Temperature control agent as well as exothermic composition and warming material therewith

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 pocket 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 heat devices for relieving pain through heat, and in everyday items such as hand warmers and other warming devices for protection against the cold.

[0003] The heat generating composition used in such a heating material most generally contains as its components metal powder such as iron powder, salt such as salt, water, and a moisture retaining agent such as activated carbon, and generates heat by the heat of oxidation generated when the metal reacts with oxygen. Therefore, in the past, the heat generating properties have been adjusted to be within a desired range according to the purpose of the heating material by controlling the amount of oxygen inflow through the breathability, moisture permeability, and material of the breathable packaging material of the bag containing the heat generating composition, particularly the breathable (porous) film.

[0004] These methods can be used to adjust the maximum temperature, rise time, duration, etc. of heat generation, and products are designed to optimize these when used under certain conditions. However, strictly controlling the performance of packaging materials is a burden in terms of 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 usage mode or pinholes in the bag, the originally expected performance may not be achieved and safety problems may occur.

[0005] For example, the heating temperature of a typical disposable hand warmer can fluctuate due to changes in the environmental temperature and the amount of air supplied to the hand warmer caused by moving between 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 the like reduces heat dissipation, causing the temperature to rise and creating the risk of low-temperature burns. Disposable hand warmers for shoes are intended for use in environments where the inflow of air is restricted, and are manufactured using packaging materials with relatively high breathability. However, in actual use, the amount of air supplied to each type of shoe varies, causing temperature variations, and the temperature can rise sharply when the shoes are taken off.

[0006] The same problem exists with medical heating materials, which require more accurate temperature control. For example, a transdermal medical hot compress that combines a heating element and a drug is said to have the advantage of increasing efficacy and reducing the amount of drug by increasing the efficiency of transdermal absorption by heat, but as mentioned above, the stability of the heating temperature is incomplete with conventional temperature control, and there is a problem that the dosage of the drug is not stable due to the unstable temperature. Furthermore, there is a need for a heating element that can be used for a short time as an alternative to moxibustion that does not use fire, but moxibustion uses a high temperature range, so disposable hand warmer technology that lacks temperature stability is risky 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] In addition, thermal materials are made up of relatively stable components and can be stored for a certain period of time at room temperature while blocking out oxygen, but temperature changes during storage, especially exposure to high-temperature environments, can reduce preservability 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] JP 2001-170099 A [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 heating material (particularly control of the maximum heat generation temperature) more easily and at lower cost, which can be used in place of or in combination with conventional temperature control by controlling the supply of oxygen or air with a breathable film, etc., and for preventing or reducing the decrease in heat generation temperature caused by deterioration of the heating material over time and the effects of storage at high temperatures, and a heating material using the same. Another aim of the present invention is to provide a more advanced temperature control means that can be used for heating materials for medical use, and to provide an improved heating 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 thermal material containing a heat generating composition that reacts with oxygen to generate heat, the temperature control agent being characterized in that it contains one or more aliphatic compounds that are in a particulate form that does not pass through a 60 mesh standard sieve (standard dimension 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 dimension 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 which contains a metal powder, a salt, water and activated carbon and generates heat by reacting with oxygen, the heat generating composition further containing the temperature control agent according to any one of [1] to [3] above; [5] The heat-generating composition according to the above [3], wherein the heat-generating composition is in a solid form; [6] A heating material comprising a bag or container containing the heat-generating composition according to [4] or [5], at least a portion of which is breathable; [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. Effect of the Invention

[0012] According to the present invention, a simple, low-cost, 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 a thermal material with excellent temperature stability and high safety can be realized, with a stable maximum heat generation temperature even after long-term storage. 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 bedding; - A highly safe disposable warmer for shoes that provides stable heat regardless of the type of shoes and does not cause a sudden rise in temperature even when the shoes are taken off; - A transdermal medical hot compress with high temperature stability, high safety and effectiveness; - A heating material for use as a meridian stimulation device such as moxibustion, which can be used safely by controlling the maximum temperature even in the high temperature range etc. will be provided. [Brief description 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 that a sample passed through a 60-mesh standard sieve (standard dimension according to JIS Z8801-1: 250μm), and "16~60mesh" indicates that a sample passed through a 16-mesh standard sieve (standard dimension according to JIS Z8801-1: 1000μm) but not a 60-mesh standard sieve (standard dimension according to JIS Z8801-1: 250μm) was used (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. [Diagram 2] FIG. 2 shows the change in maximum temperature over time for the results shown in FIG. [Diagram 3] Figure 3 shows the results of a time-dependent deterioration test in which a heating element containing 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 two weeks of storage, (C) after four weeks of storage, and (D) after six weeks of storage. [Figure 4] FIG. 4 shows the change in maximum temperature over time for the results shown in FIG. [Diagram 5] Figure 5 shows the results of a deterioration test over time 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 shows the change in maximum temperature over time for the results shown in FIG. [Figure 7]Figure 7 shows an example of the structure of the meridian stimulating heating device (moxibustion device) of the present invention. Panel A is a cross-sectional view of the moxibustion device, Panel B is a perspective view of the exothermic composition tablet (1), Panel C is a perspective view of the exothermic composition tablet (1) placed in the container body (2), and Panel D is a perspective view of the container body (2) containing the exothermic composition tablet (1) together with the adhesive-treated top material (adhesive tape) (3) attached thereto. The exothermic composition tablet (1) in Figure 7 is shown diagrammatically in the form before water (or salt water) is added (before swelling). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Temperature Control Agent The temperature control agent of the present invention is characterized in that it contains one or more aliphatic compounds having a melting point of 35°C to 65°C and a water solubility (g / 100mL) 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 thermal material, but is generally preferably 38°C to 60°C. In this specification, the term "aliphatic compound" means an organic compound in which all carbon atoms in the molecule are connected in a single chain, or a carbon atom chain that has a branched structure but does not contain a cyclic structure, such as an anhydride of a chain dicarboxylic acid, an imide, a lactone of an oxyacid, or a cyclic ether, which has a cyclic structure containing oxygen or nitrogen, but is closely related to the parent chain compound, and includes compounds 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 paraffin waxes such as vegetable, animal or petroleum-based, myristyl myristate, polyester polyols, polyoxyethylene fatty acid diesters, etc. In this specification, higher α-olefin polymers refer to copolymers of two or more α-olefins having 10 to 35 carbon atoms, or copolymers 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 copolymers 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 crystallized, but a side chain crystalline polyolefin having a certain long chain α-olefin in the side chain is preferred. Side chain crystalline polyolefins have a sharp melting behavior. They are convenient because they are not sticky when not melted. Such side chain crystalline polyolefins are manufactured and sold under the trade name of "HS Crysta" (Toyokuni Seiyu) and are commercially available. Similarly, paraffin wax (e.g., Nippon Seiro), myristyl myristate (e.g., Croda Japan), polyester polyol (e.g., DIC, Toyokuni Seiyu), polyoxyethylene fatty acid diester (e.g., Sanyo Kasei), and higher α-olefin polymers are also commercially available.

[0017] The melting point is measured 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 and sealed by applying a certain pressure. Using the Al container and clamp cover as a reference, the temperature is raised from the estimated melting point of -50°C to the estimated melting point of +30°C 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 of -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 on the DSC curve due to the endothermic heat associated with the melting of the sample.

[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, but pellets, blocks, etc. are crushed (for example, frozen crushed) before mixing. After crushing, the particle size is controlled to be within a predetermined range. In this specification, the particle size of the aliphatic compound is shown by classification using a standard sieve (Tyler sieve). The size of the sieve openings is generally shown in "mesh" or "μm" (the standard size (μm) of the openings of metal sieves in JIS Z8801-1 (2006), also called nominal size), and the correspondence between them is publicly known. For the temperature control agent of the present invention, a commercially available aliphatic compound can be appropriately selected and used as is, or it can be sieved (classified) using various standard sieves into particles that pass and particles that do not pass, and appropriately selected and blended to show the 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 (openings 250 μm). The aliphatic compound further desirably has a particulate form that passes through a 16 mesh standard sieve (1000 μm openings). 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 distribution.

[0020] In this specification, "not passing through" a sieve with a certain mesh size means that 60% or more of the total do 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 pass 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 specific theory, but is generally believed 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, and covers the periphery of the iron powder, inhibiting the oxidation reaction and suppressing the temperature rise. In addition, 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 the environmental temperature during storage compared to when finer particles are used, and it is considered that accidental melting of the temperature control agent (and a drop 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 (1000 μm opening) tend to take longer to dissolve and delay the cessation of the reaction, which is considered to result in a higher maximum temperature. In particular, when used in a heat generating composition in the form of a tablet, it is considered that the dispersion state is likely to be biased, and therefore the time to reach the maximum temperature is likely to vary.

[0022] The maximum temperature and heat generation pattern to be achieved vary depending on the application 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 hot pack 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 will rise to 43°C or higher, 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. Also, when applying a hot pack warmer directly to the skin to the delicate abdomen of a woman to relieve menstrual pain, a mild heat generation of 40°C or less is preferable.

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

[0025] Thus, since there are maximum temperatures and heat generation patterns suitable for each of the various thermal materials, in order to realize this, 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 a temperature control agent, and the amount to be added, the method of addition, the addition of optional components, etc. can be designed. 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 metal powders may be used as long as they generate heat of oxidation. 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 a water-retaining agent other than activated carbon (e.g., water-absorbent polymer, vermiculite, sawdust, silica-based material, etc.). In addition, various other conventionally known components may be added as necessary.

[0028] Examples of the blending of these components include, for example, 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 water-retaining agent other than activated carbon, with the weight of the heat-generating composition being 100%. In the heat-generating composition of the present invention, 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 water-retaining agent other than activated carbon, and 5-30 parts by weight, preferably 10-30 parts by weight of an excipient are preferable. The blending amount of the temperature control agent can be appropriately selected according to the purpose of use of the warming material and the maximum temperature to be achieved, as described above. For example, the temperature control agent of the present invention is added in an amount of 3-40 parts by weight, preferably 3-30 parts by weight, to 100 parts by weight of the heat-generating composition having such a blending, and mixed.

[0029] The exothermic composition can be produced by mixing the above-mentioned essential components and optional components selected as necessary, by a known method, 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 a known method, for example, into a cube shape by tableting or into a sheet shape by rolling. When the exothermic composition is molded 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 obtain a tablet-shaped solid form by tableting, a binder such as crystalline cellulose is added in an amount of 10 parts by weight or more, preferably in the range of 10 to 30 parts by weight, per 100 parts by weight of the exothermic composition, to obtain a tablet having a desired appropriate hardness. Such a solid exothermic composition is preferable in order to prevent poor sealing caused by adhesion of powder to the sealed portion of the bag or container during sealing and to eliminate variation in the exothermic temperature. In addition, salts may be mixed at the same time as the powder raw material is mixed with the exothermic composition, or it may be added as salt water.

[0030] The exothermic composition of the present invention containing such a temperature control agent can be tested in a JIS S4100 exothermic test by measuring the temperature change over time when reacted with oxygen in the air via a breathable packaging material (for example, 17,000 to 18,000 seconds / 100 cc (JIS P8117 method (Gurley method)) used in a bag for containing the exothermic composition, to confirm whether or not the desired maximum temperature has been achieved. Note that the exothermic test performed for this purpose may be performed 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 bag for containing the exothermic composition. The bag filled with the exothermic composition can be used as a heating material (for example, a non-stick type warmer) as it is. In general, the bag for containing the exothermic composition is formed so that at least a part of it has air permeability.

[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 objects to be heated such as the human body or clothing) depending on the selection of the breathable packaging material. Therefore, any known material can be appropriately selected and used so that these characteristics fall within the desired range depending on the purpose of use.

[0033] For general human body warmers, etc., breathable packaging materials with a breathability of 10,000 to 40,000 seconds / 100cc (JIS P8117) are used. For shoe warmers, for example, breathable packaging materials with a breathability of 2,000 to 7,000 seconds / 100cc are used. Therefore, as the breathable packaging material for the exothermic composition storage bag, a packaging material with a breathability of 2,000 to 40,000 seconds / 100cc is generally used. For heating materials designed to be used at high temperatures and / or for a short period of time, such as a meridian stimulating heating device, a packaging material with a breathability of 0 to 10,000 seconds / 100cc can be used. By using the temperature control agent of the present invention, precise control of breathability is not required depending on the application of the heating material, and the allowable range of breathable packaging materials that can be used is expanded.

[0034] The breathable packaging material used in the present invention for the bag may be a film or sheet that is entirely or partially breathable. Generally, the breathable packaging material is a single-layer or laminated porous film or sheet used alone or in combination with a woven fabric or nonwoven fabric, or a single-layer or laminated non-porous film or sheet with pinholes, used alone or in combination with a woven fabric or nonwoven fabric. In the present invention, the term "film" refers mainly to a single body (including single-layer and laminated bodies; the same applies below) or a relatively thin body, and the term "sheet" refers mainly to a single body or a laminate of two or more single bodies or a relatively thick body, but the two are not strictly distinguished from each other.

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

[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. A stretched porous film generally contains an inorganic filler, and exhibits breathability by forming continuous pores by stretching, and the breathability can be controlled by controlling the pore size, etc.

[0037] When laminating, it is usually performed by a lamination method, but is not limited to this. Any conventionally known method can be applied for lamination. For example, it may be a method of laminating with thermal bonding or an adhesive such as a hot melt adhesive or an acrylic or urethane adhesive, and it may be a full-surface bonding or a partial bonding to maintain flexibility. 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 mechanical suitability. As the nonwoven fabric that may be laminated with the above-mentioned film, those conventionally used in technical fields such as heating elements and medical heating devices can be suitably used. Examples of the nonwoven fabric 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 examples of the nonwoven fabric include spunbond, thermal bond, and spunlace types. The basis weight of the nonwoven fabric varies depending on the specific gravity of the nonwoven fabric material and the bulkiness due to differences in the interlacing 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 nonwoven fabric such as nylon or polyester fiber is laminated onto a stretched porous film of a thermoplastic synthetic resin are widely used.

[0040] A part of the bag, for example the back side packaging material of the 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 is no particular limitation on the material, thickness, configuration, etc., so long as it is suitable for forming the exothermic composition-containing bag.

[0041] The bag for containing the exothermic composition can be manufactured by gluing the periphery of the packaging material as described above by a method commonly used in this technical field. The warming material can basically be manufactured by sealing the exothermic composition of the present invention in the bag. In general, the manufacture of the bag and the manufacture of the exothermic material are continuous, and first, the periphery of the overlapped packaging material is heat sealed or glued with an adhesive, leaving a part, and the exothermic composition is poured in through the open part, and then the opening is glued and the exothermic composition is sealed in.

[0042] Moreover, for items such as moxibustion tools that have a small application area and / or a short usage time, they 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, too, packaging materials of various materials as described above can be appropriately used for manufacturing the lid (top material) and the container body. For example, the top material (FIG. 7) may contain layers such as a sealant material (3a), a nonwoven fabric (3b), an adhesive (3c), and a release paper (3d) as necessary. As a specific example, from 3a onwards, LLDPE (30 μm) / PET spunlace nonwoven fabric (30 g / m 2) / SIS-based hot melt adhesive / PET separator (38 μm). As mentioned above, in the case of items that utilize high temperature and / or short-term heat generation such as moxibustion tools, 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 The thermal material may be only a bag filled with the heat generating composition of the present invention (for example, a disposable warmer that does not stick) or only a container (for example, a moxibustion tool) as described above, but additional elements can be added as necessary. These various elements are known and may be integrated into the bag, or may be provided as separate members to be combined when used. Examples of additional elements include various fixing means and various parts to be combined when used (for example, containers containing fragrances or medicines, sheets containing water or cosmetics, etc., which are used depending on the purpose of the thermal material). Examples of fixing means include an adhesive layer or a poultice layer formed on a part of the surface of a bag or container for containing the heat generating composition so that the thermal material can be attached, a band-shaped member for wrapping around and fixing the target to be heated, a mask, supporter, or wristband with a pocket for storing the heat generating material, etc. For the purpose of temperature regulation, 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 thermal material. The heating material of the present invention may be used by combining various drugs or fragrances such as camphor and menthol with the adhesive layer, the poultice layer, or other components, or with the heat generating composition, and / or the packaging material or container. For example, as a hot receptor, 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, nonyl acid vanillyl amide, etc. can be added to the adhesive. As a cold receptor, l-menthol, peppermint, dl-camphor, peppermint oil, thymol, oxalic acid menthyl ethyl amide, etc. can be added to the adhesive.

[0044] The bag or container of the thermal material containing at least the heat generating 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, it is particularly preferable to use an outer bag that has low oxygen permeability to reduce the oxidation reaction of iron during storage and that includes an aluminum layer with low water vapor permeability to reduce the release of water vapor from the outer bag. EXAMPLES

[0045] <Manufacture 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 Fig. 7 was manufactured as follows. The raw materials for the heat generating composition were iron powder (Powdertech Co., Ltd., reduced iron powder "RDH-3M"), activated carbon (Osaka Gas Chemicals Co., Ltd., wood powder activated carbon "Shirasagi S5"), water-absorbent polymer (Sanyo Kasei Co., Ltd., polyacrylic acid resin "ST-500D"), crystalline cellulose (Asahi Kasei Chemicals Co., Ltd., crystalline cellulose "Ceolas TG-101"), salt (Nihon Kaisui Co., Ltd., powdered salt "EF-300"), and 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 iron powder, 3.5 parts activated carbon, 5 parts water-absorbent polymer, 20 parts crystalline cellulose, 3.5 parts salt, and 25 parts aliphatic compound as a temperature regulator (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 Manufacturing Co., Ltd., poured onto a PET film in the form of a plate with a thickness of about 2 mm, and cooled at room temperature. The completely solidified plate was coarsely crushed by hand into pieces of about 10 mm square. This coarsely crushed material was then crushed in a stainless steel coffee mill (product number HG6063, sold by Unox Co., Ltd.). The crushed product was manually sieved using a JIS standard stainless steel sieve (Tokyo Screen Co., Ltd., frame dimensions: diameter 200×60 mm, specification: JIS Z8801-1:2000) to obtain a test sample of the temperature control agent.

[0047] First, taking into consideration the bulk density and particle size, the following ingredients were weighed and added to a beaker in the following order: cellulose, aliphatic compound, water-absorbent 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 pressed into tablets using Fuji Yakuhin Kikai's "Desktop Prototype Tablet Press Quick Mini FY-TQM-30" (tabletting pressure 15KN). A pressing die with a diameter of 16.9mm and a receiving die with an inner diameter of 17mm 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 (upper: cylindrical rod, lower: receiving wooden mold with holes) was prepared, and the pressing surface of the cylindrical rod was heated to 200°C with a laboratory hot stirrer or hot plate. A moldable nonwoven fabric (Asahi Kasei Corporation, Thermoformable Nonwoven Fabric Smash "Y15200 200g / m 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 CO., LTD.)) was attached to the top of the container with a household iron. 0.8 g of water was added to the topping material for every 2 g of tablets using a syringe. The container was sealed in an airtight outer bag (PET 12 μm / aluminum foil 7 μm / LLDPE 50 μm (TOHO KAKAKOU 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. The measuring device used was a differential scanning calorimeter (DSC6220, all manufactured by Seiko Instruments Inc.) connected to a fully automatic cooling unit and an analysis system (EXSTAR6000 thermal analysis rheology system, software was DSC Muse measurement software and DSC Muse standard analysis software), and the sample containers used were an open-type sample container made of aluminum, φ5.2 H2.5 (50 μl), and an open-type sample container made of aluminum (crimp cover).

[0052] 5mg to 15mg of sample was placed in an Al container, and an Al crimp cover was placed on top of it and sealed by applying a certain pressure. The Al container + clamp cover was used as a reference, and the temperature was raised from the estimated melting point of -50°C to the estimated melting point of +30°C 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 as explained above from the endothermic peak that appeared on the DSC curve due to the endothermic heat associated with 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 limit amount at which the compound 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.) were 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 carried out at 50°C and 35% humidity using Advantec Toyo Co., Ltd.'s THE051FA low temperature thermohygrostat. 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 using an Arrhenius plot, storage in a warehouse, and shipping in marine containers.

[0056] <Heat generation test of moxibustion tools> The heat generation test was performed following the method of JIS S4100 "disposable moxibustion" under the conditions of an ambient temperature of 20±1℃, wind speed of 0.5 m / s or less (windless condition), ambient humidity of 55-70%, and heating part of the heating device consisting of a heater and a circulating thermostatic water bath at 30±1℃. Since the moxibustion tool 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 performed using a tank-shaped heater measuring W615 x D410 x H60 mm (using 8 mm thick polyvinyl 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 (polyvinyl chloride plate) controlled to 30°C. The moxibustion tool sample was placed with the container body facing down, and a temperature measurement sensor was attached to approximately the center of the bottom surface with double-sided tape, and then attached to the polyvinyl 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 is clear that the maximum heat generation temperature of the heat-generating material using the heat-generating composition containing the temperature control agent of the present invention is hardly affected by long-term storage. Therefore, the heat-generating material using the heat-generating composition containing the temperature control agent of the present invention has high temperature stability and high safety, and can maintain the designed heat generation performance for a long period of time.

[0060] This application is based on a Japanese patent application, Patent Application No. 2018-018047, filed on February 5, 2018, and the contents of the specification and claims of 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 3d Release paper

Claims

1. A temperature controller for controlling the maximum temperature of a heating material containing an exothermic composition that reacts with oxygen to generate heat and reducing the aging deterioration of the heating material, 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) 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 has a water solubility (g / 100 mL) at 20°C of 5 or less, 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.

2. A method for producing a temperature controller for controlling the maximum temperature of a heating material containing an exothermic composition that reacts with oxygen to generate heat and reducing the aging deterioration of the heating material, which has a melting point of 35°C or higher and 65°C or lower, and has a water solubility (g / 100 mL) at 20°C of 5 or less, and pulverizes and sieves an aliphatic compound selected from the group consisting of higher α-olefin polymers, paraffin waxes, myristyl myristate, polyester polyols, and polyoxyethylene fatty acid diesters to obtain a powder in a particulate form that passes through a 16-mesh standard sieve (reference dimension according to JIS Z8801-1: 1000 μm) and does not pass through a 60-mesh standard sieve (reference dimension according to JIS Z8801-1: 250 μm).

3. A method for controlling the maximum temperature of a heating material containing an exothermic composition that reacts with oxygen to generate heat and reducing the aging deterioration of the heating material, which 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 in a particulate form that 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 has a water solubility (g / 100 mL) at 20°C of 5 or less, and includes the step of containing the temperature controller in the exothermic composition. A method for manufacturing a thermogenic material comprising a thermogenic composition that generates heat upon reaction 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) 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 wax, myristyl myristate, polyester polyol, and polyoxyethylene fatty acid diester as a temperature control agent in the thermogenic composition, and a step of accommodating the thermogenic composition in a bag or container at least a part of which has air permeability, and a method comprising the above steps.

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