JP7110690B2 - Non-aqueous exothermic composition and thermal product - Google Patents

Description

TECHNICAL FIELD The present invention relates to a non-aqueous exothermic composition and a thermal product using the same.

Precise temperature control is required for local heating of the body, taking into account the avoidance of low-temperature burns and adaptation to temperature-sensitive areas such as the face and eyes. As a conventional technology, there is a chemical body warmer that generates heat due to oxidation. In addition, heat generation using the heat of hydration or heat of dissolution of inorganic salts has a simple composition, but it is difficult to control the temperature during use. was necessary. Furthermore, when a water-absorbing agent is used, the occurrence of temperature unevenness becomes a problem.

As a temperature control technology, for example, by using a powdered superabsorbent polymer together with a substance (exothermic agent) that generates heat by hydration, the amount of water in contact with the exothermic agent is not affected by the amount of water added. is known to enable stable heat generation by keeping constant (Patent Document 1: Japanese Unexamined Patent Application Publication No. 2003-24365). However, in order to generate heat with this technique, it was necessary to immerse part or all of the body to which the thermal composition was applied in warm water of 33 to 45°C.

JP 2003-24365 A

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a non-aqueous exothermic composition capable of generating heat at room temperature and capable of temperature control, and a thermal product using the same.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) one selected from inorganic anhydrides and their hydrates that generate heat when reacting with water and have a reaction heat of 10 to 500 kJ / mol. A mixture of the above and (B) a water-soluble cellulose ether containing a methoxy group as a substituent quickly generates heat at room temperature with water, and can be maintained at a constant temperature of 38 to 55 ° C., especially around 40 to 45 ° C. for a long time. It was discovered that it can be done, and it came to make this invention.

Accordingly, the present invention provides the following non-aqueous exothermic compositions and thermal products.
[1]. (A) One or more selected from inorganic anhydrides and hydrates thereof that generate heat when reacting with water and have a reaction heat of 10 to 500 kJ/mol, and (B) Water-soluble containing a methoxy group as a substituent A non-aqueous exothermic composition containing cellulose ether and generating heat when water is added.
[2]. The non-aqueous exothermic composition according to [1], wherein the component (B) is a water-soluble cellulose ether having 1.5 to 2.0 moles of methoxy groups per glucose unit.
[3]. The non-aqueous heat-generating composition according to [1] or [2], wherein the component (B) is methylcellulose.
[4]. The non-aqueous exothermic composition according to any one of [1] to [3], wherein component (A) is selected from a mixture of aluminum and calcium hydroxide or calcium oxide, calcium oxide, magnesium chloride and calcium chloride. .
[5]. The non-aqueous heat-generating composition according to any one of [1] to [4], wherein the non-aqueous heat-generating composition is combined with a non-woven fabric, woven fabric, knitted fabric or absorbent cotton to form a sheet.
[6]. A thermal product comprising the non-aqueous heat-generating composition according to any one of [1] to [5] and water, wherein the non-aqueous heat-generating composition and the water are isolated, the non-aqueous heat-generating composition and water A thermal product having means for contacting the

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a non-aqueous exothermic composition capable of generating heat at room temperature and capable of temperature control, and a heating product using the same.

FIG. 12 is a diagram showing measurement positions in Example 11; FIG. 11 is a configuration diagram of an eye mask used in Example 12;

The present invention will be described in detail below.
[(A) component]
(A) one or more selected from inorganic anhydrides and their hydrates that generate heat when reacting with water and have a reaction heat of 10 to 500 kJ/mol (heat amount per mol of inorganic anhydride or hydrate); be. Such components include calcium chloride (hereinafter, heat of reaction +43 kJ/mol), magnesium chloride (+12 kJ/mol), chlorides such as aluminum chloride, sulfates such as magnesium sulfate, aluminum sulfate, calcium sulfate, sodium carbonate, Carbonates such as potassium carbonate, inorganic substances such as oxides such as calcium oxide (+65 kJ/mol), hydrates thereof, mixtures of aluminum and calcium hydroxide (+377 kJ/mol), and aluminum and calcium oxide A mixture (+442 kJ/mol) and the like can be mentioned, and one type can be used alone or two or more types can be used in appropriate combination. Among them, a mixture of aluminum and calcium hydroxide (+377 kJ/mol), a mixture of aluminum and calcium oxide (+442 kJ/mol), calcium oxide, magnesium chloride, Calcium chloride is preferred, and a mixture of aluminum and calcium hydroxide, calcium oxide, magnesium chloride, and calcium chloride are more preferred from the viewpoint of heat generation speed.

In particular, when the component (A) is a mixture of (A-1) aluminum and (A-2) calcium hydroxide or calcium oxide, the mixing ratio (mass ratio) is from the viewpoint of reaction efficiency to (A-1 )/(A-2) is preferably 0.1 to 10, more preferably 0.2 to 5.

Component (A) is preferably in the form of powder, and in this case the average particle size is preferably 5 to 2,000 μm. The average particle diameter of component (A) is the cumulative average diameter D ₅₀ (median diameter) of volume-based particle size distribution measured by laser scattering diffraction particle size distribution measurement.

The content of component (A) is preferably 40 to 99% by mass, more preferably 50 to 90% by mass in the non-aqueous heat-generating composition. Further, the area for spreading the non-aqueous heat-generating composition is preferably 500 to 10,000 mg, more preferably 1,000 to 5,000 mg, for example, in the case of 7 cm×6 cm (about 42 cm ² ). When it is equal to or higher than the above lower limit, the temperature and durability of heat generation become better, and when it is equal to or lower than the upper limit, excessive temperature rise can be further prevented.

[(B) Component]
It is a water-soluble cellulose ether containing a methoxy group as a substituent. This component is a water-soluble polymer compound that gels when heated and returns to the original aqueous solution when cooled, and contains a methoxy group as a substituent. As such, nonionic water-soluble polymer compounds such as methylcellulose and hydroxypropylmethylcellulose are preferable, and methylcellulose is more preferable. In this component, when the temperature rises, the methoxy groups in the polymer are hydrophobized between molecules to form cross-linking points, causing gelation. The number of moles of methoxy groups introduced per glucose unit of cellulose is preferably 1.5 to 2.0. In the present invention, "water-soluble" means that the solubility in 10,000 mL of water at 20°C exceeds 1 g.

The reason why the temperature can be controlled by combining the components (A) and (B) is unknown, but when the temperature rises due to the heat of reaction between the component (A), which is a heating element, and water, the (B ) component causes gelation at a certain temperature, water is taken into the gel, and the reaction between the water and the heating element is stopped, thereby suppressing excessive heat generation. Furthermore, when the temperature drops due to heat dissipation, the gel returns to the aqueous solution and the reaction between the water and the heating element resumes, generating heat. It is considered that this repetition realizes the temperature control action.

The viscosity of the 2 mass % aqueous solution of component (B) at 20° C. is preferably 50 to 8,000 mPa·s, more preferably 100 to 4,000 mPa·s, from the viewpoint of the gelation temperature. In addition, when the viscosity is less than 600 mPa s, the 17th revision Japanese Pharmacopoeia Viscosity Measurement Method 1 (capillary viscometer method) at 20 ° C ± 0.1 ° C, and 20 when it is 600 mPa s or more ℃ ± 0.1 ℃, 17th revision Japanese Pharmacopoeia viscosity measurement method 2 (single cylindrical rotational viscometer method).

Component (B) is preferably in the form of powder, and in this case the average particle size is preferably 5 to 2,000 μm. The average particle diameter of component (B) is the cumulative average diameter D ₅₀ (median diameter) of volume-based particle size distribution measured by laser scattering diffraction particle size distribution measurement.

The content of component (B) is preferably 1 to 55% by mass, more preferably 10 to 20% by mass, in the non-aqueous heat-generating composition. When the temperature is equal to or higher than the above lower limit, the temperature does not become too high, and when the temperature is equal to or lower than the upper limit, heat build-up becomes better.

The content mass ratio of component (A) to component (B) represented by (B)/(A) is preferably 0.01 to 1.0, more preferably 0.1 to 0.3, and 0.01 to 0.3. 13 to 0.3 is more preferred. When the content is equal to or higher than the above lower limit, heat buildup is not excessively caused by high temperatures, and when the content is equal to or lower than the upper limit, heat build-up can be maintained.

The non-aqueous heat-generating composition of the present invention can contain optional components as long as they do not affect the effects of the present invention. Inorganic compounds, inorganic salts, hydrates thereof, organic acids and salts thereof may be added to control the gelation temperature. Examples include sodium chloride, sodium hydroxide, sodium sulfate, sodium nitrate, sodium bromide, sodium phosphate, ferric chloride, citric acid, sodium citrate and the like. Alcohols, polyhydric alcohols and sugar alcohols can also be added. Among these components, sodium chloride, sodium hydroxide, sodium sulfate, sodium nitrate, sodium bromide, sodium phosphate, citric acid, sodium citrate, sugar alcohol and the like are preferred.

[Production method]
The non-aqueous heat-generating composition of the present invention is obtained by powder-mixing component (A) and component (B) in a predetermined ratio.

[Non-aqueous exothermic composition]
The non-aqueous heat-generating composition of the present invention is preferably a mixed powder containing components (A) and (B), does not contain water, and generates heat when water is added. The temperature at which water is added to generate heat may be room temperature, or may be 1 to 30°C. Moreover, the maximum temperature reached by the non-aqueous heat-generating composition is preferably 35 to 55°C, more preferably 40 to 45°C. The duration of heat generation from the maximum temperature to 38° C. is preferably 10 minutes or longer, more preferably 30 minutes or longer. Although the upper limit is not particularly limited, it may be 2 hours or less. If the composition is not a non-aqueous heat-generating composition, the components (A) and (B) cannot be mixed, or the maximum temperature reached becomes too high, making suitable temperature control impossible.

The non-aqueous heat-generating composition may be combined with non-woven fabric, woven fabric, knitted fabric or absorbent cotton and formed into a sheet. As a combination method, for example, the non-aqueous heat-generating composition may be enclosed in a bag-like nonwoven fabric or the like, the non-aqueous heat-generating composition may be wrapped in a sheet-like nonwoven fabric or the like, or the sheet-like nonwoven fabric or the like may be folded in two. A non-aqueous exothermic composition may be filled during this time. By using non-woven fabrics, woven fabrics, knitted fabrics or absorbent cottons together in this manner, water can be rapidly diffused, and contact between the non-aqueous heat-generating composition (powder) and water can occur immediately and uniformly. It leads to homogenization. Non-woven fabrics, woven fabrics, knitted fabrics or absorbent cottons are preferably hydrophilic fibers in order to quickly conduct water. Either natural or synthetic fibers may be used, and natural fibers include cotton and synthetic fibers include rayon and the like. Also, the basis weight is preferably 10 to 130 g/m ² . By making the basis weight equal to or higher than the lower limit, the amount of water to be conveyed is increased, and the amount of water to be diffused is increased. In addition, by setting the content to the upper limit or less, it is possible to provide a thin and soft feel, and to prevent the contact between the mixed powder and water from being reduced due to excessive water absorption.

[How to use and thermal products]
The non-aqueous heat-generating composition of the present invention is a non-aqueous heat-generating composition that generates heat when water is added. The amount of water is not particularly limited as long as it generates heat, but it is preferably 0.5 to 5 times (mass) the amount of component (A). As for the method of use, water may be added to the non-aqueous exothermic composition in a container to generate heat. In this case, the container for containing the non-aqueous heat-generating composition is not particularly limited, and may be a bag, bottle, can, plastic container, or glass container, and is not particularly limited as long as it can withstand the temperature.

The water may be prepared by the user, or a heating product containing the non-aqueous exothermic composition and water separately may be used. Water is not particularly limited, and may contain other components, and may be a composition containing water, for example, a gel composition containing water. As a specific thermal product, for example, a thermal product that contains a non-aqueous heat-generating composition and water, and that the non-aqueous heat-generating composition and water are shut off, and the non-aqueous heat-generating composition and water are brought into contact with each other. and a heating product comprising a non-aqueous exothermic composition and a gel composition containing water, wherein the non-aqueous exothermic composition and the gel composition containing water are mixed at the time of use. Heating products to be used and the like can be mentioned. These are preferable because the heat generating effect can be obtained anywhere.

In the case of a thermal product having a non-aqueous exothermic composition and a gel composition containing water, the gel composition may include polyhydric alcohols such as glycerin, butylene glycol, propylene glycol, pentanediol, hexanediol, polyethylene glycol, hydroxy Polymer compounds such as propylcellulose, hydroxypropylmethylcellulose, xanthan gum, tamarind gum, carboxyvinyl polymer, sodium carboxymethylcellulose, carrageenan, pectin, sodium hyaluronate, and sodium alginate can be blended. When these are blended, the amount of polyhydric alcohol in the gel composition is preferably 0.01 to 5 times (mass) that of water, and the amount of polymer compound is 0.01 to 0.5 times that of water. A double (mass) range is preferred.

Containers filled with the non-aqueous exothermic composition and water (or a composition containing water) in the case of thermal products include plastic and aluminum bags, and the materials include polyethylene, polypropylene, and polyester. , plastic films such as polyvinyl chloride, laminated films having an aluminum layer, and the like can be used. In the case of a non-aqueous heat-generating composition in which component (A) is a mixture of aluminum and calcium hydroxide or calcium oxide, fine holes should be made in the bag in order to quickly release hydrogen gas, which will be described later. The size of fine holes is preferably 50 to 1,000 μm, and the number of holes is appropriately set depending on the size of the holes described above, but is preferably 3 to 20. Depending on the size of the hole, the vicinity of the hole may be filled with absorbent cotton or the like together with the non-aqueous heat-generating composition.

Furthermore, by wrapping in an air-permeable sheet, water vapor can be provided, which is effective for moisturizing. When the component (A) is a mixture of aluminum and calcium hydroxide or calcium oxide, it is possible to provide hydrogen gas, which is known to have antioxidant effects, and antioxidative effects on the skin and eyes can be expected. Therefore, a further effect can be imparted while heating. Furthermore, by adjusting the air permeability of the air-permeable sheet, the passage of hydrogen gas can be controlled, and by moderate expansion of the bag body, it is possible to provide fit and massage feeling to the application site. In addition, the effect of warm compresses on the eyes and around the eyes is known, and the fit is required for areas with large unevenness, and it is also known that oxidative stress is involved in dry eyes, etc. be.

The air permeable sheet is preferably waterproof, and its air permeability is preferably 1,000 to 30,000 sec/100 cc, more preferably 2,000 to 20,000 sec/100 cc, and 3,000 to 10,000 sec/100 cc. is more preferred. When the air permeability is set to the upper limit or lower (the air permeability is higher than the lower limit), gaps are less likely to occur due to expansion, and the fit is improved, the thermal sensation is improved, and the pressurization is increased to provide a massage sensation. If the air permeability is above the lower limit (air permeability is below the upper limit), the contact area around the eyes will improve because it does not expand too much, and the fit will improve, and the thermal sensation will be good, and the pressurization will also give a massage feeling. can get. The air permeability is the required time (seconds) for 100 cc of water to pass through, obtained from the Oken type air permeability test, and the higher the value, the lower the air permeability.

Means for blocking the non-aqueous heat-generating composition and water are not particularly limited, but the non-aqueous heat-generating composition and water are separately enclosed in a waterproof bag such as a multi-chamber container made of plastic, aluminum, or the like. method. As means for bringing the non-aqueous heat-generating composition into contact with water, for example, by applying a force from the outside to any of the enclosed bags, the part where the non-aqueous heat-generating composition and water are cut off opens. , a method in which the non-aqueous heat-generating composition and water are brought into contact with each other. As such, for example, easy peel and the like can be mentioned. In the case of packaging in the air-permeable sheet, the entire heating product may be packaged, or the non-aqueous heat-generating composition portion may be packaged. Alternatively, the non-aqueous exothermic composition can be put into a container such as plastic, aluminum, bottle, can, etc., added with water at the time of use, mixed, and applied directly to the body. As in the case of the above example of the thermal product, the multi-chambered container may be filled with water in advance, and the product may be brought into contact with the water during use.

The application site of the non-aqueous heat-generating composition or heating product of the present invention is not particularly limited, and it can be used anywhere on the body. It can be a thermal product in the form of an eye mask. Further, by providing an adhesive layer on one side of the sheet, the sheet can be used as a thermal product of a type to be attached to the skin (for eyes, waist, legs, shoulders, neck, etc.). In addition, the exothermic composition can be used as an external preparation for the skin (including the scalp) that reacts with water at the time of use to warm the skin.

EXAMPLES Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise specified, "%" in the composition indicates mass %, and ratio indicates mass ratio. The average particle diameter of the components (A) and (B) is the cumulative average diameter D ₅₀ (median diameter) of volume-based particle size distribution measured by laser scattering diffraction particle size distribution measurement.

[Examples 1 to 6]
(A-1) aluminum and component (B) were placed in a bag-shaped container (made of polyethylene) and mixed, and then (A-2) calcium hydroxide was added and mixed to obtain a non-aqueous exothermic composition (raw material are all powders, same below). 5 g of water was added to the obtained mixed powder and lightly mixed. The temperature and time of the exothermic composition were measured by the following methods.

[Examples 7 to 10]
Components (A) and (B) were placed in the same bag-like container as in Example 1 and mixed to obtain a non-aqueous exothermic composition. 5 g of water was added to the obtained mixed powder and lightly mixed. The temperature and time of the exothermic composition were measured by the following methods.
The (A) calcium oxide used in Examples 7 and 8 was obtained by pulverizing coarse granules and sieving through a 1,000 μm filter. (A) magnesium chloride used in Examples 9 and 10 was a powder with an average particle size of 10 to 100 μm. All of the components (B) were powders with an average particle size of 50 to 100 μm.

[Comparative Examples 1 to 3]
Aluminum and component (B') were placed in the same bag-shaped container as in Example 1 and mixed (no mixing was performed in Comparative Example 1), and calcium hydroxide was further added and mixed to obtain a non-aqueous exothermic composition. 5 g of water was added to the obtained mixed powder and lightly mixed. The temperature and time of the exothermic composition were measured by the following methods.

[Comparative Example 4]
The component (B) was placed in the same bag-like container as in Example 1 to obtain a non-aqueous exothermic composition. 5 g of water was added to the obtained mixed powder and lightly mixed. The temperature and time of the exothermic composition were measured by the following methods.

[Measuring method]
A thermometer was used to directly measure the temperature of the exothermic composition, and the highest temperature reached was measured. Furthermore, the time (duration time) for the temperature to drop to 38° C. was measured. The results are shown by the following evaluation criteria.
<Evaluation criteria>
・ Maximum temperature ◎: 40 ℃ or more and 45 ℃ or less ○: 35 ℃ or more and less than 40 ℃, over 45 ℃ and 55 ℃ or less ×: less than 35 ℃, over 55 ℃ ・ Duration of 38 ℃ or more (until it drops to 38 ℃) time of)
◎: 30 minutes or more ○: shorter than 30 minutes

[Example 11]
(I) 3 g of the exothermic composition of Example 3 was evenly filled in a non-woven fabric of 14 cm x 6 cm while it was folded in half, placed in a bag (made of polyethylene, 7 cm x 6 cm), and 5 g of water was added.
(II) 3 g of the exothermic composition of Example 3 was put into the same bag as in (I) so as to be flat and spread uniformly to a size of 7 cm x 6 cm, and 5 g of water was added.
Regarding the above (I) and (II), the temperature was measured at the measurement positions (1) to (4) in FIG. 1 by the above measurement method. Table 4 shows the results.

As is clear from the above results, (I) combined with the nonwoven fabric had a temperature of 42 to 45°C, and (II) without combination had a temperature of 39 to 48°C. was uniform.

[Example 12]
An eye mask having the structure shown in FIG. 2 was produced by the following method.
A bag body 2 is used in which the chamber is divided into two by an easy peel 1 and communicated with each other by an external force. The first chamber 3 was filled with 5 g of water, and the second chamber 4 was filled with 3 g of the exothermic composition of Example 3 in the same manner as in Example 11. 500 μm in diameter, not shown) were opened (insert absorbent cotton or the like in the vicinity of the holes as necessary). Two bag bodies 2 in which the water or the like is enclosed in a waterproof air permeable bag-shaped sheet 5 having an air permeability shown in Table 5 are sealed so that both ends become the first chambers 3, wrapped and packaged. A body (about 25 cm x about 6 cm) 6 was obtained. An eye mask was produced by attaching rubber bands 7 to both ends of the package as ear hooks. The material of the bag and the size of the bag containing the exothermic composition were the same as in Example 11, and the size of the bag containing water was 6×4 cm. The obtained eye mask was subjected to the following sensory evaluation by a specialized panelist. Table 5 shows the results.

・Fitting
◎: Fits well around the eyes 〇: Slightly fits around the eyes / Feeling of massage ◎: Very pleasant 〇: Quite pleasant temperature) was measured from the outside.)
◎: Fairly warm and very warm 〇: Slightly warm

If the air permeability is too high (low air permeability, the same applies below), gaps will occur and the fit tends to decrease, and if the air permeability is too low (high air permeability, the same applies below), excessive expansion There was a tendency for the contact area around the eyes to decrease and the fit to decrease. If the air permeability is too high, there is a tendency that the expandability is lost, the pressure is reduced, and the feeling of massage tends to decrease. On the other hand, if the air permeability is too high, the thermal sensation tends to decrease due to the lack of expandability and gaps are generated. . The air permeability is based on the Oken type air permeability test.

[Example 13]
The final package obtained in Example 12 (using a film with an air permeability of 3,900 sec/100 cc) (the size of the package is about 25 cm x about 6 cm) was directly attached to one side of the package without attaching rubber. Adhesive tape (Nitofit, manufactured by Nitto Denko Co., Ltd.) was used to impart skin adhesiveness to obtain a patch-type thermal product. The thermal product of Example 13 had excellent thermal sensation, and the temperature from the outside of the package (5 minutes after the easy peel was broken) was 44°C. It could be applied to the neck, arms, shoulders, waist, legs, etc., and the fit to the neck was particularly good due to moderate expansion.

[Example 14]
A patch-type thermal product was obtained in the same manner as in Example 13 using an air permeability of 210 sec/100 cc (3M Microporous Film, manufactured by 3M Japan Ltd.). The thermal product of Example 14 had excellent thermal sensation, the temperature from the outside of the package (5 minutes after the easy peel was broken) was 44° C., and it did not expand, so it was easy to apply even inside clothes. It was possible to locally warm the body, promoting blood flow and relaxing effects. Also, the pain in my lower back and knees was reduced. Furthermore, the generation of water vapor and hydrogen can keep the skin moisturized and can be expected to have an antioxidant effect.

[Example 15]
A thermal gel having the following composition was prepared. This warming gel was mixed with water at the time of use and applied directly to the body.

The temperature when mixed with water was 43° C., indicating excellent thermal properties. There was no feeling of coldness when applying the gel, and it was possible to apply it comfortably. It could also be used as a massage agent. In addition, similar results were obtained even when hydroxypropyl cellulose and xanthan gum were in the ranges of 20 to 200 mg and 50 to 500 mg, respectively.
In addition, samples were prepared using polyethylene glycol instead of glycerin, and sodium alginate, carrageenan, sodium carboxymethylcellulose, polyethylene oxide, and carboxyvinyl polymer instead of xanthan gum. These also had the same thermal properties and usability as Example 15 using glycerin, and a relaxing effect was obtained. These could also be used as massage agents. Water is the amount to be mixed at the time of use.

[Example 16]
A gel pack having the following composition was prepared. The exothermic composition was mixed in the amounts shown in Table 7. For component 1, after uniformly dispersing components 2 to 4, add to component 1 heated to 70° C. or higher and stir well to obtain a mixture of components 1 to 4, then add a mixture of components 5 to 7, It was obtained by adding to a mixture of components 1 to 4 and stirring. The mixing ratio (mass ratio) of the exothermic composition: 1st agent: 2nd agent was 1:5:1. The exothermic composition, agents 1 and 2 were sealed in separate pouch containers (made of aluminum), respectively, and the exothermic composition, agents 1 and 2 were mixed in a glass container at the time of use.

The temperature immediately after mixing the exothermic composition, the 1st agent and the 2nd agent was 45° C., indicating excellent thermal properties. It was warm when applied and allowed local warming to the body. Promotes blood flow and relaxes. The mixture of the exothermic composition, agent 1 and agent 2 was gel-like at first, but after a while it became pack-like and could be peeled off.

The raw materials used in the above examples are shown below. In addition, unless otherwise specified, the amount of each component in the table is the amount in terms of pure content.
・ Aluminum: powder with an average particle size of 20 to 200 μm, “reagent”, manufactured by Wako Pure Chemical Industries, Ltd. ・ Calcium hydroxide: powder with an average particle size of 1 to 50 μm, “reagent”, manufactured by Kanto Chemical Co., Ltd. ・Oxidation Calcium: Powder obtained by crushing coarse granules and sieving at 1,000 μm, “Reagent”, manufactured by Showa Kagaku Co., Ltd. Magnesium chloride: Powder with an average particle size of 10 to 100 μm, “Anhydrous magnesium chloride catalyst grade”, Maruyasu Methyl cellulose manufactured by Sangyo Co., Ltd.: "Product name: Metrose SM", manufactured by Shin-Etsu Chemical Co., Ltd., 2% by mass aqueous solution concentration; 100 to 8,000 mPa s (20 ° C.)
MC4000 has a 2% by mass aqueous solution viscosity (20°C) of 4,000 mPa s, and the number of moles of methoxy groups introduced per glucose unit is 1.8.
MC100 has a 2% by mass aqueous solution viscosity (20° C.) of 100 mPa s, and the number of moles of methoxy groups introduced per glucose unit is 1.8.
Carboxymethylcellulose sodium: "Product name: P-815C", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 1 mass% aqueous solution viscosity: 1,000 to 2,000 mPa s, degree of etherification: 0.82
・Hydroxypropyl cellulose: “Product name: NISSO HPC-L”, manufactured by Nippon Soda Co., Ltd. ・Xanthan gum: “Product name: Echo Gum T”, manufactured by DSP Gokyo Food & Chemical Co., Ltd. ・Sodium alginate: “Product name: Kimika Algin I-3", Kimika Co., Ltd. Carrageenan: "Product name: GENOVISCO PJ-JPE, GENOGEL WR-80-J" Sansho Co., Ltd. Polyethylene oxide: "Product name: POLYOX", Nippon Colorcon Joint Carboxyvinyl polymer manufactured by the company: "Product name: CARBOPOL 974P NF Polymer", LUBRIZOL ADVANCED MARIALS INC. Paraffin, "Product name: Refined paraffin wax", Nikko Rica Co., Ltd., Glycerin, "Product name: Nikkoku Concentrated Glycerin," Sakamoto Pharmaceutical Co., Ltd., Polyethylene glycol: "Reagent, Macrogol 400" , Kanto Kagaku Co., Ltd. Non-woven fabric: "Product name: AS-40 (fiber type: synthetic fiber, basis weight 40 g / m ² )" Daiwabo Polytec Co., Ltd. Non-woven fabric: "Product name: Oikos AP2060 (fiber Seed: natural fiber, basis weight 60 g/m ² )”, manufactured by Nisshinbo Textile Co., Ltd.,
・Waterproof and air-permeable sheet, "Product name: BREATHRON", air permeability of 1,500-28,000 sec/100 cc, using nylon-based non-woven fabric as a composite material, made by Nitto Denko Co., Ltd. ・Bag body, "Multi-chamber container (Easy peel design)", manufactured by Fujimori Industry Co., Ltd. Tamarind gum: "Product name: Gryloid 6C" manufactured by DSP Gokyo Food & Chemical Co., Ltd. Citric acid: "reagent", Wako Pure Chemical Industries, Ltd.・Sodium citrate: “Reagent”, Wako Pure Chemical Industries, Ltd. ・Methylparaben: “Methyl paraoxybenzoate”, Ueno Pharmaceutical Co., Ltd. ・Butylene glycol: “1,3-butylene glycol”, Daicel Chemical Industries Made by Co., Ltd.

1 easy peel 2 bag 3 first chamber 4 second chamber 5 waterproof air permeable sheet 6 package 7 rubber (ear hook)

Claims (7)

(A) a mixture of aluminum and calcium hydroxide or calcium oxide, one or more selected from calcium oxide, magnesium chloride and calcium chloride , and (B) methyl cellulose
A non-aqueous exothermic composition that generates heat by adding water. 2. The non-aqueous exothermic composition according to claim 1, wherein the component (B) is methyl cellulose in which the number of moles of methoxy groups introduced per glucose unit is 1.5 to 2.0. 3. The non-aqueous exothermic composition according to claim 1, wherein a 2% by mass aqueous solution of component (B) has a viscosity at 20° C. of 50 to 8,000 mPa·s. The non-aqueous heat-generating composition according to any one of claims 1 to 3, wherein the content of component (A) is 40 to 99% by mass in the non-aqueous heat-generating composition. The content ratio of the component (A) to the component (B) represented by (B)/(A) is from 0.01 to 1.0, the non-metal according to any one of claims 1 to 4 Water-based exothermic composition. The non-aqueous heat-generating composition according to any one of claims 1 to 5 , wherein the non-aqueous heat-generating composition is combined with a non-woven fabric, woven fabric, knitted fabric or absorbent cotton to form a sheet. A thermal product comprising the non-aqueous heat-generating composition according to any one of claims 1 to 6 and water, wherein the non-aqueous heat-generating composition and water are isolated, wherein the non-aqueous heat-generating composition and water are separated from each other. A thermal product having means for contacting the

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