin material, and the term "sheet" primarily refers to a single material, a laminate of two or more single materials, or a relatively thick material, although no strict distinction is made between the two.

[0035] The resin constituting the film is generally a thermoplastic synthetic resin. 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. They can be appropriately selected depending on the purpose, the required heat generation amount, temperature, the heat-generating composition to be used, etc.

[0036] In the present invention, a stretched film, preferably a stretched porous film or a sheet containing the same, is suitably used as the breathable film or sheet. Stretched porous films generally contain an inorganic filler, and exhibit breathability by forming continuous pores through stretching. The breathability can be controlled by controlling the pore size, etc.

[0037] Lamination is usually performed by lamination, but is not limited to this. Any conventionally known method can be used for lamination. For example, lamination may be performed by thermal bonding or with an adhesive such as a hot melt adhesive or an acrylic or urethane adhesive. Full-surface bonding or partial bonding to maintain flexibility may also be used. Preferably, a curtain spray method or a dry lamination method is used.

[0038] Nonwoven fabrics are used in breathable packaging materials from the viewpoints of reinforcing the strength of the packaging material and improving its mechanical properties. Nonwoven fabrics that may be laminated with the above-mentioned film are preferably those conventionally used in technical fields such as heating elements and medical heating devices. Examples include those containing artificial fibers such as nylon, vinylon, polyester, rayon, acetate, acrylic, polyethylene, polypropylene, and polyvinyl chloride, and natural fibers such as cotton, hemp, and silk, and include nonwoven fabrics in the form of spunbond, thermalbond, and spunlace. The basis weight of nonwoven fabrics varies depending on the specific gravity of the nonwoven material and the bulkiness resulting from differences in the entanglement method, but is generally about 10 g / m 2 ~about 200g / m 2 A thickness of about 20 g / m is particularly suitable.2 ~about 100g / m 2 is preferred.

[0039] In particular, breathable sheets in which a stretched porous film of a thermoplastic synthetic resin is laminated with a nonwoven fabric of nylon, polyester fiber, or the like are commonly used.

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

[0041] The bag for containing the exothermic composition can be manufactured by using the above-mentioned packaging material and gluing the periphery by a method commonly used in this technical field. The thermal material can basically be manufactured by sealing the exothermic composition of the present invention in this bag. Generally, the manufacture of the bag and the manufacture of the exothermic material are continuous, and first the periphery of the overlapping packaging material is heat-sealed or glued together with an adhesive, leaving a small portion unsealed, the exothermic composition is poured through the opening, and then this opening is glued together and the exothermic composition is sealed inside.

[0042] Furthermore, moxibustion tools, which have a small application area and / or a short usage time, may be stored in a container with a thickness of, for example, several mm to several cm, rather than in a flat bag. In this case, the lid (top material) and the container body can be manufactured using various packaging materials as described above. For example, the top material (FIG. 7) can contain layers such as a sealant material (3a), a nonwoven fabric (3b), an adhesive (3c), and a release paper (3d) as needed. A specific example is a top material made of, in order from 3a, an LLDPE (30 μm) / PET spunlace nonwoven fabric (30 g / m 2)The composition can be: / SIS-based hot melt adhesive / PET separator (38 μm). As mentioned above, in the case of moxibustion tools and other devices that utilize high temperatures and / or short-term heat generation, packaging materials with very high breathability can be used, so nonwoven fabric may be used alone for the top material and / or the container body.

[0043] heating material As described above, a thermal material can be simply a bag filled with the exothermic composition of the present invention (e.g., a disposable warmer that does not stick) or a container (e.g., a moxibustion tool). However, additional elements can be added as needed. These various elements are known and may be integrated into the bag or provided as separate components to be combined at the time of use. Examples of additional elements include various fastening means and various parts to be combined at the time of use (e.g., a container containing fragrances or medicines, a sheet containing water or cosmetics, or other components used depending on the intended use of the thermal material). Fixing means include, for example, an adhesive layer or poultice layer formed on the surface of a portion of the bag or container containing the exothermic composition to allow the thermal material to be applied; a band-like member to be wrapped around the target to secure it; a mask, supporter, or wristband with a pocket for containing the exothermic material. For purposes such as temperature regulation, a base may be provided between the container and the adhesive layer to adjust the distance and / or space between the application site and the thermal material. The heating material of the present invention may be used by combining various chemicals or fragrances such as camphor or menthol with the adhesive layer, poultice layer, or other components, or with the exothermic composition, and / or packaging material or container. For example, hot receptors such as capsicum tincture, capsicum extract, capsicum powder, ginger tincture, ginger extract, ginger powder, fennel tincture, fennel extract, fennel powder, capsaicin, capsaicin derivatives, vanillyl butyl ether, vanillyl alkyl ether, and nonylic acid vanillylamide can be added to the adhesive. Cool receptors such as l-menthol, peppermint, dl-camphor, peppermint oil, thymol, and oxalic acid menthyl ethylamide can be added to the adhesive.

[0044] The bag or container of the thermal material containing at least the exothermic composition is sealed in an outer bag that blocks oxygen and is stored until use. Such outer bags are also known. For long-term storage, outer bags that have low oxygen permeability to minimize oxidation of iron during storage and that include an aluminum layer with low water vapor permeability to minimize the release of water vapor from the outer bag are particularly preferred. [Example]

[0045] <Manufacturing of moxibustion tools> A moxibustion tool consisting of a container body (2) containing a heat-generating composition tablet (1) and a top material (3), similar to the example shown in Figure 7, was manufactured as follows: The raw materials for the heat-generating composition were iron powder (Powder Tech Co., Ltd., reduced iron powder "RDH-3M"), activated carbon (Osaka Gas Chemicals Co., Ltd., wood-flour activated carbon "Shirasagi S5"), water-absorbent polymer (Sanyo Chemical Co., Ltd., polyacrylic acid resin "ST-500D"), crystalline cellulose (Asahi Kasei Chemicals Corp., crystalline cellulose "Ceolas TG-101"), salt (Nihon Kaisui Co., Ltd., powdered salt "EF-300"), and the aliphatic compounds described below (α-olefin: Toyokuni Oil Mills Co., Ltd., HS Crysta-6100), paraffin wax: Nippon Seiro Co., Ltd., SP-0145). The composition of the exothermic composition was 45 parts of iron powder, 3.5 parts of activated carbon, 5 parts of water-absorbing polymer, 20 parts of crystalline cellulose, 3.5 parts of salt, and 25 parts of an aliphatic compound as a temperature control agent (all "parts" are by weight).

[0046] The aliphatic compounds were crushed and sieved as follows. Each aliphatic compound was melted at 100°C in a low-temperature dryer manufactured by Isuzu Motors, Ltd., poured onto a PET film in the form of a plate approximately 2 mm thick, and cooled to room temperature. The completely solidified plate was coarsely crushed by hand into approximately 10 mm square pieces. This coarsely crushed material was then crushed in a stainless steel coffee mill (product number HG6063, sold by Unox Corporation). The crushed product was manually sieved using a JIS standard stainless steel sieve (Tokyo Screen Co., Ltd., frame dimensions: diameter 200 x 60 mm, specification: JIS Z8801-1:2000) to obtain a test sample of the temperature control agent.

[0047] First, taking into consideration bulk density and particle size, the following ingredients were weighed and added to a beaker in this order: cellulose, aliphatic compound, water-absorbing polymer, activated carbon, salt, and iron. The ingredients were mixed thoroughly with a medicine spoon to eliminate uneven distribution of each ingredient. 2g of this mixed ingredient was weighed out and compressed into tablets using Fuji Yakuhin Kikai's "Quick Mini FY-TQM-30 Tabletop Prototype Tablet Press" (tabletting pressure 15KN). A 16.9mm diameter pressing die and a 17mm inner diameter receiving die were used to produce cylindrical tablets with a diameter of 17mm and a thickness of 7mm.

[0048] A container for containing the exothermic composition tablets was manufactured as follows. First, a wooden prototype mold (top: cylindrical rod, bottom: receiving wooden mold with holes) was prepared, and the pressing surface of the cylindrical rod was heated to 200°C using a laboratory hot stirrer or hot plate. A moldable nonwoven fabric (Asahi Kasei Corporation, thermoformable nonwoven fabric Smash "Y15200 200g / m2) was placed on the receiving wooden mold. 2 ") was pressed with a heated rod to produce a cup-shaped molded article.

[0049] Tablets were placed in the molded nonwoven fabric container body, and a topping material (OPP 20 μm / LLDPE 30 μm (Toho Kako Co., Ltd.)) was attached to the top of the container using a household iron. 0.8 g of water was added to 2 g of tablets through the topping material using a syringe. The container 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 pressing 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 (1 g tablets) with a diameter of 14 mm and a thickness of 4 mm. 0.3 g of water was added per 1 g tablet.

[0051] <Melt point and solubility measurements> The melting points of each aliphatic compound were measured using a differential scanning calorimeter (DSC6220, manufactured by Seiko Instruments Inc.) connected to a fully automatic cooling unit and an analysis system (EXSTAR6000 thermal analysis rheology system, using DSC Muse measurement software and DSC Muse standard analysis software). The sample containers used were an open-type aluminum sample container, φ5.2 H2.5 (50 μl), and an open-type aluminum sample container (crimp cover).

[0052] 5 mg to 15 mg of sample was placed in an aluminum container, and an aluminum crimp cover was placed over it and sealed by applying a certain pressure. Using the aluminum container and crimp cover as a reference, the temperature was raised at a rate of 5°C / min from the estimated melting point of -50°C to +30°C. After holding for 5 minutes, the sample was cooled at the same rate and held at the estimated melting point of -50°C for 5 minutes. This cycle was repeated twice, and the DSC curve for the second run was measured. The melting point was determined as described above from the endothermic peak that appeared on the DSC curve due to the endothermic heat generated by the melting of the sample.

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

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

[0055] The storage test was conducted at 50°C and 35% humidity in an Advantech Toyo Co., Ltd. low-temperature, constant temperature and humidity chamber, model THE051FA. Two weeks of storage at 50°C is equivalent to one year of storage at room temperature. Similarly, four weeks at 50°C is equivalent to two years at room temperature, and six weeks is equivalent to three years. The temperature of 50°C was set taking into consideration conversion to room temperature in an Arrhenius plot, as well as warehouse storage and sea container transport.

[0056] <Heat generation test of moxibustion tools> The heat generation test was carried out following the method of JIS S4100 "Disposable Moxibustion Equipment" under the conditions of an ambient temperature of 20±1℃, a wind speed of 0.5 m / s or less (windless condition), an ambient humidity of 55-70%, and a heating part temperature of 30±1℃ in a heating device consisting of a heater and a circulating thermostatic water bath. Since the moxibustion equipment is attached directly to the skin when in use, it was attached directly to the surface of the heater and measured.

[0057] The heat generation test was carried out using a tank-type heater measuring W615 x D410 x H60 mm (using an 8 mm thick vinyl chloride plate) placed in a constant temperature room at 20°C and 65% humidity, with hot water circulating at 8 L / min from an attached circulating constant temperature water bath, and the surface temperature of the heater (vinyl chloride plate) was controlled to 30°C.The moxibustion tool sample was placed with the container body facing downwards, and a temperature measurement sensor was attached to approximately the center of the bottom surface with double-sided tape, and then attached to the vinyl chloride plate on the surface of the heater (the temperature measurement device was a Chino Graphic Recorder KR2S00, and the sensor was an ST-22E-005 from Anritsu Meter Co., Ltd.).

[0058] The results are shown in Figures 1 to 6.

[0059] From the above results, it was revealed that the maximum heat generation temperature of the heating material using the heat generating composition containing the temperature regulating agent of the present invention is hardly affected by long-term storage. Therefore, the heating material using the heat generating composition containing the temperature regulating agent of the present invention is not only highly temperature stable and safe, but also able to maintain the designed heat generation performance for a long period of time.

[0060] This application is based on Japanese patent application No. 2018-018047 filed on February 5, 2018, and the contents of the specification and claims of Japanese patent application No. 2018-018047 are incorporated herein by reference. [Explanation of symbols]

[0061] 1. Heat-generating composition 2 Container (main body) 3 Top material 3a sealant 3b Non-woven fabric 3c adhesive agent 3D release paper

Claims

1. A temperature control agent for controlling the maximum temperature of a thermal material containing a heat-generating composition that generates heat by reacting with oxygen and reducing deterioration of the thermal material over time, a temperature control agent which is in a particulate form that does not pass through a 60-mesh standard sieve (standard dimension according to JIS Z8801-1: 250 μm) but passes through a 16-mesh standard sieve (standard dimension according to JIS Z8801-1: 1000 μm), has a melting point of 35°C or higher and 65°C or lower, and has 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 wax, myristyl myristate, polyester polyols, and polyoxyethylene fatty acid diesters; A temperature control agent containing 35 to 80% by weight of metal powder, 1 to 20% by weight of activated carbon, 1 to 10% by weight of salts, and 5 to 45% by weight of water, with the weight of the heat generating composition being 100%, and used in an amount of 3 to 40 parts by weight per 100 parts by weight of the heat generating composition excluding the temperature control agent (wherein the metal powder, the salts, the activated carbon, and the temperature control agent are mutually different components).

2. A temperature control agent as described in claim 1, wherein the heat generating composition includes a binder and is molded into a solid form (wherein the metal powder, the salts, the activated carbon, the binder and the temperature control agent are mutually different components).

3. A method for producing a temperature control agent according to claim 1 or 2, comprising the steps of crushing and sieving an aliphatic compound selected from the group consisting of higher α-olefin polymers, paraffin wax, myristyl myristate, polyester polyols, and polyoxyethylene fatty acid diesters, which have a melting point of 35°C or higher and 65°C or lower and a water solubility (g / 100mL) of 5 or less at 20°C, to obtain a particulate powder that passes through a 16-mesh standard sieve (standard dimension according to JIS Z8801-1: 1000μm) but does not pass through a 60-mesh standard sieve (standard dimension according to JIS Z8801-1: 250μm).

4. A method for controlling the maximum temperature of a thermal material containing a heat-generating composition that generates heat upon reaction with oxygen, and reducing deterioration of the thermal material over time, the method comprising the step of incorporating the temperature control agent according to claim 1 or 2 into a heat-generating composition containing 35 to 80% by weight of metal powder, 1 to 20% by weight of activated carbon, 1 to 10% by weight of salts, and 5 to 45% by weight of water, with the weight of the heat-generating composition being 100%, in an amount of 3 to 40 parts by weight per 100 parts by weight of the heat-generating composition excluding the temperature control agent.

5. A method for producing a thermal material containing a heat-generating composition that reacts with oxygen to generate heat, A step of incorporating the temperature control agent according to claim 1 or 2 into an exothermic composition in an amount of 3 to 40 parts by weight per 100 parts by weight of the exothermic composition containing 35 to 80% by weight of metal powder, 1 to 20% by weight of activated carbon, 1 to 10% by weight of salts, and 5 to 45% by weight of water, with the weight of the exothermic composition being 100%, and not including the temperature control agent; a step of housing the exothermic composition containing the temperature control agent in a bag or container having at least a portion thereof breathable; A method comprising:

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