JP2007186627A - Method for producing hydrous exothermic composition and apparatus for producing hydrous exothermic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an exothermic composition having functions to obtain a hydrous exothermic composition and to provide an apparatus for producing the hydrous exothermic composition. <P>SOLUTION: The method for producing the hydrous exothermic composition comprises producing a raw material for the exothermic composition consisting essentially of iron powder, a carbon component, a reaction accelerator and water. The method is characterized as follows. A step of metering a powder raw material and feeding the powder raw material, a step of transporting the powder raw material while mixing the powder raw material, a step of metering a liquid raw material and feeding the liquid raw material, a step of bringing the raw material into contact with an oxidizing gas, a step of replenishing the liquid and a step of transporting the powder and the liquid while mixing the powder with the liquid in a cylindrical body arranged in a transverse direction are successively carried out. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method and apparatus for producing a heat-generating composition for a heating element, and more specifically, using a mixing and conveying device comprising a cylindrical casing extending substantially horizontally and having a screw, and an oxidizing gas, Production of a hydrous exothermic composition for continuously producing a hydrous exothermic composition having excellent exothermic properties and excellent moldability and compression resistance by contact with at least essential components of the exothermic composition The present invention relates to a method and an apparatus for producing a hydrous exothermic composition.

  Disposable warmers are generally well known as products used by causing air (oxygen) to act on an exothermic mixture such as iron powder.

It is known that iron powder is the most common metal powder used in these crystallizations, and salt, water, etc. are used as reaction aids, and water retention agents that carry these substances. It is also well known that activated carbon, vermiculite, diatomaceous earth, wood powder, or a water-absorbing polymer is used as a mixture.
In addition, conventionally, an exothermic composition manufacturing apparatus measures a predetermined amount of two or more powders such as iron powder and water retention agent (oxidant), which are raw materials of chemical warmers, water, etc., and a mixing tank or the like. A batch plant is generally used in which a predetermined amount is added and mixed, and then transferred to another container and stored for a certain period of time to make a heat generating composition. After that, it is generally transferred to a discharge position for filling and filled in a bag or the like to produce a heating element.

  Patent Document 1 proposes an exothermic composition in which manganese dioxide, cupric oxide, and iron tetroxide are mixed with other exothermic composition components.

  Patent Document 2 proposes a heating element in which a heating composition mainly composed of an oxidation accelerator such as iron, water, and salt is stored in a breathable container after reaching 40 ° C.

  In the case of a disposable body warmer, it is desired to raise the temperature immediately after opening (for example, Patent Documents 1 and 2).

  As for the mixing device for warmers, Patent Document 3 and Patent Document 4 disclose a powder mixing device for warmers that can efficiently mix powder using a vertically extending cylindrical body. Has been.

Patent Document 5 discloses a powder material mixing and conveying method as a powder material mixing and conveying method of the exothermic composition.
This is because the exothermic composition powder mixed is sprayed from the upper surface of the nonwoven fabric, and then the nonwoven fabric is vibrated to hold the exothermic composition powder in the voids of the nonwoven fabric, and the wood pulp nonwoven fabric is stacked thereon. The sheet is heated and pressure-bonded with an embossing roll heat compressor and formed into a sheet shape. After cutting, salt water is added to form a sheet-like heating element. ) Is added.

Conventional production methods of exothermic compositions mainly consist of a batch method, in which exothermic compositions are prepared in advance and stored in a sealed container such as a bag, and then a necessary amount is taken out and used.
However, after these exothermic compositions are mixed and prepared, they are stored in a hopper or in a bag and temporarily stored in a storage place. It must be manufactured and stored in large quantities, the storage method and storage location must be secured, and the proportion of the composition of the exothermic composition changes during storage, and the expected exothermic performance There was an inconvenience that there was some drowning that could not be obtained.

The manganese dioxide, cupric oxide, and iron tetroxide of Patent Document 6 are catalysts and cannot be used as exothermic substances. Also, when they are added to the exothermic composition, the contact between the iron tetroxide and the iron powder surface is not sufficient, and there is no effect as described, and usually the heating element is used to warm the human body or object. In a low temperature region of about 30 to about 90 ° C. used for the purpose, there is a problem that the exothermic rising property is hardly effective and the duration of heat generation becomes shorter as the addition ratio increases.
In Patent Document 2, it took 25 minutes to reach the exothermic composition to 40 ° C., and industrial mass production was difficult.
In patent document 3 and patent document 4, since it is a method and an apparatus which produces continuously using the cylinder extended in the perpendicular direction, adjustment of the amount of moisture to add is difficult, and the exothermic composition obtained by the method and apparatus The quality of the was never satisfactory. Furthermore, it has been difficult to produce an exothermic composition having a large amount of water and having excess water.
In Patent Document 5, an exothermic composition containing moisture cannot be produced, and there is difficulty in handling such as the exothermic composition powder flying during the process, and further mixing of the exothermic composition powder component and moisture (saline solution). However, the process is complicated, and there are problems in terms of quality, manufacturing, and cost.

  As in the conventional batch-type exothermic composition manufacturing method, the raw material components of the exothermic composition are supplied to the same place at the same time and mixed at that place, classification occurs depending on the mixing time, and the time elapses. In order to obtain a composition having a large change in composition ratio, stable composition ratio, and uniform exothermic composition, the mixing time and take-out time had to be strictly controlled.

Japanese Patent Laid-Open No. 53-60885 JP-A-57-10673 JP-A-9-254901 JP-A-9-323032 Japanese Patent Laid-Open No. 10-99367 Japanese Patent Laid-Open No. 53-60885

  The problem of the present invention is that the components are continuously mixed and fed into the small compartments, the components are continuously mixed and conveyed, and by contacting with the oxidizing gas, the oxidation reaction occurs immediately upon contact with the air, It generates heat, then starts abrupt reaction, changes to a mild reaction at a certain temperature, is inexpensive and can be produced at the point of use of the exothermic composition, industrial mass production is possible, An object is to provide a method and apparatus for producing a heat generating composition having a function for obtaining a water-containing heat generating composition containing a water amount capable of generating heat or a water amount higher than that.

The present inventor has made extensive studies and solved the above problems to complete the present invention.
The method for producing a hydrous exothermic composition according to the present invention is a method for producing a hydrous exothermic composition for producing a raw material of an exothermic composition containing iron powder, a carbon component, a reaction accelerator, and water as essential components. In a cylindrical body arranged in a lateral direction, a step of measuring and supplying a powder raw material, a step of conveying the powder raw material while mixing, a step of measuring and supplying a liquid raw material, an oxidation It is characterized in that a contact step with a sex gas, a liquid replenishment step, and a step of conveying the powder and the liquid while mixing are sequentially performed.
Further, the present invention according to claim 2 is a water-containing exothermic composition manufacturing method according to claim 1, wherein the exothermic composition raw material has a water content of 0.5 to 20% by weight and an excess water amount. The dynamic water value is less than 0.01, and the liquid replenishment step and the liquid replenishment step are performed. In the next contact step with the oxidizing gas, the temperature of the iron powder is 1 ° C. or more. It is characterized by raising the temperature.
Moreover, the present invention described in claim 3 is the method for producing a hydrous heat generating composition according to claim 1 or 2, wherein the iron powder and the carbon component are supplied from an independent raw material supply port of the powder. Features.
Moreover, the present invention according to claim 4 is the method for producing a hydrous heat generating composition according to any one of claims 1 to 3, wherein the temperature of the mixture after contact with the oxidizing gas is 30 ° C to 60 ° C. After that, water is replenished.
Further, the present invention according to claim 5 is the method for producing a hydrous exothermic composition according to claim 4, wherein the hydrous exothermic composition obtained by the method comprises an excess water having a mobile water value of 0.01 or more. It is an exothermic composition.
The invention according to claim 6 is characterized in that, in the method for producing a hydrous exothermic composition according to claims 1 to 5, at least the contact step with the oxidizing gas is heated to a predetermined temperature and maintained. To do.
Moreover, the hydrous exothermic composition manufacturing apparatus of the present invention includes a plurality of powder raw material metering ports and a plurality of liquids in the longitudinal direction of the tubular body arranged in the lateral direction. A raw material metering supply port is provided, and a raw material mixing device, a transport device, and an oxidizing gas supply device are provided between the supply ports.
Moreover, the present invention described in claim 8 is the water-containing exothermic composition manufacturing apparatus according to claim 7, wherein each of the supply ports is provided in a plurality of independent apparatuses.
Further, the present invention according to claim 9 is the water-containing heat generating composition manufacturing apparatus according to claim 7 or 8, wherein the oxidizing gas supply device is formed by communicating an upper part of the cylindrical body with the atmosphere. It is characterized by being made.
Further, the present invention described in claim 10 is characterized in that, in the water-containing exothermic composition manufacturing apparatus according to any one of claims 7 to 9, the mixing device is constituted by a screw.
Moreover, the present invention described in claim 11 is the water-containing exothermic composition manufacturing apparatus according to claim 10, wherein the screw has one or more paddles.
Moreover, the present invention described in claim 12 is the water-containing exothermic composition manufacturing apparatus according to any one of claims 7 to 11, characterized in that the transport device is a belt conveyor.
The invention according to claim 13 is the apparatus for producing a hydrous heat generating composition according to claim 12, characterized in that a heating means is provided in at least a part of the conveying device.

The present inventor has made extensive studies and solved the above problems to complete the present invention.
The method for producing a water-containing exothermic composition of the present invention is a method in which an exothermic composition raw material containing iron powder, a carbon component, a reaction accelerator, and water as essential components is continuously measured using a metering device, and a powder-based raw material and water content are measured. It is divided into system raw materials and has a water supply port, a water replenishment port, and at least two powder supply ports, and is conveyed to the mixing and conveying device extending substantially horizontally while being continuously divided and mixed. To make contact with oxidizing gas, and then replenish water, then transport while mixing, so that solid powder supply process, solid mixing and transport process, moisture supply process, contact process with oxidizing gas, water replenishment It is preferable to perform a process and a solid-liquid mixing conveyance process in this order.
Further, in the method for producing a hydrous exothermic composition, the exothermic composition raw material has a water content of 0.5 to 20% by weight with respect to the total weight by using a metering supply device, and has an easy water value indicating an excess water amount. Weigh continuously so as to be less than 0.01, and divide into powder-based raw materials and moisture-based raw materials, have a water supply port, a water supply port, and at least two powder supply ports, and are almost horizontal It is conveyed to the extended mixing and conveying apparatus while continuously dividing and mixing, then brought into contact with the oxidizing gas, mixed with the oxidizing gas, and a temperature rise of 1 ° C. or more from the temperature of the iron powder raw material. And then transporting it, replenishing the water so that the desired mobile water value can be obtained, and further transporting while mixing, so that the solid powder supply process, the solid mixing and transport process, the water supply process, and the oxidizing property The gas contact process, hydration process, and solid-liquid mixing and transport process are performed in this order Door is preferable.
In addition, the method for producing a hydrous exothermic composition includes: the exothermic composition raw material as iron powder, a carbon component reaction accelerator, and moisture as essential components, and at least an iron powder as a powdery solid material, and a powdered solid with independent carbon components It is preferable that one component is supplied to each of the system raw material supply ports.
Further, in the method for producing a hydrous exothermic composition, the metering and feeding device comprises a solid metering and feeding device, a liquid metering and feeding device, and a liquid metering and replenishing device. The solid metering and feeding device comprises a screw feeder, a vibration feeder, a rotary feeder, and a metering hopper. At least one selected from the group consisting of a communication pipe tank type device, a tubing pump type device, a pump pumping type device, and a pressurized needle ejection type device. It is preferable that the mixing and conveying device and the oxidizing gas contact mixing and conveying device are at least one selected from a screw conveyor with a paddle, a coil screw conveyor with a paddle, and a mixing belt conveyor.
Also, the method for producing a hydrous exothermic composition includes the above-mentioned powdered solid raw material supplying step, solid-liquid mixing and conveying step, moisture-based liquid supplying step, contact step with oxidizing gas, moisture-based liquid replenishing step, and solid-liquid mixing and conveying step. Is preferably performed by a combination of at least two or more independent devices.
In the method for producing a hydrous exothermic composition, the temperature of the exothermic mixture after contact with the oxidizing gas is preferably 30 ° C to 60 ° C and then replenished with moisture.
In the method for producing a hydrous exothermic composition, the hydrous exothermic composition is preferably an excess hydrous exothermic composition having an easy water value of 0.01 or more.
In the method for producing a hydrous exothermic composition, it is preferable to keep at least the contact step with the oxidizing gas heated to a desired temperature.
The water-containing exothermic composition manufacturing apparatus of the present invention is at least a solid raw material that is continuously weighed using a metering supply device, extends substantially horizontally, and receives the raw material from the metering device near one end. Two or more supply ports for receiving two or more parts and one or more supply ports for one or more water-based liquid raw material supply ports and two or more water-based liquid material supply ports for receiving two or more liquid raw materials. A mixing and conveying apparatus in which a contact portion with an oxidizing gas is formed between the water-based liquid raw material supply port and the water-based liquid raw material replenishment port, and a discharge port is formed near the other end. The raw material of the exothermic composition is dividedly supplied, conveyed while being continuously divided and mixed, then brought into contact with the oxidizing gas, then replenished with water, and further conveyed while mixing to obtain a solid powder. Supply process, solid mixing and conveying process, moisture Feeding step, the contacting step with an oxidizing gas, hydration step, it is preferred to carry out the solid-liquid mixture conveying step in this order.
A hydrous exothermic composition production apparatus is a hydrous exothermic composition production apparatus comprising a metering supply device and a mixing and conveying device, and (a) extends in a substantially horizontal direction from the metering supply device near one end. Two or more supply ports for receiving and supplying powdered solid materials, and one or more supply ports for supplying and supplying aqueous liquid materials and one or more supply ports for supplying liquid materials. A cylindrical casing in which a contact portion with an oxidizing gas is formed between the gas supply port and the discharge port, and a discharge port is formed in the vicinity of the other end, and (b) is provided rotatably inside the cylindrical casing, It is preferable that the mixing / conveying apparatus includes a screw having a maximum width smaller than the inner diameter of the cylindrical casing, and (c) a driving means for driving the screw to rotate.
In the hydrous exothermic composition manufacturing apparatus, the oxidizing gas contact mixing region provided in the cylindrical casing is preferably a region where the upper side of the mixing cylindrical body communicates with the atmosphere.
Moreover, in the hydrous heat generating composition manufacturing apparatus, it is preferable that the screw has one or more paddles.
Further, the hydrous exothermic composition manufacturing apparatus includes a solid raw material supply unit, a solid mixing conveyance unit, a liquid raw material supply unit, an oxidizing gas contact unit, a liquid raw material replenishment unit, and a solid-liquid mixing conveyance unit. It is preferable to be composed of a combination of at least two independent mixing and conveying apparatuses.
In the hydrous exothermic composition manufacturing apparatus, it is preferable that at least the oxidizing gas contact portion of the mixing and conveying apparatus is a belt conveyor.
Moreover, it is preferable that the heating exothermic composition manufacturing apparatus is provided with a heating means in at least a part of the mixing and conveying apparatus.
In the hydrous exothermic composition production apparatus, it is preferable that at least a part of at least one cylindrical casing of the mixing and conveying apparatus is made of at least one selected from a detachable type and an openable type.
The hydrous exothermic composition manufacturing apparatus includes (a) a plurality of raw material tanks that contain iron powder, a carbon component, a reaction accelerator, and water as essential components, and that supply the raw materials of the exothermic composition that generates heat in contact with air; (B) It is preferable that a metering supply (input) device is provided below each of the raw material tanks and measures and supplies the raw material.
Further, in the hydrous exothermic composition continuous production method, the powder supply mixing unit, the liquid supply mixing unit, and the solid-liquid mixing unit (screw mixer) are each selected within an angle of 30 degrees above and below the horizontal. In addition, it is preferable that the exothermic composition is continuously produced by extending at an arbitrary angle.
Further, in the water-containing exothermic composition continuous production method, the solid supply mixing unit and the liquid supply mixing unit are each arranged in any combination of at least one or more, and the exothermic composition is supplied, mixed and conveyed, and continuously. In particular, it is preferable to produce an exothermic composition.
Moreover, in the said water-containing exothermic composition continuous manufacturing method, in the said solid supply mixing part, a liquid supply mixing part, and a solid-liquid mixing part, at least 1 part consists of an apparatus independent of other 2 parts, a solid supply mixing part and liquid It is preferable that each of the exothermic compositions is arranged in the order in which there is a solid-liquid mixing section after the combination of the supply mixing sections so that the exothermic composition is supplied, mixed and conveyed to continuously produce the hydrous exothermic composition.
Further, in the water-containing exothermic composition continuous production method, at least one of the water supply and the water replenishment is performed by an independent mixing and conveying device, and in the independent mixing and conveying device, the exothermic composition powder mixture is generated by gravity. First and second opposite to each other forming a vertical path, connected to a water source and having at least one nozzle directed to the vertical path of the exothermic composition powder mixture flow Water is sprayed on both sides of the flow of the exothermic composition powder mixture falling along the vertical path from at least one of the nozzle sets of the nozzle set, and the sprinkled exothermic composition powder mixture is mixed and conveyed in the next step. It is preferable.
Moreover, in the said hydrous exothermic composition continuous manufacturing method, it is preferable that the mobile water value of the said hydrous exothermic composition is 0.01-50.
Moreover, in the said hydrous heat_generation | fever composition continuous manufacturing method, it is preferable to use the belt conveyor at least 1 place as a means to convey the mixture supplied from the discharge port of the said mixing and conveying apparatus to the following supply port.
Further, in the hydrous exothermic composition continuous production method, the hydrous exothermic composition produced by the hydrous exothermic composition production method is packaged with a breathable packaging material, and the peripheral portion of the hydrous exothermic composition is sealed, It is preferable to process the packaging material into a sealed bag-like material to continuously produce a heating element.
Further, the above-mentioned hydrous heat generating composition continuous production apparatus preferably comprises a mixing and conveying apparatus provided with a shutter that can be opened and closed at the outlet of the mixing cylindrical body.
Further, in the water-containing exothermic composition continuous production apparatus, in the solid supply mixing unit, the liquid supply mixing unit, and the solid-liquid mixing unit, at least one part is an apparatus independent of the other two parts, and the solid supply mixing unit and the liquid It is preferable that each of the exothermic compositions is arranged so as to be supplied, mixed and transported in the order in which there is a solid-liquid mixing part after any combination of the supply mixing parts.
Moreover, in the said hydrous exothermic composition continuous manufacturing apparatus, the said powder supply mixing part, a liquid supply mixing part, a solid-liquid mixing part, and a solid-liquid oxidation mixing part (screw mixer) are each within 30 degrees up and down with respect to the horizontal. It is preferable that the exothermic composition is continuously produced by extending at an arbitrary angle selected within the angle of.
Further, in the water-containing exothermic composition continuous production apparatus, each of the solid supply mixing unit and the liquid supply mixing unit is arranged in any combination of at least one or more, and the exothermic composition is supplied, mixed and conveyed, and continuously. In particular, it is preferable to produce an exothermic composition.
Further, in the water-containing exothermic composition continuous production apparatus, in the solid supply mixing unit, the liquid supply mixing unit, and the solid-liquid mixing unit, at least one part is an apparatus independent of the other two parts, and the solid supply mixing unit and the liquid It is preferable that each of the exothermic compositions is arranged so as to be supplied, mixed and conveyed in the order of the solid-liquid mixing part and the solid-liquid oxidation mixing part after any combination of the supply mixing parts.
Moreover, in the said hydrous heat_generation | fever composition continuous manufacturing apparatus, it is preferable that the solid-liquid oxidation mixing part was integrated into at least 1 part in the said solid supply mixing part, a liquid supply mixing part, and a solid-liquid mixing part.
Further, in the water-containing exothermic composition continuous production apparatus, the liquid supply and mixing device is located below the discharge end of the powder mixing and conveying device and above the supply port of the liquid mixing and conveying device. A vertical path of the flow of the exothermic composition powder mixture is formed between the discharge end of the conveying device and the supply port from the liquid mixing and conveying device, and is connected to a water supply source, each of which is the exothermic composition powder At least one first and second set of nozzles facing each other with at least one nozzle directed at the vertical end of the flow of the mixture, the nozzle falling along the vertical path It is preferable that water is added by watering both sides of the exothermic composition powder mixture to be mixed, and the sprinkled exothermic composition powder mixture is mixed by a liquid mixing and conveying device.
Further, in the hydrous heat generating composition continuous production apparatus, a paddle shaft to be inserted into a hole provided so as to intersect the axis of the rotation shaft of the screw is provided, and a boss portion to which the paddle of the screw is detachably attached is provided. It is preferable to include paddle angle adjusting means capable of adjusting the mounting angle by removably laying on both ends of the paddle shaft.
Further, in the hydrous heat generating composition continuous production apparatus, a gland packing for sealing a bearing is provided at the base end of the shaft of the screw, the casing is divided in the axial direction of the screw, and the base end of the shaft is further provided. Each part has a resin-made seal that can be divided in the axial direction, and each pressing plate part of the pressing plate that is divided in the axial direction in correspondence with each divided casing part. Is preferably attached to the inner wall of each casing part.
Moreover, in the said hydrous heat generating composition continuous manufacturing apparatus, while the inside of a casing is divided into the base end part side and the screw blade side by the said pressing board, it is preferable to provide the mechanism by which this base end part side is pressurized.
Further, the water-containing exothermic composition continuous production apparatus includes a mechanism in which the inside of the casing is partitioned into a base end side and a screw blade side by the mixing device pressing plate, and the base end side is pressurized. preferable.
Moreover, it is preferable that the said hydrous heat generating composition continuous manufacturing apparatus is provided with the opening-and-closing means comprised so that at least one of the side part of the casing of the said mixing conveyance apparatus, a bottom part, a front part, and a rear part can be opened and closed.
Moreover, in the said hydrous exothermic composition continuous manufacturing apparatus, it is preferable to provide a belt conveyor as means for conveying to the next supply port at the discharge port of at least one mixing and conveying device of the mixing and conveying device.
Further, in the hydrous exothermic composition continuous production apparatus, the hydrous exothermic composition is packaged with a breathable packaging material at the most downstream outlet of the hydrous exothermic composition production apparatus, and the peripheral edge of the hydrous exothermic composition It is preferable to seal the part and attach to the main body of the packaging machine structure for processing the packaging material into a sealed bag-like product to form a heating element manufacturing apparatus.

1. According to the apparatus for producing a hydrous exothermic composition of the present invention, by mixing two or more kinds of powders such as a water retaining agent such as iron powder and wood powder, which are raw materials of the heating element, with water while avoiding contact with air. It is possible to produce a warmer that suppresses the oxidation reaction and has a desired exothermic performance. In addition, since the powder is mixed inside a substantially sealed mixing cylinder, there is little dust scattering and a uniform water-containing heat generating composition can be obtained.
2. The device for producing a hydrous exothermic composition with a mixing screw with a paddle according to the present invention can give a complicated movement to a powder as compared with a device combining a mixing screw and a mixing cylinder having a normal shape. The mixing effect of the powder liquid mixture can be further improved, and a uniform hydrous exothermic composition is obtained.
3. The water-containing exothermic composition production apparatus of the present invention is horizontally extended, so that a water-containing exothermic composition can be obtained in which water supply is simple, there is little variation in water between lots per hour, and water is uniformly mixed. .
4). According to the method and apparatus for producing a hydrous exothermic composition of the present invention, all raw materials of the hydrous exothermic composition are continuously fed, mixed, and transported, that is, a powder supply mixing unit and a liquid supply mixing unit. The material required for the screw mixer equipped with the solid-liquid mixing part is continuously supplied by changing the input position, mixed while feeding, mixed roughly, and then mixed in the solid-liquid mixing part. Therefore, it has a wide range of water content, from a hydrous exothermic composition that generates heat immediately upon contact with air, to a hydrous exothermic composition that has excess water and generates heat after the surplus water sits on a water absorbing material, etc. A highly water-containing exothermic composition can be produced continuously and in a short time.
5). An iron powder, a reaction accelerator and water as essential components, a water content of 0.5 to 20% by weight, and a reaction mixture having an easy water value of less than 0.01 indicating an excess water amount are subjected to contact treatment with an oxidizing gas. By using it as a raw material, the reaction activity of the reactive mixture with oxygen is increased, and a mass production method of an active exothermic composition can be achieved.
6). The exothermic composition having a good exothermic rising property can be obtained by the manufacturing method of contacting the oxidizing gas according to the present invention, and warms up twice or more faster than the conventional product not performing the oxidizing gas contact processing.
7). Since the exothermic composition of the present invention has a good exothermic startability, the amount of carbon components such as activated carbon can be reduced by 10 to 20% or more compared to conventional crystals not treated with oxidizing gas, which is advantageous in terms of cost. is there.
8). By preparing the amount of surplus water in the exothermic composition based on the mobile water value (for example, 0.01 end, 0.01-20, over 20-50, etc.), various exothermic compositions with good exothermic startability can be obtained. Therefore, various molding methods can be selected, and manufacturing methods and applications are expanded.
9. The heating element using the exothermic composition of the present invention also has good heat build-up, and has a heat build-up that warms immediately after use from the outer bag during use, and does not have a frustrating feeling that does not warm up easily, and has an excellent feeling of convenience. A heating element can be manufactured.
10. In addition, by making use of moldability, a heating element with a plurality of separate heating parts arranged and fixed apart can be made, fits well to the warmed part of the body, etc., has excellent feeling of use, and is flexible As a result, a heating element having excellent heat generation can be obtained.
l1. The exothermic composition of the present invention has an excellent exothermic startability, warms up twice or more faster than conventional products, and immediately produces a sufficiently exothermic heating element.
12 Since the heat build-up property is good, the stool dose of carbon components such as activated carbon can be reduced by 10 to 20% or more compared to conventional products that do not use activated iron powder.
13. Due to the formability, various methods such as filling method and through-molding method can be adopted, both filling and laminating are possible, and production speed from low speed to high speed can be adopted, so the production system according to the production environment Can be taken.
14 Because of its formability, it can be used in a variety of shapes, from ultra-thin to thick, rectangular, foot-shaped, dumbbell-shaped, dotted, linear, etc., from straight to curved, and from small to large.
15. Since it is excellent in compression workability that can significantly prevent deterioration in heat generation characteristics due to compression of the heat generating composition, it is possible to maintain heat generation for a long time even as an ultra-thin heating element.

Moreover, the hydrous exothermic composition manufacturing apparatus may be provided with a shutter that can be opened and closed at the outlet of the mixing cylindrical body of the hydrous exothermic composition manufacturing apparatus.
Further, by using a cylindrical body having an opening with a cover in the cylindrical casing of the hydrous exothermic composition manufacturing apparatus, cleaning after operation becomes very simple.
Here, in the manufacturing method and the manufacturing apparatus, the cylindrical casing preferably extends substantially horizontally, but it may extend at an arbitrary angle within 30 degrees above and below the horizontal.
In addition, an endless belt such as a belt conveyor is used for transporting the mixture between the mixing and transporting device and the mixing and transporting device, and transporting the exothermic composition between the mixing and transporting device and the downstream heating element manufacturing device, etc. May be.
The exothermic composition manufactured using the hydrous exothermic composition manufacturing method and / or the hydrous exothermic composition apparatus of the present invention is an activated exothermic composition, and the iron powder therein is an active iron powder.
That is, the hydrous exothermic composition manufacturing method and the hydrous exothermic composition device of the present invention are a hydrous exothermic composition manufacturing method and a hydrous exothermic composition manufacturing device that involve contact treatment with an oxidizing gas.
Further, by using a cylindrical casing made of at least one selected from a detachable type and an open / close type for the cylindrical casing (cylindrical body) of the hydrous exothermic composition manufacturing apparatus, cleaning after operation becomes very simple. .

The method for producing a hydrous exothermic composition and the hydrous exothermic composition device of the present invention is a method of continuously dispersing and feeding components into small compartments, and continuously mixing and conveying the components, thereby allowing a stable composition to generate heat or It is a custom-made exothermic composition manufacturing method and manufacturing apparatus in which an exothermic composition containing a moisture amount higher than that is created at a necessary time.
That is, in order to achieve uniform mixing of each component, components are introduced into a small section from a plurality of locations, and the plurality of small spaces are moved while continuously moving the small space divided into a plurality of mixtures. Is a method and apparatus that repeats mixing and conveying to achieve uniformization as a whole, and continuously supplies and mixes necessary materials to produce a high-quality water-containing exothermic composition continuously and in a short time. A hydrous exothermic composition production method and a hydrous exothermic composition production apparatus.
Therefore, according to the method and apparatus for producing a hydrous exothermic composition of the present invention, a powder supply mixing unit, a liquid supply mixing unit, and a solid-liquid mixing unit are provided to supply, mix, and convey all raw materials of the hydrous exothermic composition. The water content ranges from a hydrous exothermic composition that generates heat immediately upon contact with air to a hydrous exothermic composition that has excess water and generates heat after the surplus water sits on a water absorbent or the like. Widely, a high-quality water-containing exothermic composition with little change in composition ratio over time can be produced continuously and in a short time.

The hydrous exothermic composition of the present invention is a hydrous exothermic composition in which iron powder, a carbon component, a reaction accelerator (such as an inorganic electrolyte) and water are essential components and contact treatment with an oxidizing gas is performed.
Furthermore, in addition to the essential components, a water retention agent, a water-absorbing polymer, a hydrogen generation inhibitor, a molding aid, a pH adjuster, an aggregate, a functional substance, a polyoxyethylene alkyl ether nonion, an amphoteric ion, an anion, Cationic surfactants, hydrophobic polymer compounds such as polyethylene and polypropylene, organosilicon compounds such as dimethyl silicone oil, far infrared radiation materials such as pyroelectric materials and ceramics, negative ion generators such as tourmaline, FeCl _{2 and the} like Exothermic aids, metals other than iron such as silicon and aluminum, metal oxides other than iron oxide such as manganese dioxide, acidic substances such as hydrochloric acid, maleic acid and acetic acid, fibrous materials such as pulp, fertilizer components such as urea, Contains at least one selected from an additional component consisting of a humectant such as glycerin and D-sorbitol, a release agent or a mixture thereof. You may have.
The components of the hydrous exothermic composition of the present invention are appropriately selected and used as raw materials for any components of exothermic compositions that have been disclosed in the past or are commercially available or used in known disposable warmers or heating elements. it can.
In addition, the packaging material used for the heating element using the heating composition of the present invention may be any packaging material that has been disclosed in the past, is commercially available, or is used for known disposable warmers or heating elements. It can be appropriately selected and used.

The mixing ratio of the hydrous exothermic composition is not particularly limited, but with respect to 100 parts by weight of iron powder, 1.0 to 50 parts by weight of a carbon component, 1.0 to 50 parts by weight of a reaction accelerator, It is a mixture containing 1.0 to 60 parts by weight of water as an essential component.
Furthermore, you may add the following to the said hydrous heat_generation | fever composition in the following mixture ratio.
That is, with respect to 100 parts by weight of iron powder, water retaining agent 0.01 to 10 parts by weight, water-absorbing polymer 0.01 to 20 parts by weight, pH adjuster 0.01 to 5 parts by weight, hydrogen generation inhibitor 0.01 ~ 12 parts by weight, metals other than iron 1.0-50 parts by weight, metal oxides other than iron oxide 1.0-50 parts by weight, surfactant 0.01-5 parts by weight, hydrophobic polymer compound, bone Materials, fibrous materials, functional materials, organosilicon compounds, pyroelectric materials are each 0.01 to 10 parts by weight, moisturizers, fertilizer components, exothermic assistants are each 0.01 to 10 parts by weight, molding aids, The release agent is 0.001 to 5 parts by weight and 0.01 to 1 part by weight of the acidic substance, respectively. In addition, you may make it mix | blend a magnetic body further and should just determine a mixing | blending ratio suitably as needed.
This blending ratio can also be applied to a reaction mixture and an exothermic mixture. The mobile water value of the reaction mixture is usually less than 0.01.
Moreover, you may make it mix | blend a magnetic body further and should just determine a mixing | blending ratio suitably as needed.

The hydrous exothermic composition of the present invention has a mobile water value of less than 0.01, no excess water, no moldability, and a hydrous heat generating composition with an easily mobile water value of 0.01 or more and less than 14 and surplus. Immediately after the production of the exothermic composition having water, moldability, and leaving in air in a 20 ° C. environment without wind, a moldable excess water exothermic composition that generates heat of 1 ° C. or more within 5 minutes; A water-containing exothermic composition having an easy water value of 14 to 50, surplus water, moldability, but does not generate heat even when it comes into contact with air until a predetermined amount of water is removed from the system by water absorption or the like, There is a surplus water exothermic composition that generates heat only when it is in contact with air (oxygen) after removing excess surplus water by water absorption or warm air drying.
In particular, immediately after the production of the exothermic composition, the moldable excess water exothermic composition that generates heat of 1 ° C. or more within 5 minutes after being left in air at 20 ° C. without air. The water value is preferably from 0.01 to less than 14, more preferably from 0.01 to 13.5, still more preferably from 0.01 to 13, even more preferably from 1 to 13. More preferably, it is 1-12, More preferably, it is 3-12, More preferably, it is 3-11.

The term “to generate heat with a temperature rise of 1 ° C. within 5 minutes after being left in air in a 20 ° C. environment immediately after production” means a ripening period such as 24 hours after production of the exothermic composition. 5 minutes when the exothermic composition is left on a non-water-absorbing material such as a polyethylene film, a polyester film or a sheet in air at 20 ° C. without air immediately after the production of the exothermic composition. The exothermic composition generates heat with a temperature increase of 1 ° C.
In the following exothermic composition temperature rise measurement method, the temperature rise within 5 minutes is preferably 1 ° C or higher, more preferably 10 ° C or higher, still more preferably 20 ° C or higher, and further preferably within 3 minutes. Further, the temperature rise is 10 ° C. or more.
Here, the exothermic composition temperature rise measuring method uses the exothermic composition immediately after production or the exothermic composition molded body, and the sample is in contact with air when measuring under the condition of no wind and ambient temperature of 20 ± 1 ° C. Measure while ready.
1. In the case of the exothermic composition 1) A magnet is provided so as to cover the shape of the punched hole of the mold in the vicinity of the center of the back surface of the support plate made of vinyl chloride (thickness 5 mm × length 600 mm × width 600 mm).
2) Place the temperature sensor on the center of the support plate.
3) A polyethylene film with a thickness of 25 μm × length 250 mm × width 200 mm with an adhesive layer having a thickness of about 80 μm is attached to the support plate via the adhesive layer so that the center of the polyethylene film comes to the sensor.
4) On the central part of the polyethylene film, place a template plate of length 250 mm x width 200 mm with a hole 80 mm long x 50 mm wide x 3 mm high, place a sample near the hole, and place a push-in plate The sample is moved along the template, and the sample is pushed into the punched hole. The sample is scraped along the template surface while being pushed (mold press molding), and the sample is filled into the die. Next, temperature measurement is started except for the magnet under the support plate.
The exothermic temperature is measured using a data collector, measuring the temperature for 10 minutes at a measurement timing of 2 seconds, and determining the heat generation startability with the temperature after 3 minutes.
2. For exothermic composition molded bodies,
1) to 3) are the same as in the case of the exothermic composition.
4) Place the exothermic composition molded body on the center of the polyethylene film,
Start temperature measurement.
The exothermic temperature is measured using a data collector, measuring the temperature at 2 seconds for 10 minutes, and measuring the temperature at 0 minutes, 1 minute, 3 minutes, 5 minutes, 6 minutes, and 7 minutes. The exothermic property is determined at a temperature within 5 minutes.

The raw material for the hydrous exothermic composition of the present invention contains iron powder, a carbon component, a reaction accelerator and water as essential components, and in addition to the essential components, a water retention agent, a water absorbing polymer, a hydrogen generation inhibitor, a molding aid Agents, mold release agents, pH adjusters, aggregates, functional substances, nonionics such as polyoxyethylene alkyl ethers, zwitterionic, anionic and cationic surfactants, hydrophobic polymer compounds such as polyethylene and polypropylene, dimethyl silicone Organosilicon compounds such as oil, far infrared radiation materials such as pyroelectric materials and ceramics, negative ion generators such as tourmaline, exothermic aids such as FeCl2, metals other than iron such as silicon and aluminum, iron oxides such as manganese dioxide Other metal oxides, acidic substances such as hydrochloric acid, maleic acid and acetic acid, fibrous materials such as pulp, fertilizer components such as urea, glycerin and D-sorbitol At least one selected from humectant or additional components consisting of a mixture of equal may contain.
The powder raw material is insoluble in water such as iron powder, and the liquid raw material is liquid such as water or an aqueous solution of a reaction accelerator.
In addition, the component of the raw material of the hydrous exothermic composition of the present invention is appropriately selected from any components of the exothermic composition that has been disclosed in the past or is commercially available or used for known disposable warmers or heating elements. Can be used.

Among the components constituting the exothermic composition of the present invention, the maximum particle size of the solid component excluding the reaction accelerator, the water-soluble substance and water is preferably 1 mm or less, more preferably 500 μm or less, still more preferably 300 μm or less. More preferably, it is 250 micrometers or less, More preferably, it is 200 micrometers or less, More preferably, it is 100 micrometers or less.
In addition, in the components constituting the exothermic composition, the particle size of 80% or more of the water-insoluble solid component excluding the reaction accelerator, the water-soluble substance and water is preferably 300 μm or less, more preferably 250 μm or less. More preferably, it is 200 μm or less, more preferably 150 μm or less, more preferably 90% or more of the particle size is 150 μm or less, and still more preferably 90% or more of the particle size is 100 μm or less.
The moldability and shape retention of the moldable excess water exothermic composition are improved as the particle size of the water-insoluble solid component excluding the reaction accelerator, the water-soluble substance and water is smaller.

The iron powder is not limited, but cast iron iron powder, atomized iron powder, electrolytic iron powder, reduced iron powder, sponge iron powder, and iron alloy powder thereof can be used as an example. Furthermore, these iron powders may contain carbon or oxygen, or may contain other metals, such as iron containing 50% or more of iron. The type of metal contained as an alloy or the like is not particularly limited as long as the iron component acts as a component of the exothermic composition, but examples include metals such as aluminum, manganese, copper, and silicon, and semiconductors. The metal of the present invention includes a semiconductor.
In the iron powder of the present invention, the content of metals other than iron is usually 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the entire iron powder.

The water may be from a suitable source. There are no restrictions on the purity and type.
The water content preferably contains 1 to 70% by weight of the exothermic composition.
In the case of a reaction mixture and an exothermic mixture before contact treatment with an oxidizing gas, 0.5 to 20% by weight of the reaction mixture or the exothermic mixture, more preferably 1 to 20% by weight, still more preferably 3 to 20% by weight. %, More preferably 4 to 15% by weight.

  The carbon component is not limited as long as it contains carbon as a component. Examples thereof include carbon black, graphite, activated carbon, carbon nanotube, carbon nanohorn, fullerene and the like. It may have conductivity by doping or the like.

The reaction accelerator is not limited as long as it can accelerate the exothermic reaction.
Metal halides such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ferrous chloride, ferric chloride, or potassium sulfate, sodium sulfate, magnesium sulfate, copper sulfate, ferrous sulfate, ferric sulfate, etc. Examples of the inorganic electrolyte are as follows.

  The water retaining agent is not limited as long as it can retain water. Examples include wood powder, pulp powder, activated carbon, vermiculite, terra balloon, and fossil.

  The molding aid, in combination with moisture, improves the strength of the water film, strengthens the aggregation between the composition material particles of the exothermic composition such as iron powder, improves the strength of the exothermic composition molded body, There is no limitation as long as the maintenance of this can be strengthened, but there are water-soluble polymers, hydrophilic polymers, inorganic compounds, and the like.

As molding aids, cellulose-based, starch-based, poly (meth) acrylic acid (salt, ester) -based, syrup-based, seaweed, plant mucilage, microbial mucilage, protein-based, polysaccharide-based, organic-based, Examples include inorganic and synthetic polymer molding aids and the like. For example, cellulose derivative-based molding aids such as carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose, ethyl acetate, and hydroxymethyl cellulose, starch-based water-absorbing agents such as dextrin, pregelatinized starch, and starch for processing; Syrups such as acrylate, corn syrup, and mannit syrup, seaweed extracts such as carrageenan and agar, plant resin mucilage such as gum arabic, tantum gum and caraya gum, and mucous substances produced by microorganisms such as xanthan gum, julan gum, pullulan and guardland , Animal proteins such as gelatin, albumin and casein, plant proteins such as soy protein and wheat protein, polysaccharide thickeners such as plant fruit mucous substances such as pectin and arapinogalactan, guar gum, locust peanut gum, tamarin Plant seed mucous substances such as seed gum, tara gum, alginates such as sodium alginate, gum arabic, tragacanth gum, locust pea gum, guar gum, gum arabic, pectin, corn starch, etc., bentonite, montmorillonite, kaolin, sodium silicate, aluminum silicate Inorganic materials such as stearate, polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate emulsion, acrylic sulfonic acid polymer material, poly-N-vinylacetamide, or methylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxypropyl Methylcellulose, methylcellulose, carmellose sodium, carboxyvinyl polymer, ethylene-maleic anhydride copolymer Examples include maleic anhydride copolymers such as coalescence, acrylic acid-starch copolymers, microcrystalline cellulose, N-vinylacetamide copolymers, etc., alone or in combination of two or more.
Conventionally known water-soluble polymers and thickeners can also be used.
The water-soluble cellulose ether described in JP-A-2003-301200 is also useful in the present invention, and the description of this JP-A is also incorporated herein by reference in its entirety.

  The release agent is not limited, but includes lubricating oil composed of mineral oil, synthetic oil, animal and vegetable oil, etc., high viscosity lubricating oil such as grease, natural wax, synthetic wax, silicone oil, fluororesin, stearic acid And stearates and the like.

The water-absorbing polymer is not particularly limited as long as it has a crosslinked structure and has a water absorption ratio of 3 times or more with respect to its own weight. Moreover, what cross-linked the surface may be used. Conventionally known water-absorbing polymers and commercially available ones can also be used.
Examples of the water-absorbing polymer include a crosslinked poly (meth) acrylic acid, a crosslinked poly (meth) acrylate, a crosslinked poly (meth) acrylate having a polyoxyalkylene group, a crosslinked poly (meth) acrylamide, Copolymer cross-linked product of (meth) acrylate and (meth) acrylamide, copolymer cross-linked product of hydroxyalkyl (meth) acrylate and (meth) acrylate, starch-poly (meth) acrylonitrile graft copolymer Examples include saponified products, starch-poly (meth) acrylic acid (salt) graft cross-linked copolymers, polyisobutylene maleic acid (salt) cross-linked polymers, and the like. These may be used alone or in combination of two or more.

The pH adjuster is not limited as long as the pH can be adjusted. There are weak salts of alkali metals or alkaline earth metals, hydroxides, Na ₂ CO ₃ , NaHCO ₃ , Na ₃ PO ₄ , Na ₂ HPO ₄ , Na ₅ P ₃ O ₁₀ , Ca (OH) _2, etc. As an example.

  The hydrogen generation inhibitor is not limited as long as it suppresses the generation of hydrogen. As an example, at least one sentence selected from the group consisting of sulfur compounds, oxidizing agents, alkaline substances, sulfur, antimony, selenium and tellurium is composed of two or more kinds. Examples of sulfur compounds include compounds with alkali metals and alkaline earth metals, metal sulfides such as calcium sulfide, metal sulfites such as sodium sulfite, and metal thiosulfates such as sodium thiosulfate.

  The aggregate is not particularly limited as long as it is useful as a filler and / or useful for making the exothermic composition porous. Fossil coral (coral fossil, weathered reef coral, etc.), bamboo charcoal, Bincho charcoal, silica-alumina powder, silica-magnesia powder, kaolin, crystalline cellulose, colloidal silica, pumice, silica gel, silica powder, mica powder, clay, talc, Examples include synthetic resin powders and pellets, foamed synthetic resins such as foamed polyester and polyurethane, algae, alumina, and fiber powder.

  Examples of the fibrous material include, for example, plant fibers (cotton, wood pulp, etc.), animal fibers (wool, goat hair, etc.), mineral fibers (asbestos, etc.), and synthetic fibrous materials. Examples thereof include semi-synthetic fibers (acetate, triacetate, oxide acetate, promix, chlorinated rubber, hydrochloric acid rubber, etc.), metal fibers, carbon fibers, and glass fibers. Also, polyolefins such as high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, etc., polyester, polyvinylidene chloride, starch, polyvinyl alcohol or polyvinyl acetate, single fibers such as copolymers or modified products thereof, or these A core-sheath composite fiber having a resin component in the sheath can be used.

  The fibrous material preferably has an average fiber length of 0.1 to 50 mm, more preferably 0.2 to 20 mm.

The functional substance may be any substance as long as it has some function such as medicinal effect and aroma. Perfumes, herbs, herbs, herbal medicines, transdermal drugs, pharmaceutically active substances, fragrances, lotions, emulsions, poultices, fungicides, antibacterial agents, bactericides, deodorants or deodorants, magnetic substances, etc. As an example.
Furthermore, specific examples of functional substances include acidic mucopolysaccharides, chamomiles, horse chestnuts, vitamin E, nicotinic acid derivatives, blood circulation promoters such as alkaloid compounds; horse chestnuts, flavone derivatives, anthocyanidins, Swelling improvers such as vitamin P, goldfish, silanol, terminaria, mayus; aminophylline, tea extract, caffeine, xanthene derivative, inosit, dextran sulfate derivative, horse chestnut, escin, anthocyanidin, organic iodine compound, hardwood leather, horsetail, Slimming agents such as mannenrou, ginseng, hyaluronidase; analgesics such as indomethacin, dl-camphor, ketoprofen, shoga extract, red pepper extract, methyl salicylate, glycol salicylate; Chromatography, rosemary, citron, Jenipa, peppermint, eucalyptus, rosewood, include perfumes orange etc., it can be used one or more kinds.

  The percutaneously absorbable drug is not particularly limited as long as it is percutaneously absorbable. For example, skin stimulants, analgesic anti-inflammatory agents such as salicylic acid and indomethacin, central nervous system agents (sleep sedatives) , Antiepileptics, neuropsychiatric agents), diuretics, antihypertensives, lotus vasodilators, antitussives, antihistamines, arrhythmic agents, cardiotonic agents, corticosteroids, local anesthetics, and the like. These drugs are used alone or in combination of two or more as required.

  Examples of the humectant include polyols such as glycerin, ceramides, and collagens.

In the manufacturing method using the hydrous exothermic composition and / or the hydrous exothermic composition apparatus of the present invention, a uniform hydrous exothermic composition can be obtained without being classified over time, with a small change in composition ratio, and easily. By making contact with an oxidizing gas with a dynamic water value of 0 or less and a water content of 0.5 to 20% by weight based on the total weight, pits and oxide films are formed on the surface of the iron powder within a short time. Is estimated to occur. As a result, a water-containing exothermic composition can be obtained that comes into contact with air and has a fast onset of heat generation and a high rate of heat generation.
The water content before contact with the oxidizing gas of the present invention is preferably 0.5 to 20% by weight, more preferably 0.5 to 15% by weight, even more preferably 1 to the total weight. -7% by weight, more preferably 2-6% by weight.

  The water | moisture content in this invention means aqueous solution, such as water or reaction promoter (electrolytes, such as salt) aqueous solution.

The mechanism by which the heat build-up property is remarkably improved is not understood in detail even though the hydrous exothermic composition, in particular, the excess water exothermic composition having an easy-moving water value of 0.01 or more has surplus due to the oxidizing gas treatment. However, by oxidizing gas treatment,
1) Pits and the like are generated on the surface of the iron powder, the surface area is increased, and the moisture retention is increased.
2) A heat generation accelerator or water adheres to the oxide film, cracks or grooves formed on the iron surface and activates the iron surface against the oxidation reaction.
3) It is presumed that the exothermic composition treated with oxidizing gas is activated against oxidation, for example, by activating the iron surface by generating specific iron oxide on the iron powder surface, or a combination thereof. The present invention has been developed and completed based on these.

The method for analyzing the thickness of the iron oxide film of the active iron powder is Auger electron spectroscopy, and the method for measuring the amount of wustite is X-ray analysis.
In the Auger electron spectroscopy, the ratio of the peak intensity (Io) of O (oxygen) to the peak intensity (Ii) of Fe (Io) when sputtering with Ar at a sputtering rate of 11 nm / min in terms of Fe in the depth direction. / Ii) refers to a portion where 0.05 or more. Therefore, the thickness of the iron-containing film of iron on the surface of the iron powder is a distance in terms of Fe from the surface of the iron powder to a depth where (Io / Ii) is 0.05. Measurement conditions are sputtering time: 15 minutes, sputtering speed: 11 nm / min (Fe conversion). As the sputtering time of the Auger electron spectroscopy elapses, Io decreases and Ii increases. The thickness of the iron oxide film can be calculated by converting the sputtering time from the iron powder surface to the depth at which (Io / Ii) is 0.05.

The amount of wustite is an X-ray intensity ratio based on the following formula from the integrated intensity of the peak of the 110 plane of iron (αFe) and the integrated intensity of the peak of the 220 plane of FeO (wustite) using an X-ray analyzer. As a percentage.
Wustite amount (%) = 100 × (KFeO / KαFe)
Integral intensity of KFeO: FeO (wustite) 220 face peak KαFe: Integral intensity of 110 face peak of iron (αFe) Iron powder having an iron oxide film other than iron powder (carbon component, reaction accelerator) If the mixture is prepared using a mixture containing water, water, etc., the iron powder may be separated from the mixture after preparation with a magnet or the like and measured as a sample. In addition to the exothermic composition, when analyzing the exothermic composition or exothermic composition molded body in the exothermic body, in a nitrogen atmosphere, disperse the exothermic composition or exothermic composition molded body in ion-exchanged water substituted with nitrogen, A measurement sample is obtained by separating iron powder with a magnet and drying it under a nitrogen atmosphere.

The active iron powder is such that at least a part of the surface of the iron powder is covered with an iron oxide film, one of which has a thickness of 3 nm or more, and at least a central region of the active iron powder and It is an active iron powder having a region of an iron component not containing oxygen in at least one region selected from a region below the iron oxide film.
The thickness of the iron oxide film which is an oxygen-containing film covering the surface of the iron powder is not limited as long as it is 3 nm or more using Auger electron spectroscopy, but is usually 3 nm or more, preferably 3 nm to 100 μm. More preferably 30 nm to 100 μm, still more preferably 30 nm to 50 μm, still more preferably 30 nm to 1 μm, still more preferably 30 nm to 500 nm, still more preferably 50 nm to 300 nm. By making the thickness of the iron-containing film of iron 3 nm or more, the iron-containing film of iron can exert the effect of promoting the oxidation reaction, and contact the oxidizing gas such as air to start the oxidation reaction immediately. Can do.
If the thickness of the iron oxygen-containing coating is 100 μm or more, the heat generation time may be shortened, but it can be used depending on the application.
The other is an active iron powder having wustite, and the amount of wustite is usually 2 to 50% by weight, preferably 5.01 to 50% by weight, as an X-ray intensity ratio with iron. Preferably it is 5.01 to 40 weight%, More preferably, it is 6 to 40 weight%, More preferably, it is 7 to 30 weight%, More preferably, it is 7 to 25 weight%. Even if it exceeds 50% by weight, the heat buildup is good, but the heat generation duration is shortened. If it is less than 2% by weight, the heat build-up property becomes dull.

  In addition, the active iron powder of the present invention seems to have an iron oxide film which is a film made of iron containing oxygen such as iron oxide, hydroxide, oxyhydroxide on the surface of the iron powder, In the exothermic composition to which other components are added, the surface is at least partially oxidized, and a reaction active part mainly composed of oxide, hydroxide, chlorine ion, hydrogen ion, etc. is generated, and an exothermic reaction occurs. Property and hydrophilicity are improved, and formability, heat build-up property, and utilization rate of iron are remarkably improved. Since the surface of hydrated iron oxide (amorphous) has chemical activity and adsorbs other substances such as water, the partially oxidized iron powder has hydrophilicity, improves moldability, and has an iron oxide coating. It seems that the iron oxide compound is effective in improving the heat buildup.

The hydrous exothermic composition manufacturing method and the hydrous exothermic composition continuous device of the present invention continuously mix and convey the components by continuously dispersing and feeding the components into small compartments, and the moisture amount capable of generating heat or more It is a custom-made exothermic composition manufacturing method and a hydrous exothermic composition manufacturing apparatus that are prepared when the exothermic composition contained is used.
That is, in order to achieve uniform mixing of each component, components are introduced into a small section from a plurality of locations, and the plurality of small spaces are moved while continuously moving the small space divided into a plurality of mixtures. Is a method and apparatus that repeats mixing and conveying to achieve uniformization as a whole, and continuously supplies and mixes necessary materials to produce a high-quality water-containing exothermic composition continuously and in a short time. A hydrous exothermic composition production method and a hydrous exothermic composition production apparatus.
Therefore, according to the method and apparatus for producing a hydrous exothermic composition of the present invention, a powder supply mixing unit, a liquid supply mixing unit, and a solid-liquid mixing unit are provided to supply, mix, and convey all raw materials of the hydrous exothermic composition. By performing continuously, the water content range is wide, from the hydrous exothermic composition that generates heat immediately upon contact with air to the hydrous exothermic composition that has surplus water and generates heat after the surplus water sits on a water absorbent or the like. A high-quality water-containing exothermic composition can be produced continuously and in a short time.

As the continuous metering supply device used in the present invention, any device can be used as long as it can continuously supply a constant amount, and examples thereof include a powder metering device, a liquid metering device, and a liquid metering device. .
Although there is no restriction | limiting in a powder measurement supply apparatus, A screw feeder, a vibration feeder, a rotary feeder, a measurement hopper etc. are mentioned as an example. At least one selected from
The liquid metering supply device and the liquid metering replenishing device are not limited, but examples include a communication pipe tank type device, a tubing pump type device, a pump pumping type device, and a pressurized needle ejection type device.
For screw feeders, it can be set to an arbitrary supply amount by controlling the number of rotations of the screw, the opening of the gate, etc., and for the vibration feeders, by controlling the frequency, amplitude, etc. it can. The measurement of the supply amount can be obtained from the supply volume of the powder or the change in the weight of the powder raw material hopper or feeder.

  In the present invention, the mixing device and the conveying device can also be used as one mixing and conveying device. As a mixing and conveying device, the powder raw material can be efficiently mixed and can be conveyed while maintaining a mixed state, and in particular, the powder raw materials of exothermic compositions having different bulk specific gravity can be mixed uniformly, There is no limitation as long as the powder mixture of the exothermic composition has a mechanism for feeding in the conveying direction while stirring so as not to classify, but a mixing and conveying apparatus comprising a screw and a cylindrical body (that is, a cylindrical casing) An example is a belt conveyor with a mixing function.

As a mixing and conveying apparatus consisting of a screw and a cylindrical body (that is, a cylindrical casing), for example, a screw conveyor with a paddle provided with blades on the screw portion of the screw conveyor, a baffle plate on the coil portion of the coil screw conveyor, or An example is a coil screw conveyor with paddles provided with blades.
As a belt conveyor with a mixing function, a baffle plate and a belt conveyor are combined, and a baffle belt conveyor having a mixing function and a conveying function, or a belt conveyor with a paddle, that is, a paddle conveyor having blades provided on a rotating shaft in a trough. Is given as an example. The belt conveyor with a mixing function is preferably a belt conveyor with a mixing function with a cover from the viewpoint of preventing the raw material of the exothermic composition from scattering. As the belt conveyor with a mixing function, a conventionally disclosed belt conveyor or a known belt conveyor or a belt conveyor with a mixing function can be appropriately selected and used.
In addition, any material can be used without particular limitation as long as it has the above-described mixing and conveying function.

  As a method for installing the mixing and conveying apparatus, it is extended almost horizontally. However, “almost horizontally” means that the apparatus is installed horizontally at the conveyance direction or at an arbitrary angle within 30 degrees above and below the horizontal. preferable. The angle is preferably within 30 degrees in the vertical direction, more preferably within 20 degrees in the vertical direction, more preferably within 10 degrees in the vertical direction, further preferably within 5 degrees in the vertical direction, and further preferably within 3 degrees in the vertical direction. It is.

  The length of the mixing and conveying apparatus is not limited as long as the exothermic composition can be produced, but is preferably 0.25 to 7 m, more preferably 0.25 to 5 m, still more preferably 1 to 5 m, and further Preferably it is 1-4 m, More preferably, it is 1-3 m.

  Further, the inner diameter of the cylindrical casing (that is, the cylindrical body) is not limited, but is preferably 25 to 500 mmφ, more preferably 25 to 300 mmφ, still more preferably 50 to 250 mmφ, and further preferably. Is 50-200 mmφ.

  Although there is no restriction | limiting as a rotational speed of a mixing conveyance apparatus, Preferably it is 20-2000 rpm.

Hereinafter, a method for producing a hydrous exothermic composition and an apparatus for producing a hydrous exothermic composition of the present invention will be described.
First, the water-containing exothermic composition manufacturing apparatus of the present invention will be described in detail.
FIG. 1 (a) is a cross-sectional explanatory view showing an apparatus for producing a hydrous heat generating composition for a heating element according to an embodiment of the present invention, and FIG. 1 (b) is a perspective view showing a breathable cover having a ventilation portion or a breathable surface. FIG. 1 (c) is a cross-sectional view showing the relationship between the mixing cylindrical body and the mixing screw, and FIGS. 2 to 11 are the hydrous exothermic composition manufacturing apparatus for a heating element, paddle, mixing cylindrical body and mixing screw, and mixing, respectively. It is a figure which shows another Example of this invention which concerns on a cylindrical body.

  FIG. 1 shows a hydrous exothermic composition manufacturing apparatus (hereinafter simply referred to as a manufacturing apparatus) 1. In addition, in order to make it easy to understand, a part of the mechanism of the mixing cylindrical body is omitted. Further, a sample collection port 58 with a shutter is provided between the liquid exothermic composition material supply port 11 and the oxidizing gas (air etc.) intake port 12. Further, a temperature detector 53 is provided before and after the intake port for the oxidizing gas (air or the like). Thus, in principle, it is preferable to provide the sample-collecting port 58 with a shutter and the temperature detector 53 in the hydrous exothermic composition production apparatus layer 1.

  The manufacturing apparatus 1 extends substantially horizontally, supplies iron powder and other additives (water retention agent, water, etc.) that are raw materials of the exothermic composition to the cylindrical casing 7, and inside the cylindrical casing 7, A device for mixing, stirring and discharging. In the upper part of the upstream side of the cylindrical casing 7, a first tank for storing iron powder, a second tank for storing activated carbon as a carbon component, a third tank for storing wood powder as a water retention agent, and a water-absorbing polymer are stored. A fourth tank and a fifth tank containing a mixture of sodium sulfite and slaked lime are provided (24). Further, on the middle stream side, a sixth tank (25A) for containing water and a seventh tank (25B) for containing a sodium chloride aqueous solution as a liquid raw material are provided. A screw 8 is rotatably provided inside the cylindrical casing 7. Further, a motor 18 for rotating the screw 8 is provided at the upstream end of the cylindrical casing 7, and a discharge port 13 of the cylindrical casing 7 is provided downstream of the cylindrical casing 7. . In the vicinity of the outlets opened to the lower part of the first tank to the seventh tank, weighing / feeding devices 26 and 27 conventionally used for weighing and charging the raw materials in the respective tanks are arranged. Yes.

Cylindrical casing 7 consists of straight pipes, such as an acrylic pipe, a stainless steel pipe, and an iron pipe, and the opening of the upstream end and the downstream end is sealed by the upstream lid and the downstream lid, respectively. On the upstream side, the first exothermic supply port to the fifth supply port, which are the powder exothermic composition raw material supply port 10, are formed, and on the middle stream side, the moisture which is the liquid exothermic composition raw material supply ports 11A and 11B. A sixth supply port for the supply port and a seventh supply port for the sodium chloride supply port are formed, and the first to seventh supply ports are connected to the first supply port through the powder or liquid metering supply devices 26 and 27, respectively. The outlets of the first tank to the seventh tank are connected to each other. Furthermore, although not shown, a coupling for rotatably supporting the mixing screw is fixed to the upstream end portion. On the other hand, a discharge port 13 having a size smaller than the inner diameter of the mixing cylinder is formed slightly upstream from the downstream end. The discharge port 13 may be provided with a shutter that can be opened and closed.
In addition, mixing is being performed inside the cylindrical casing 7 via the sixth supply port 11A and the seventh supply port 11B, which are the liquid heating composition raw material supply ports 11 at the upper and lower middle sides of the cylindrical casing 7. Since salt water can be directly injected into the powder, it is not necessary to consider loss of salt water, and optimal salt water can be adjusted. The saline to be injected may be simple water. In this case, a reaction accelerator such as an inorganic electrolyte such as salt may be added as a powdery powder from the powder heating composition raw material port 10.

  In addition, although the present Example demonstrated and demonstrated the example which inject | pours water from a 6th supply port, this invention is not limited to this, Water is supplied to the 2nd tank by the side of the wood flour which is the said water retention agent. The water retention agent may be preliminarily made to contain water by injection. In this case, it is necessary to consider moisture loss.

  Moreover, although the present Example demonstrated and demonstrated the example of the cylindrical casing 7 of a straight pipe, this invention is not limited to this, You may change a shape suitably. For example, if the cylindrical casing 7 has a tapered shape, that is, if the inner diameter decreases toward the downstream side, the powder accumulated on the downstream side of the cylindrical casing 7 is guided to the root of the screw. Or the mixture moving between the cylindrical casing 7 and the screw can be brought back toward the screw center again to further improve the mixing state.

  In this embodiment, the cylindrical casing 7 is described with an example in which the inner diameter is the same on the upstream side and the downstream side. However, the present invention is not limited to this, and the cylindrical casing 7 You may form so that an internal diameter may become small as it goes downstream, and the said mixing cylindrical body and the mixing screw 8 are the outermost part of the inner surface of the said cylindrical casing 7, and the outermost part of the screw 8 as it goes downstream. As described above, the powder can be brought closer to the screw 8 side. Therefore, as another example, for example, the above-described operation can be achieved even by combining a straight tubular casing 7 and a screw whose outer diameter increases toward the downstream side.

Moreover, a straight pipe is adopted as the cylindrical casing 7, and a mixed state can also be improved by fixing a cylindrical baffle plate whose thickness increases toward the downstream side to the inner peripheral surface thereof by adhesion or the like. it can.
In this case, the baffle plate may be provided only in the vicinity of the downstream side of the mixing cylindrical body, or may be provided in a plurality of locations including the central portion on the middle stream side and the vicinity of the upstream side.

  The first tank to the fifth tank 24 employ a tapered hopper that becomes thinner as it goes downward. In the present embodiment, the example of seven tanks has been described. However, the present invention is not limited to this, and when an additive other than those described above is added, a tank is appropriately added. Alternatively, some components may be combined to reduce the tank as appropriate.

  In addition, the cylindrical casing 7 is provided with a shutter-equipped discharge port having two discharge ports, a first discharge port and a second discharge port, and the first and the latter hydrous heat generating composition are discharged from the first discharge port and disposed of. Then, the high-quality hydrous exothermic composition in the intermediate period may be discharged from the second discharge port and conveyed to the downstream packaging mechanism.

  FIG. 1C shows a cross-sectional view of an example of the present invention in which the screw shaft 9 is shifted from the center of the cylindrical casing 7 in the direction of gravity. The screw 8 has a screw thread spirally extending around the shaft 9 so that the maximum width is smaller than the inner diameter of the cylindrical casing 7 in order to obtain a clearance allowing movement of the powder or solid-liquid mixture. For example, stainless steel or iron with chrome plating can be used. The pitch of the screw 8 is appropriately selected depending on the degree of mixing. Further, the pitch between the upstream side and the downstream side may be changed.

  A commercially available motor is employed as the motor 18 for driving the screw 8 to rotate, and the rotational speed of the motor is controlled by an inverter (control panel).

  When performing a mixed manufacturing operation using the manufacturing apparatus 1 of FIG. 1, first, the first supply port to the fifth supply port 10 on the upstream side are fed into the sealed cylindrical casing 7 from the first tank to the fifth tank. Through the metering / feeding device 26, iron powder, activated carbon as a carbon component, wood flour as a water retention agent, a water-absorbing polymer, and a mixture of sodium sulfite and slaked lime are weighed and charged. Further, saline or water is injected through the sixth supply port 11A which is a water injection port. Inside the cylindrical casing 7, the screw 8 is rotated by a motor 18 in a direction in which the mixture moves toward the downstream side. In this case, mixing occurs by dropping another raw material added from the supply port to the raw material moving from the upstream side. Furthermore, since the moving speed toward the downstream side of the wall surface of the cylindrical casing 7 and the wall surface of the screw 8 and other portions is different, they are mixed uniformly.

Further, as shown in FIG. 2, the paddle 17 is attached to the screw 8 or the baffle plate or the taper is installed to return to the upstream side of the mixing unit. The body repeats two movements: 1) a movement that is lifted and raised from below by the thread of the screw 8 and 2) a movement that falls between the screw 8 and the inner wall of the cylindrical casing 7. , And evenly mixed.
At this time, since the powder is mixed inside the sealed mixing cylinder, it hardly scatters to the outside of the mixing cylinder. Moreover, since there is almost no time to touch air (particularly, oxygen), the exothermic composition generates less heat in the downstream packaging mechanism (hopper and packaging mechanism body) (not shown) after mixing. When mixing of the exothermic composition is completed, if the shutter is opened, the powder can be easily transferred to the hopper of the packaging mechanism by freely falling through the discharge port.

  In the screw 8 shown in FIG. 2, the plate paddle 17 is alternately formed on the upstream side, and the bolt-type rod paddle 17 is alternately formed on the downstream side. However, the present invention is not limited to this, It goes without saying that these types and sizes (width, length, and thickness) may be appropriately changed independently.

  FIG. 2 shows the manufacturing apparatus 1 in which a plurality of paddles 17 are disposed at the peripheral end of the screw 8. In the case of the manufacturing apparatus 1 in FIG. 2, the powder and the water-containing exothermic composition are forcibly formed by the paddle 17 between the screw 8 and the inner wall of the cylindrical casing 7 together with the operations 1) and 2). Movement in the circumferential direction is given, and as a result, the mixing effect of the powder and the hydrous exothermic composition can be further improved.

  As long as the paddle 17 can give the movement of the powder or the hydrous heat generating composition in the circumferential direction, the shape and the number of the paddles 17 may be appropriately changed. For example, if a substantially wedge-shaped or substantially rectangular paddle 17 that extends in the axial direction of the screw 8 is adopted as the shape, it is possible to give more powder and a water-containing exothermic composition to the movement in the circumferential direction. . Further, regarding the number of sheets, if there is at least one paddle 17, circumferential movement can be imparted to the powder and the water-containing exothermic composition. More preferably, if paddles 17 having different shapes or a plurality of paddles 17 are arranged alternately, it is possible to more effectively impart circumferential movement to the powder. A boss part to which the paddle 17 is detachably attached may be provided at a desired position of the rotating shaft of the screw 8 or the screw part, or a paddle angle adjusting means capable of adjusting the attachment angle may be provided.

  Moreover, although the paddle 17 of FIG. 2 is being fixed perpendicularly with respect to the screw 8, you may attach so that an angle can be changed. If the angle of the paddle 17 can be changed, it is possible to flexibly cope with various conditions such as the particle size and viscosity of the powder and the water-containing exothermic composition. The direction of movement and the like can also be adjusted, and more suitable powder and water-containing exothermic composition can be mixed.

7A shows the surface (plate) paddle 17, FIG. 7B shows the bolt-type rod paddle 17, and FIG. 7C shows the rod (band) paddle 17.
7D and 7E are partially enlarged sectional views of the paddle 17 attached to the screw 8. FIG.

  In FIG. 5, a paddle 17 is formed on the screw 8, one powder exothermic composition raw material supply port 10 and one liquid exothermic composition raw material supply port 11 are provided to the manufacturing apparatus 1, and a powder exothermic composition raw material is provided. The manufacturing apparatus 1 is provided with a gas injection nozzle (gas supply port 59) of nitrogen, air, or the like so that a raw material bridge does not occur in the vicinity of the drop port inside the cylindrical casing 7 of the supply port 10. More suitable powder and water-containing exothermic composition can be mixed by the action of gas injection and paddle.

FIG. 3 includes a screw 8 with a paddle 17 and a cylindrical casing 7 having functions of supplying powder (powder-based powder) raw material, powder mixing and conveying, supplying water-based liquid raw material, and solid-liquid mixing and conveying. Mixing device (second unit) and a mixing device (second unit) comprising a screw 8 with a paddle 17 and a cylindrical casing 7 having functions of oxidizing gas processing ventilation, replenishment of water-based liquid raw material, and solid-liquid mixing and conveyance ) And a hydrous exothermic composition production apparatus comprising two machines.
The connecting portion between the first discharge port 13 and the second raw material supply port is covered with a cover.
Solid liquid-liquid mixing is sufficiently performed by the latter mixing device to obtain a uniform water-containing exothermic composition.
By strengthening the solid-liquid mixing section, the production rate of the hydrous exothermic composition is also improved.

  FIG. 4 includes a screw 8 with a paddle 17 and a cylindrical casing 7 having functions of supplying powder (powder-based powder) raw material, powder mixing and conveying, supplying water-based liquid raw material, and solid-liquid mixing and conveying. A mixing device (first device), a mixing device (including a screw 8 with a paddle 17 and a cylindrical casing 7 having a function of oxidizing gas processing ventilation and solid-liquid mixing and conveyance, and a heating device by a heater 52 ( (2nd machine) and water-containing heat generation consisting of three machines: a screw 8 with a paddle 17 and a mixing device (third machine) comprising a cylindrical casing 7 having functions of replenishment of water-based liquid raw material and solid-liquid mixing and conveyance 1 is an example of a composition manufacturing apparatus 1. Each function can be sufficiently performed, and a uniform hydrous exothermic composition can be produced at high speed.

  FIG. 5 is an example of a mixing device that has a function of oxidizing gas processing aeration and solid-liquid mixing and conveyance, and has a heating device by supplying heated gas, and includes a screw 8 with a paddle 17 and a cylindrical casing 7. .

FIG. 6 shows a state in which the hydrous exothermic composition discharged from the production apparatus is placed on the belt conveyor 30 and conveyed to the next step. Examples of the next step include a water-based liquid raw material supplying step, an oxidizing gas treatment venting step, a water-based liquid raw material replenishing step, a molding step, a breathable packaging step and a non-breathable packaging step. In addition, in the manufacturing apparatus 1 composed of a plurality of mixing apparatuses with divided or enhanced functions, the connection between the mixing apparatuses is made from the first machine to the second machine, from the second machine to the third machine, etc. May be used.
Further, a gas supply port 59 for supplying a gas such as air or nitrogen is provided in the vicinity of the outlet of the raw material supply port in the cylindrical body of the mixing apparatus for preventing bridging of the raw material of the exothermic composition. A gas such as air or nitrogen is preferably injected from the gas supply port 59.
Similarly, the other mixing apparatus of the present invention may be provided with a gas supply port.

FIG. 8A shows a notch type of the screw 8, and the blade 9 of the screw is provided with a plurality of notch portions 61 at regular intervals.
A paddle 17 is attached to the notch 61. The paddle 17 may have a certain angle.
Further, the end portion of the notch 61 may be bent almost in parallel with the screw shaft 9 to form the paddle 17. When the paddle (scraping plate) 17 is provided in the notch 61 of the blade 9A of the screw 8, the stirring and mixing ability of the object to be processed (reaction mixture, exothermic mixture, exothermic composition) can be improved, which is excellent. Quality products can be obtained stably. Further, by appropriately combining the notch 61 of the blade 9A of the screw 8 and the paddle (scraping plate) 17, the entire area of the apparatus can be made a stirring region, and adhesion and solidification of the exothermic composition can be prevented. Can do.
FIG. 8B is a cross-sectional view taken along the line ZZ.

FIG. 9A shows a U-shaped cylindrical casing 7, which is an upper detachable type in which the screw shaft 9 is provided by shifting in the direction of gravity from the center of the cylindrical casing 7 and an opening cover 21 is provided in the upper opening. 3 is a cross-sectional view of a U-shaped cylindrical casing 7. FIG. This is because the upper part is made removable so that cleaning after manufacture can be performed easily.
FIG. 9B is a cross-sectional view of the cylindrical casing 7 with the upper opening cover 21 of FIG. 9A removed.
FIG. 9C shows a U-shaped cylindrical casing 7, which has an opening in the upper part and the lower part, and is provided by shifting the screw shaft 9 in the direction of gravity from the center of the upper open cylindrical casing 7. Further, the detachable open / close type U-shaped cylindrical casing 7 has an upper opening portion of the cylindrical casing 7 made detachable, provided with an opening cover 21 and further provided with an opening / closing portion on the side portion. The opening / closing means of the lower opening is made to be an opening / closing type, one side of the hinge 57 is attached to the opening cover 21, the other side is attached to one side of the lower opening of the cylindrical casing 7, and the other side of the opening cover 21 is attached. Sectional drawing of an example of this invention fastened with the fastener 23 on the other one surface side of the lower opening part of the cylindrical casing 7 is shown.

FIG. 10 is a perspective view of a cylindrical casing 7 having an opening / closing part at the upper part and the lower part, with the upper detachable type and the lower part being an opening / closing type.
It makes cleaning and maintenance after production easier.
The screw shaft 9 is provided so as to be shifted from the center of the upper open cylindrical casing 7 in the direction of gravity. Further, the upper opening of the cylindrical casing 7 is detachable, the opening cover 21 is provided, and the opening and closing means for the lower opening is opened and closed. The other side of the hinge 57 is attached to one side of the lower opening of the cylindrical casing 7, and the other side of the opening cover 21 is attached to the other side of the lower opening of the cylindrical casing 7. It is fastened with a fastener 23 on one side.

The belt conveyor includes a belt conveyor having a conveying function and a mixing belt conveyor having a conveying function and a mixing function. The mixing belt conveyor is combined with a baffle plate, and a baffle plate belt capable of mixing raw materials of the exothermic composition. Examples include conveyors and belt conveyors with paddles.
When a belt conveyor having only a conveying function is used for the contact portion with the oxidizing gas, the reaction mixture, which is a raw material mixture of the exothermic composition before the contact treatment with the oxidizing gas, is thinly and / or on the belt conveyor. The layers may be stacked loosely and transported so that they can be sufficiently in contact with the oxidizing gas.

  FIG. 11 is a perspective view of a belt conveyor 29 with a paddle, which is an example of a solid-liquid mixing apparatus. A pair of pulleys 47, 48 are pivotally supported on the apparatus base, and a belt of flexible rubber is stretched between the pulleys 47, 48 to form a belt conveyor 30. The pulley 48 is driven to rotate to rotate the belt.

The belt that runs on the upper side of the belt conveyor 30 is provided with a plurality of rollers 36 on both sides of the belt conveyor 30 along the longitudinal direction of the belt conveyor 30 to support the belt. A trough portion is formed by being bent upward by a roller 36 supporting the side line.
On the inner side of the trough portion of the upper belt, a rotating shaft obtained by writing several sets of paddles 31 at regular intervals is suspended from the lower ends of a pair of suspension members 37 at both ends, and is freely rotatable. One end thereof is supported by a drive motor 18 so as to be rotated.

  On the charging side of the belt conveyor 30, a bottomless container-shaped supply rod is suspended on the upper belt, and the hydrous exothermic composition is charged into the container. As the belt conveyor 30 moves, the hydrous exothermic composition moves toward the discharge port. The paddle rotating body is attached to the rotating shaft as a set of four plate-like paddles 31 in the middle. The mixture is stirred and mixed by the rotating paddle 31 group. After sufficient mixing and stirring, the hydrous exothermic composition is discharged from the outlet to the next step.

  For example, the water-containing exothermic composition roughly mixed from the powder / liquid supply / mixing device or the liquid supply / mixing device may be transferred to the belt conveyor 29 (FIG. 11) with a paddle and replaced with the solid-liquid mixing device.

FIG. 12 is a sectional view of a belt conveyor 30 with a cover 42 and a paddle 31 as an example of a solid-liquid mixing apparatus. The upper part of the apparatus is separated from the outside by a cover 42. If the air-permeable cover 41 is used as the cover 41, the cover 41 can be used as an apparatus for performing oxidizing gas treatment.
A pair of pulleys are pivotally supported on the apparatus base, and a belt of flexible rubber is stretched between the pulleys to form a belt conveyor 30. The belt is driven by a drive motor to rotate the discharge pulley. Run around.
The belt of the trough portion is supported by a roller 36 and a pair of side rollers 36 at the bottom, and is formed in an arc shape. Further, the upper side line portion is formed by a pair of rollers 36 and the outer edge of the belt is outside. Is trying to expand.
The relationship between the upper belt curved in a trough shape and the paddle 31 is arranged so that the tip of the paddle 31 is close to the inner surface of the bottom of the belt formed in a substantially arc shape like the roller 36 without contacting. The suspension member is fixed to the apparatus main body independently of the base of the belt conveyor 30.

  For example, the powder-liquid supply mixing apparatus or the water-containing exothermic composition roughly mixed from the liquid supply mixing apparatus is transferred to a belt conveyor 29 (FIGS. 11 and 12) with a paddle, and this conveyor is replaced with a solid-liquid mixing apparatus or an oxidizing gas. There are no particular restrictions on the relationship between the center of the casing and the center of the screw used as a processing device, as long as the mixture or composition is mixed and conveyed, but it is displaced to the center of the casing and lowers the center of the screw, i.e. Shifting in the direction of weight is preferable for mixed conveyance.

  The manufacturing apparatus 1 of the present invention can improve the uniformity of component mixing and the production speed by dividing each function and combining a plurality of mixing apparatuses having the function. Further, since the manufacturing apparatus 1 is a horizontal type, it is possible to easily divide functions and increase the size of the apparatus as compared with a vertical manufacturing apparatus.

In the manufacturing apparatus 1 of the present invention, the necessary amount can be obtained by appropriately changing the specifications of the cylindrical casing 7 and the screw 8, for example, by changing the rotational speed of the screw 8, the pitch of the screw 9, the inner diameter of the cylindrical casing 7, or the like. The hydrous exothermic composition can be continuously produced at the required speed. Moreover, you may use suitably the screw which changed the depth of a groove | channel, such as a shallow groove screw, a deep groove screw, and the multistage groove screw in which the depth of a groove changes with positions.
Even when the functions of the manufacturing apparatus 1 of the present invention are divided, those described in the manufacturing apparatus 1 of the present invention can be used.

Further, in order to increase the mixing effect, a screw shaft in which a baffle plate whose outer peripheral portion is fixed to the inside of the mixing tube is formed in the cylindrical casing 7 and a slit is formed in the vicinity of the baffle plate is provided. It is formed so that the thread is periodically interrupted, such as by providing a part in which no thread is formed in one region of the manufacturing apparatus 1 or the screw 8 in which one or more sheets are arranged substantially vertically in the center. The manufacturing apparatus 1 can also be used.
Further, a plurality of guide members having projecting portions projecting inwardly inside the cylindrical casing 7 are arranged, the interval between the screw 8 and the inner wall of the cylindrical casing 7 is reduced, By partially changing the maximum width of the eight threads, the threads may be formed such that the large width portion and the small width portion are separated from each other.

  The exothermic composition supply apparatus for storing and supplying to the molding apparatus the hydrous exothermic composition discharged from the outlet of the mixed cylindrical body as a molding and sealing mechanism on the downstream side of the manufacturing apparatus 1 configured as described above. Connected to the lower end of the exothermic composition supply device, a molding device for molding the hydrous exothermic composition into a molded body, and the molded body is enclosed between a non-breathable base material and a breathable coating material A heating device manufacturing apparatus is configured by attaching a sealing device for manufacturing the heating element and a packaging device for sealing the heating element with a non-breathable packaging material.

  The functions in the manufacturing apparatus described above can be appropriately selected and combined.

  Next, the method for producing a hydrous exothermic composition of the present invention will be described using the hydrous exothermic composition producing and producing apparatus of FIG.

The hydrous exothermic composition manufacturing process for continuously producing the hydrous exothermic composition by continuously supplying and mixing the raw materials, the predetermined amount of the hydrous exothermic composition raw material is measured from each source tank, and the mixed cylindrical body This is carried out by supplying to a predetermined supply port and mixing.
Powdered powder raw materials such as iron powder, activated carbon, water retention agent, reaction accelerator (inorganic electrolyte, etc.), water-absorbing polymer, hydrogen generation inhibitor, etc. and aqueous solution of sodium chloride, which is a reaction accelerator (inorganic electrolyte, etc.) Used as a liquid raw material. The powder raw material is a powdery raw material. Moreover, even if it is a powder raw material, when it is a solution such as water, it is handled as a liquid raw material. Water and a reaction accelerator (inorganic electrolyte, etc.) aqueous solution are liquid raw materials.

In the process of producing the hydrous exothermic composition, the driving device 18 is operated, and the screw in the cylindrical casing 7 is rotated at a predetermined rotational speed so as to send the input raw material from the upstream side having the supply port to the downstream side having the discharge port. Let me.
Next, the metering / feeding device 26 passes through the first supply port to the seventh supply port 10, 11 on the upstream side from the first tank to the seventh tank 24, 25 A, 25 B to the inside of the sealed cylindrical casing 7. 27, iron powder, activated carbon as a carbon component, wood powder as a water retention agent, a water-absorbing polymer, and a mixture of sodium sulfite and slaked lime are weighed and fed to the first supply port of the mixed cylindrical body. Iron powder, activated carbon at the second supply port, wood powder at the third supply port, water-absorbing polymer at the fourth supply port, a mixture of sodium sulfite and slaked lime at the fifth supply port, and water at the sixth supply port A sodium chloride aqueous solution is supplied to the mouth in this order.
As a result, mixing of powdery powders (hereinafter referred to as “powder”) occurs in a small section formed by the wall of the cylindrical casing 7 and the pitch of the screw 9. It is supplied to the mouth and supplied to the raw material or raw material mixture to be mixed, and is supplied and mixed in a small section, so that the mixing efficiency is good.
When a powder mixture is formed and conveyed for a certain distance while being mixed with powder, saline is supplied from the sixth supply port, and solid-liquid mixing starts. That is, in the cylindrical casing 7, the mixture moves toward the downstream side by rotating the screw 9 by the motor 18. In this case, mixing occurs by dropping another raw material added from the supply port to the raw material moving from the upstream side. Furthermore, since the moving speed toward the downstream side of the wall surface of the cylindrical casing 7 and the wall surface of the screw 8 and other portions is different, powders and powder liquid are uniformly mixed. Further, it is transported downstream while repeating solid-liquid mixing, and contacted with an oxidizing gas such as air (12), contact processing with oxidizing gas is performed, transported downstream while repeating solid-liquid mixing, The saline solution is supplied from the 7 supply port 11B, conveyed to the downstream side while repeating solid-liquid mixing, and becomes a uniform hydrous exothermic composition having a predetermined movable water value, and is discharged from the discharge port.
At this time, since the powder is mixed inside the cylindrical casing 7, the powder hardly scatters outside the cylindrical casing 7. When mixing of the exothermic composition is completed, the powder can be easily transferred to the next step by free-falling through the discharge port 13. In addition, the first and second outlets with shutters are provided, and the first and second stage hydrous exothermic compositions are discharged from the first outlet, disposed of, and disposed of in the middle period. The item may be discharged from the second discharge port and conveyed to the downstream packaging mechanism.

  Further, if the manufacturing apparatus 1 having the screw 8 with the paddle 17 shown in FIG. 2 is used, the powder is returned to the upstream of the mixing section and the powder charged into the cylindrical casing 7 is moved in two ways, that is, 1 A mixture of powder and solid-liquid mixture by repeating a) a movement that is lifted and lifted from below by the paddle 17 of the screw 8; and 2) a movement that falls between the screw 8 and the inner wall of the cylindrical casing 7. Are further uniformly mixed to obtain a uniform hydrous exothermic composition.

  The required length of the cylindrical casing 7 can be shortened by using a paddle, a baffle plate or the like and increasing the mixing efficiency.

  Even if it manufactures using each hydrous exothermic composition manufacturing manufacturing apparatus of FIGS. 2-7, since it is a manufacturing apparatus into which each process was divided | segmented, the same hydrous exothermic composition is obtained.

The hydrous exothermic composition obtained by the present invention has an easy water value of less than 0.01 and no moldability, but contains an exothermic heat composition that generates heat upon contact with air. A water-containing exothermic composition that has moldability and generates heat upon contact with air, has an easy-moving water value of more than 20 and 50 or less, and has moldability, but a predetermined amount of water is absorbed by water absorption or the like. A hydrous exothermic composition that does not generate heat even if it comes into contact with air until it is removed to the outside is obtained.
When an excellent exothermic property is desired with a hydrous exothermic composition having an easy water value of 0.01 or more and 20 to 20, an easy water value of 0.01 or more and less than 14 is preferable. More preferably, it is 0.01-13.5, More preferably, it is 0.01-13, More preferably, it is 0.01-12, More preferably, it is 1-12, More preferably, it is 3-12 It is.

Hereinafter, the manufacturing method of the exothermic mixture by the oxidizing gas contact treatment of the reaction mixture, the exothermic mixture, the exothermic composition, and the embodiment of the exothermic body will be described in detail.
The present invention uses an iron powder, a reaction accelerator and water as essential components, a water content of 0.5 to 20% by weight, and a reaction mixture having an easy water value of less than 0.01 indicating an excess water amount. The production rate of the mass production can be established by increasing the reaction speed of the contacted soot with the property gas and increasing the temperature of the reaction mixture to 1 ° C or more within 10 minutes. . By shortening the time to reach the predetermined temperature or higher, proper activation can be performed, and unnecessary oxidation of the iron powder soil can be prevented. In addition, the exothermic composition having an easy water value of 0.01 to 50 is moderately sticky by adding carbon and the like to the exothermic mixture produced by contacting the reaction mixture with an oxidizing gas and adjusting the water content. It has excellent moldability and can be applied to molding methods such as a mold-through molding method and a casting molding method, thereby producing heating elements of various shapes. In particular, exothermic compositions having an easy water value of 0.01 to 13.5 start an exothermic reaction as soon as they come into contact with air, have an excellent exothermic rising property, and have an excellent moldability. It is.

The oxidizing gas contact treatment method of the reaction mixture comprises iron powder, a reaction accelerator and water as essential components, a water content of 0.5 to 20% by weight, and a mobile water value of less than 0.01. There is no particular limitation as long as the temperature of the reaction mixture is increased to 1 ° C. or more by contact treatment with an oxidizing gas.
1. A method for producing an exothermic mixture containing iron powder, a reaction accelerator and a reaction mixture of water in an oxidizing gas atmosphere, self-exothermic reaction, partially oxidizing the iron powder, and iron powder having an iron oxide film on the surface;
2. A method for producing an exothermic mixture in which a reaction mixture of iron powder, reaction accelerator, acidic substance and water is subjected to a self-exothermic reaction in an oxidizing gas atmosphere;
3. A method for producing an exothermic mixture in which a reaction mixture of iron powder, reaction accelerator, carbon component and water is subjected to a self-exothermic reaction in an oxidizing gas atmosphere;
4). A method for producing an exothermic mixture in which a reaction mixture of iron powder, reaction accelerator, acidic substance, carbon component and water is subjected to a self-exothermic reaction in an oxidizing gas atmosphere;
5. A method for producing an exothermic mixture containing partially oxidized iron powder, wherein the reaction mixture or the exothermic mixture according to any one of 1 to 4 contains a component other than the above components, and the method according to any one of 1 to 4 is performed. ,
A method for producing an exothermic mixture, wherein the method according to any one of 6.1 to 5 is performed in an environment heated to 10 ° C. or more from the environmental temperature,
The method according to any one of 7.1 to 6 is performed by blowing an oxidizing gas, and the oxidizing gas heated to 10 ° C. or more from the ambient temperature by the method described in the method 8.7 for producing exothermic mixture A method for producing an exothermic mixture by blowing,
A method for producing an exothermic composition in which an oxidizing gas contact treatment is performed until the maximum temperature, which is the highest point of temperature increase due to an exothermic reaction, is exceeded by the method according to any of 9.1 to
10. A method for producing an exothermic mixture, wherein the oxidizing gas contact treatment is performed until the temperature exceeds a maximum temperature due to an exothermic reaction and further falls by at least 10 to 20 ° C. from the maximum temperature by the method according to any one of 10.1 to 8. ,
11. In the method described in any one of 11.1 to 8, the oxidizing gas contact treatment is performed until the maximum temperature, which is the highest temperature rise due to the exothermic reaction, is exceeded, and then the oxidizing gas is shut off, and at least the reaction mixture is included. A method for producing an exothermic composition to be held until the temperature of the object drops at least 10 to 20 ° C. from the maximum temperature,
12. A method for producing an exothermic mixture in which the reaction mixture or the exothermic mixture described in any of 12.1 to 5 is heated to 1 ° C. or higher in an oxidizing gas environment. The manufacturing method of the exothermic mixture which makes the temperature of the raw material mixture after contact with oxidizing gas 30-30 degreeC.
Etc. are mentioned as an example.
Furthermore, another component may be added to the exothermic mixture, and further an oxidizing gas treatment may be performed to form an exothermic mixture.
In addition, the environment of the reaction mixture at the time of the oxidizing gas contact treatment is restricted if it is brought into contact with the oxidizing gas in an environment of 0 ° C. or more and the temperature rise of the reaction mixture is set to 1 ° C. within 10 minutes. However, when it is performed in an open system, it may be present in a container without a lid, or it may be in a state where an oxidizing gas such as air enters through a breathable sheet-like material such as a nonwoven fabric.
The oxidizing gas contact treatment may be any of stirring, non-stirring, flowing or non-flowing, and may be a batch type or a continuous type.
The hydrous exothermic composition of the present invention is a exothermic composition containing water and generating heat upon contact with air, and corresponds to at least one of the following 1) to 4).
1) a hydrous exothermic composition using the exothermic mixture produced by the method described in any one of 1 to 12 above as an exothermic composition raw material,
2) A hydrous exothermic composition obtained by adding other components to the hydrous exothermic composition of 1),
3) A hydrous exothermic composition obtained by adjusting the water content of the hydrous exothermic composition according to either 1) or 2),
4) Water-containing exothermic composition in which moisture is replenished after the temperature of the raw material mixture after contact with the oxidizing gas is 30 ° C. to 60 ° C. Also, the timing of adding components other than the essential components and the timing of moisture adjustment There is no order restriction.
The reaction mixture of the present invention is a mixture of raw materials before contact with an oxidizing gas,
An exothermic mixture is a mixture of raw materials after contact with an oxidizing gas.

  Here, the water content in the reaction mixture, which is a mixture of impact materials before contact with the oxidizing gas, or in the exothermic mixture before further oxidizing gas treatment is usually 0.5 to 20% by weight, preferably 1 It is -15 weight%, More preferably, it is 2-10 weight%, More preferably, it is 3-10 weight%, More preferably, it is 6-10 weight%.

  The temperature of the reaction mixture after contact with the oxidizing gas is not limited as long as the temperature increase is 1 ° C. or higher, but is preferably 1 to 80 ° C., more preferably 1 to 70 ° C., and still more preferably. It is 1-60 degreeC, More preferably, it is 1-40 degreeC.

  The environmental temperature at the time of contact between the reaction mixture and the oxidizing gas is not limited as long as the temperature of the reaction mixture rises above a predetermined level, but is preferably 0 ° C or higher, more preferably 0 to 250 ° C, still more preferably. Is 10 to 200 ° C, more preferably 20 to 150 ° C, still more preferably 25 to 100 ° C, and further preferably 25 to 50 ° C.

  There is no limitation as long as the time during which the temperature rise of the reaction mixture at the time of contact between the reaction mixture and the oxidizing gas is 1 ° C. or more is within 24 minutes, but it is preferably 1 second to 24 minutes, more preferably 1 Second to 20 minutes, more preferably 1 second to 15 minutes, more preferably 1 second to 14 minutes, still more preferably 1 second to 10 minutes, and even more preferably 1 second to 7 minutes. Further, it is preferably 1 second to 5 minutes, more preferably 2 seconds to 5 minutes, still more preferably 2 seconds to 3 minutes, and further preferably 2 seconds to 1 minute.

  The temperature of the oxidizing gas is not limited as long as the environmental temperature is maintained.

The oxidizing gas may be any gas as long as it is oxidizing, but oxygen gas, air, or a mixed gas of an inert gas such as nitrogen gas, argon gas, helium gas and oxygen gas can be given as an example. . The mixed gas is not limited as long as it contains oxygen, but preferably contains 10% or more oxygen gas. Of these, air is particularly preferable.
If desired, catalysts such as platinum, palladium, iridium and their compounds can be used.
The oxidation reaction can be carried out in an oxidizing gas atmosphere with stirring, optionally under pressure and / or under ultrasonic irradiation. The optimum conditions for the oxidation reaction may be appropriately determined experimentally.

There is no restriction | limiting in the usage-amount of oxidizing gas, What is necessary is just to adjust with the kind of oxidizing gas, the kind and particle size of iron powder, a moisture content, processing temperature, a processing method, etc.
In the case of an open system, there is no limit as long as the required oxygen amount can be taken in. In order to prevent scattering of the reaction mixture and contamination of dust, the surroundings may be surrounded by a breathable material such as a nonwoven fabric or a woven fabric.
For example, when air is used in a manner in which an oxidizing gas is blown, the amount of air is preferably 0.01 to 1000 liters / minute, more preferably 0. It is 01-100 liter / min, More preferably, it is 0.1-50 liter / min. In the case of another oxidizing gas, the oxygen concentration may be converted based on the case of air.
If desired, a peroxide may be added. Examples are hydrogen peroxide and ozone.
In addition, when the treatment with the oxidizing gas is performed in an open system, it is also useful to perform forced ventilation with a fan or the like.

  Here, the state of the reaction mixture or the exothermic mixture at the time of the contact treatment with the oxidizing gas may be either a stationary state, a moving state, or a fluidized state by stirring or the like as long as the iron powder is partially oxidized, and is appropriately selected. do it. In addition, there is no restriction on the environment during the contact treatment with the mixed oxidizing gas at the time of mixing the components of the reaction mixture, the exothermic mixture and the exothermic composition and at the time of moisture adjustment, and the blowing of oxidizing gas in the oxidizing gas atmosphere Etc. are mentioned as an example.

The easy water value is a value indicating the amount of surplus water that can move out of the exothermic composition in the water present in the exothermic composition. This easy water value will be described.
No. with 8 lines written at 45 degree intervals radially from the center point under normal temperature and normal pressure. 2 (JISP 3801 type 2) filter paper is placed on a stainless steel plate, and a template of length 150 mm × width 100 mm having a hollow cylindrical hole with an inner diameter of 20 mm × height of 8 mm is placed at the center of the filter paper. Place the sample in the vicinity of the hollow cylindrical hole, move the push plate along the mold plate, put the sample into the hollow cylindrical hole while pushing the sample, and scrape the sample along the mold plate surface (mold push molding) .
Next, in order to prevent an exothermic reaction during the measurement, a non-water-absorbing 70 μm polyethylene film is placed so as to cover the hole, and further, a thickness of 5 mm × length of 150 mm × width of 150 mm is placed thereon. Place a stainless steel plate and hold for 5 minutes. Thereafter, the filter paper is taken out, and the trace of water or aqueous solution soaking is read in millimeters as the distance from the circumference that is the edge of the hole of the hollow cylinder to the tip of the soaking, along the radial line. Similarly, the heel separation 18 is read from each line to obtain a total of 8 values. Each of the eight values read (a, b, c, d, e, f, g, h) is taken as a measured moisture value. The arithmetic average of the eight measured moisture values is taken as the moisture value (mm) of the sample. In addition, the moisture content for measuring the true moisture value is the blended moisture content of the exothermic composition or the like corresponding to the weight of the exothermic composition or the like having an inner diameter of 20 mm and a height of 8 mm, and only water corresponding to the moisture content. The same measurement was performed and the same calculation was made the true moisture value (mm). The value obtained by dividing the moisture value by the true moisture value and multiplying by 100 is the easy water value. That is,
Easy water value = [moisture value (mm) / true water value (mm)] × 100
Five points are measured for the same sample, the five ready water values are averaged, and the average value is taken as the ready water value of the sample. In addition, when measuring the mobile water value of the exothermic composition in the heating element, the moisture content for measuring the true moisture value is calculated by calculating the moisture content of the exothermic composition from the moisture content measurement using an infrared moisture meter of the exothermic composition. Based on this, the amount of water necessary for the measurement is calculated, and the true water value is measured and calculated from the amount of water.
In addition, the exothermic composition having at least a movable water value of 0.01 or more and less than 14 and particularly 0.01 to 13.5 is placed a non-water-absorbing 70 μm polyethylene film so as to cover the hole, and further thereon. Instead of placing a stainless steel flat plate having a thickness of 5 mm, a length of 150 mm, and a width of 150 mm, the exothermic composition of the present invention undergoes an exothermic reaction during measurement and becomes incapable of measurement.

The moldability is a heat-generating composition molded body that is a molded body of a heat-generating composition in the shape of a punch hole by mold-through molding using a punch mold having a punch hole, and at least after molding including mold separation, It is sandwiched between the base material and the covering material, and the peripheral portion of the exothermic composition molded body can be sealed.
In the case of a heat-generating composition having moldability, a heat-generating composition molded body can be prepared by a mold forming method such as through-molding or casting.
If there is moldability, the heat-generating composition molded body is covered with at least the covering material, and the shape is maintained until the sealing portion is formed between the base material and the covering material. Since so-called sesame which is a broken piece of the exothermic composition is not scattered in the seal portion, the seal can be sealed without being broken. The presence of sesame causes poor sealing.
1) As a measuring device,
On the upper side of the endless belt that can run, a stainless steel mold (a plate with a thickness of 2 mm × length 200 mm × width 200 mm with a punched hole in which the four corners of the length 60 mm × width 40 mm are processed into R5 in the center) can be fixed. A plate is arranged, and magnets (thickness 12.5 mm × length 24 mm × width 24 mm, two magnets in parallel) are arranged on the lower side of the endless belt opposite to the plate.
The magnet covers an area larger than the area (40 mm) of the maximum cross section with respect to the direction of travel of the punching hole of the mold, and the area in the vicinity thereof.
2) As a measurement method,
A stainless steel plate having a thickness of 1 mm × length of 200 mm × width of 200 mm is placed on an endless belt of the measuring device, a polyethylene film of thickness of 70 μm × length of 200 mm × width of 200 mm is placed thereon, and a stainless steel mold is further formed thereon. Put.
Then, after fixing the scraping plate at a position of 50 mm from the advancing side end of the endless belt of the punching hole of the mold, 50 g of the exothermic composition is placed near the scraping plate between the scraping plate and the punching hole, The belt is moved at 1.8 m / min to fill the punching hole of the mold while scraping off the exothermic composition. After the mold has completely passed through the scraping plate, the running of the endless belt is stopped. Next, the mold is removed, and the exothermic composition molded body laminated on the polyethylene film is observed.
3) As a judgment method,
In the peripheral portion of the exothermic composition molded body, there is no collapsed piece of the exothermic composition molded body having a maximum length exceeding 800 μm, and the number of collapsed pieces of the exothermic composition molded body having a maximum length of 300 μm to 800 μm is 5 or less. In this case, the exothermic composition has formability.
This is an essential property for the exothermic composition used in the molding method. Without this, it is impossible to manufacture a heating element by a molding method.

As a method for measuring the temperature rise of the exothermic composition, the exothermic composition is allowed to stand for 1 hour in a non-breathable outer bag in an ambient temperature of 20 ± 1 ° C.
1) A magnet is provided in the vicinity of the center of the back surface of a vinyl chloride support plate (thickness 5 mm × length 600 mm × width 600 mm) of the support base with legs so as to cover the shape of the punched hole of the mold.
2) Place the temperature sensor on the center of the support plate.
3) Affixed to the support plate through the adhesive layer so that the center of the polyethylene film with a thickness of 254 m × length 250 mm × width 200 mm is about 80 μm thick with the adhesive layer.
4) Remove the exothermic material from the outer bag.
5) On the center of the polyethylene film, place a template plate of length 250 mm x width 200 mm with a hole 80 mm long x 50 mm wide x 3 mm high, place a sample near the hole, The sample is moved along the template, and the sample is pushed into the punch hole. The sample is scraped along the template surface while being pushed in (mold press molding), and the sample is filled into the die. Next, temperature measurement is started except for the magnet of the support plate.
The exothermic temperature is measured by using a data collector, measuring the temperature for 10 minutes at a measurement timing of 2 seconds, and determining the heat generation startability with the temperature after 3 minutes.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
Example 1
The exothermic composition manufacturing apparatus comprising a cylindrical casing having a length of 3.2 m × inner diameter of 150 mm and a screw having a length of 3.7 m × outer diameter of 130 mm × shaft diameter of 50 mm in FIG. 1 was used, and air was used as the oxidizing gas. .
In an environment of 25 ° C., the exothermic composition manufacturing apparatus is driven, and reduced iron powder (particle size of 300 μm or less) and activated carbon (particle size of 300 μm or less) are supplied from the raw material tank to the exothermic composition manufacturing apparatus via a metering supply device. 100 parts by weight of reduced iron powder (particle size of 300 μm or less) and 3.5 parts by weight of activated carbon (particle size of 300 μm or less) were supplied to the powder exothermic composition raw material supply port.
Next, 5 parts by weight of 11% saline corresponding to a mobile water value of less than 0.01 was supplied from the raw material tank to the powder exothermic composition raw material supply port via a metering supply device to obtain a reaction mixture. .
Next, 42 parts by weight of 11% saline is supplied from the raw material tank to the powder exothermic composition raw material supply port through the metering supply device to the exothermic mixture that has been subjected to the oxidizing gas contact treatment in the breathable part. Then, the mixture was transported to obtain an exothermic composition having an easy water value of 8.
The temperature rise of the exothermic mixture subjected to the oxidizing gas contact treatment in the air permeable part was 5 ° C. The mobile water value of the reaction mixture collected from the sample collection port with the shutter was 0 or less.

(Comparative Example 1)
The reaction mixture similar to that of Example 1 was not subjected to oxidizing gas contact treatment, and 11% by weight of saline was added to the reaction mixture to obtain an exothermic composition having a mobile water value of 8.

About the exothermic composition of Example 1 and Comparative Example 1, the exothermic composition exothermic test was done.
The exothermic composition of Example 1 was about 35 ° C. after 1 minute and about 55 ° C. (average of 5) after 3 minutes.
The exothermic composition of Comparative Example 1 was 23 ° C. after 1 minute, and the temperature after 3 minutes was 28 ° C. (average of 5). Comparative Example 1 was significantly slower in heating rate than Example 1. .

(Example 2)
The exothermic composition manufacturing apparatus of FIG. 1 uses the exothermic composition manufacturing apparatus consisting of a cylindrical casing of length 3.2 m × inner diameter 150 mm and a screw of length 3.7 m × outer diameter 130 mm × shaft diameter 50 mm in FIG. Air was used as the oxidizing gas.
In an environment of 25 ° C., the exothermic composition production apparatus is driven. From the reduced iron powder, activated carbon, wood powder, water-absorbing polymer, slaked lime, sodium sulfite, and raw material tank, the exothermic composition production apparatus is Reduced iron powder (particle size of 300 μm or less), activated carbon (particle size of 300 μm or less), reduced iron powder (particle size of 300 μm or less) 100 parts by weight, activated carbon (particle size of 300 μm or less) 3 per minute to each powder heating composition raw material supply port 0.5 parts by weight, 2.3 parts by weight of wood flour (particle size of 150 μm or less), 2.3 parts by weight of a water-absorbing polymer (particle size of 300 μm or less), 0.5 parts by weight of slaked lime, and 0.7 parts by weight of sodium sulfite were supplied. .
Next, 4 parts by weight of 11% saline corresponding to a mobile water value of less than 0.01 was supplied from the raw material tank to the powder exothermic composition raw material supply port via a metering supply device to obtain a reaction mixture. .
Next, 45 parts by weight of 11% saline is supplied from the raw material tank to the powder exothermic composition raw material supply port through the metering supply device to the exothermic mixture that has been subjected to the oxidizing gas contact treatment in the breathable part. The exothermic composition having a mobile water value of 10 was obtained by mixing and conveying.
The temperature rise of the exothermic mixture subjected to the oxidizing gas contact treatment in the air permeable part was 6 ° C. The mobile water value of the reaction mixture collected from the sample collection port with the shutter was 0 or less.

  When the exothermic composition exothermic test of the exothermic composition was performed, the same result as in Example 1 was obtained.

  Further, when the moldability test of the exothermic composition was conducted, the exothermic composition was below the molding degree, and even when the punching die was separated from the exothermic composition molded body, the exothermic composition molded body was not deformed, and the exothermic composition was There was no broken piece of the exothermic composition molded body in the periphery of the molded body.

(A) It is sectional drawing which shows the manufacturing apparatus of the hydrous heat_generation | fever composition concerning one embodiment of this invention. (B) It is a perspective view which shows the oxidizing gas (air etc.) intake port concerning one embodiment of this invention. (C) It is sectional drawing which shows the relationship between the cylindrical casing concerning one embodiment of this invention, and a screw. It is sectional drawing which shows the manufacturing apparatus of the hydrous heat_generation | fever composition concerning other embodiment of this invention. It is sectional drawing which shows the manufacturing apparatus of the hydrous heat_generation | fever composition concerning other embodiment of this invention. It is sectional drawing which shows the manufacturing apparatus of the hydrous heat_generation | fever composition concerning other embodiment of this invention. It is sectional drawing which shows the heating oxidation processing apparatus of the manufacturing apparatus of the hydrous exothermic composition concerning other embodiment of this invention. It is sectional drawing which shows the manufacturing apparatus of the hydrous heat_generation | fever composition concerning other embodiment of this invention. It is a side view which shows the paddle pattern concerning one embodiment of this invention. It is the side view (a) and sectional drawing (b) which show the screw with a paddle concerning one embodiment of this invention. (A) It is sectional drawing which shows the relationship between the upper open type casing and screw which concern on other one Embodiment of this invention. (B) It is sectional drawing which provided the upper open type casing cover. (C) It is sectional drawing of the upper part and side part opening-closing type | mold casing which provided the fastener and the cover. It is a perspective view which shows the upper part and side part opening-and-closing type manufacturing apparatus of the hydrous heat_generation | fever composition concerning other embodiment of this invention. It is a perspective view which shows the conveyor with a paddle for oxidizing gas contact processing of the manufacturing apparatus of the hydrous heat_generation | fever composition concerning other embodiment of this invention. It is sectional drawing of the trough part of the upper belt of the conveyor with a paddle for oxidizing gas contact processing of the manufacturing apparatus of the hydrous heat generating composition concerning other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Water-containing exothermic composition manufacturing apparatus 2 Screw type mixing apparatus 3 Powder liquid supply mixing apparatus 4 Powder supply mixing apparatus 5 Liquid supply mixing apparatus 6 Solid liquid mixing apparatus 7 Cylindrical casing 7A blade 8 Screw 9 Screw shaft 9A blade 10 Powder Body exothermic composition raw material supply port 11A, 11B Liquid exothermic composition raw material supply port 12 Dioxide gas (air etc.) intake port 13 Discharge boil 14 Powder supply mixing unit 15 Liquid supply mixing unit 16 Solid-liquid supply mixing unit 17 Paddle 18 Drive motor 19 Upper detachable casing 20 Upper detachable / lower / side opening / closing casing 21 Opening cover (cover)
22 Breathable cover 23 Fastener 24 Powder raw material storage tank 25A, 25B Water or aqueous solution tank 26 Powder metering device 27 Liquid metering device 28 Joint 29 Belt conveyor with paddle 30 Belt conveyor 30A paddle rotor 30B paddle rotor shaft 31 Paddle 32 Handle 33 Frame 34 Belt movement direction 35 Belt side edge 36 Roller 37 Hanging member 40 Bearing 42 Cover 43 Solid-liquid mixed exothermic composition 44 Solid-liquid mixed exothermic composition supply port 45 Solid-liquid mixed exothermic composition Flow 46 Solid-liquid mixed exothermic composition leak prevention device 47 Pulley 48 Pulley 50 In air 51 Ventilation part
52 heaters 53 temperature detectors 54 heaters 55 heated fluid supply ports 56 heated fluid discharge ports 57 hinges, hinges 58 sample collection ports with shutters 59 gas supply ports 60 packing 61 notches

Claims (13)

  A method for producing a hydrous exothermic composition for producing a raw material for an exothermic composition comprising iron powder, a carbon component, a reaction accelerator and water as essential components, wherein the powder raw material is disposed in a laterally arranged cylindrical body. A step of measuring and supplying, a step of conveying the powder raw material while mixing, a step of measuring and supplying a liquid raw material, a step of contacting with an oxidizing gas, a step of supplying a liquid, and the powder and the liquid A method for producing a hydrous exothermic composition, comprising sequentially carrying out the steps of conveying while mixing.   The water content of the exothermic composition raw material is 0.5 to 20% by weight, and the mobile water value indicating the excess water amount is less than 0.01, the liquid replenishing step, and the liquid replenishing step, The method for producing a hydrous exothermic composition according to claim 1, wherein the temperature is raised by 1 ° C. or more from the temperature of the iron powder in the subsequent contact step with the oxidizing gas.   The method for producing a hydrous exothermic composition according to claim 1 or 2, wherein the iron powder and the carbon component are supplied from an independent raw material supply port of the powder.   The method for producing a hydrous exothermic composition according to any one of claims 1 to 3, wherein water is replenished after the temperature of the mixture after contact with the oxidizing gas is set to 30 to 60 ° C.   The method for producing a hydrous exothermic composition according to claim 4, wherein the hydrous exothermic composition obtained by the method is an excess hydrous exothermic composition having a mobile water value of 0.01 or more.   The method for producing a hydrous exothermic composition according to claim 1, wherein at least the contact step with the oxidizing gas is maintained at a predetermined temperature.   A plurality of powder raw material metering supply ports and a plurality of liquid raw material metering supply ports are provided in the longitudinal direction of the cylindrical body disposed in the lateral direction, and the raw material mixing device and the conveying device are provided between the supply ports. And a hydrous exothermic composition manufacturing apparatus comprising an oxidizing gas supply device.   The hydrous heat generating composition producing apparatus according to claim 7, wherein each of the supply ports is provided in a plurality of independent apparatuses.   The water-containing exothermic composition manufacturing apparatus according to claim 7 or 8, wherein the oxidizing gas supply device is formed by communicating an upper portion of the cylindrical body with the atmosphere.   The hydrous exothermic composition manufacturing apparatus according to any one of claims 7 to 9, wherein the mixing device is constituted by a screw.   The water-containing exothermic composition manufacturing apparatus according to claim 10, wherein the screw has one or more paddles.   The hydrous heat generating composition producing apparatus according to any one of claims 7 to 11, wherein the conveying device is a belt conveyor.   The apparatus for producing a hydrous exothermic composition according to claim 12, wherein a heating means is provided in at least a part of the conveying device.

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