JP3344686B2 - Ink-like or cream-like heat-generating composition, heating element using the same, and method for producing this heating element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultra-thin heating element by forming an exothermic composition in the form of an ink or a cream and transferring the ink or the exothermic composition to a packaging material at a high speed. Can be produced, and the exothermic composition can be distributed in a uniform thickness in the bag, and a part or all of the exothermic composition is fixed in the bag to prevent its movement, The present invention relates to an ink-like or cream-like heat-generating composition which is flexible and extremely excellent in usability, a heating element using the composition, and a method for producing the heating element.

[0002]

2. Description of the Related Art In recent years, as a so-called disposable color trouser, a flat bag made of a film or sheet base material having air permeability or air tightness and a film or sheet cover material having air permeability. A heating element in which a heating composition is encapsulated in a body is widely used.

[0003] A heating element is also used in which an adhesive layer is formed on one surface of the bag so that it can be directly adhered to underwear or the surface of a living body. It has also been proposed to use a warm compress by containing or carrying an agent or to use a so-called drug transdermal absorbent by containing or carrying a transdermally absorbable drug (Japanese Patent Laid-Open No. 2-149272). reference).

[0004] As a method of manufacturing the heating element, generally,
After dropping the exothermic composition on a predetermined area of the base material, cover the air-permeable coating material, and further thereafter, heat seal the base material and the periphery of the coating material over the entire circumference, using a hot-melt adhesive or the like. A sealing method is employed.

[0005] The heating element thus manufactured is sealed in an airtight outer bag, stored, or provided for distribution in order to suppress an exothermic reaction until use.

Conventional heat-generating compositions include, in addition to metal powder and water, which are indispensable for the exothermic reaction, carbon components such as carbon and activated carbon for promoting heat generation, and an oxide film on the surface of the metal powder to destroy the exothermic reaction. Powders containing a metal chloride that continuously generates water and a water retention agent such as wood flour are used.

The method of dropping the powdered exothermic composition includes a method of intermittently moving the substrate and dropping the powdered exothermic composition while the substrate is stopped, and a method of dropping the substrate at a constant speed. There is a method of dropping the exothermic composition in the form of powder on the substrate while moving the dropper for dropping the exothermic composition in powder form at the same speed as the base material while moving the material. The latter is better above.

[0008]

As in the prior art, when the exothermic composition is formed in the form of a powder, the exothermic composition in the form of a powder is blended in an optimal state in which an exothermic reaction, that is, an oxidation reaction is likely to occur. It is powdery, porous, has a large surface area, is very good in contact with air, and causes an oxidation reaction immediately upon contact with air.

Therefore, while the exothermic composition is compounded at an appropriate compounding ratio, and until the exothermic composition is manufactured, dropped on a base material and coated with a coating material to produce a heating element. Oxidation reaction with air, that is, an exothermic reaction occurs, causing loss due to the exothermic reaction of the exothermic composition, deteriorating the quality of the exothermic composition, and solidifying a product generated by the exothermic reaction, causing various adverse effects. I do. Specifically, for example, the reduction in yield due to coagulation removal, difficulty in handling, the complexity of maintenance of the manufacturing equipment, restrictions on the operating time of the manufacturing equipment or the working hours of workers, difficulty in coagulation processing, etc. It causes evil.

When the heat-generating composition is in the form of a powder, as described above, an oxidation reaction with air is performed until the heat-generating element is manufactured and the obtained heat-generating element is sealed in an airtight outer bag. Occurs,
Catastrophic defects such as a decrease in the quality of the heating element and a decrease in its reliability occur.

In order to prevent such an oxidation reaction of the exothermic composition, the mixing apparatus is made airtight, and the air in the mixing apparatus is replaced with nitrogen, and then the components of the exothermic composition are uniformly mixed. Not only is the equipment complicated and expensive,
There is a problem that the exothermic composition and the exothermic body become expensive.

Further, in the method of manufacturing the heating element, in the method of intermittently moving the base material and dropping the exothermic composition while the base material is stopped, the base material is frequently stopped and started.
There is a problem that the manufacturing speed is reduced.

On the other hand, in the method of dropping the exothermic composition onto the substrate while moving the substrate at a constant speed and moving the dropper for dropping the exothermic composition at the same speed as the substrate, the substrate is stopped. Since the start-up is hardly repeated, the production speed can be increased.

However, in this case, a complicated mechanism is required to move the discharge port for dropping the exothermic composition at the same speed as the base material, and the exothermic composition is given wettability by adding moisture. And, since it is powdery and poor in fluidity, there is a large limit to the speed at which the mechanism is moved, or the heat-generating composition lacks filling properties,
There is a problem that the filling amount of the heat-generating composition varies, and the heat-generating composition is unbalanced in the packaging material, resulting in a lack of reliability.

Further, the exothermic composition is given wettability by moisture. However, since the mixing ratio of moisture is low enough to be suitable for an exothermic reaction, it is powdery and poor in fluidity. There is also the problem that it is extremely difficult to evenly distribute within a predetermined range on the substrate.

For this reason, when sealing with a covering material, the distribution of the exothermic composition is controlled to some extent by a roller or the like.
Although it is equalized, in this method, the distribution of the exothermic composition tends to be biased in the source direction of the bag material, and in order to increase the distribution amount of the exothermic composition in the destination direction of the bag material, the thickness of the heating element is increased. However, for example, it is necessary to eliminate the deviation of the distribution amount by shaking by hand at the time of use.

As a result, the entire heating element becomes thicker, about several mm, and the feel is rough and the texture is poor. In addition, the flexibility is reduced and it becomes difficult to adapt to the complicated unevenness of the body surface and the curved surface having a small curvature. In addition, there is a problem that the stretchability or the stretchability is deteriorated, the shape of the body is deformed with the movement of the body, or the ability to follow the moving body surface is poor, and a feeling of tension or discomfort occurs.

By the way, it is indispensable to reduce the thickness of the heating element in order to put the heating element in the shoe for warming, but there is a great dissatisfaction with the conventional heating element having a thickness of about several mm. .

In particular, since a conventional disposable body warmer is powder-filled with a heat-generating composition, the thickness of the heat-generating composition is not constant due to movement inside the heat-generating body. Because it is not constant, fixing it in the same place may cause burns.

In recent years, products that prevent the bias of the exothermic composition by utilizing the reduced pressure at the time of heat generation by the porous membrane have become widespread, but the shift has not been completely prevented in the manufacturing process, the transportation stage, and the use stage. is the current situation.

Further, before use, if the heating element is housed in an outer bag (storage bag), the inside of the heating element is not depressurized, and the exothermic composition can move within the heating element at the transportation stage. In order to maintain safety, it is important to maintain a uniform thickness and maintain a constant temperature distribution during heat generation. If the heat-generating composition is biased, it may be returned as a defective product at the distribution stage, It is the current situation that we respond to exchanges from
As a result, it is extremely important to ensure the uniformity of the thickness of the exothermic composition at the transportation stage.

Japanese Patent Laid-Open Publication No. Sho 62-347 proposes a method of fixing the exothermic composition with an adhesive. However, in actual production, a powder exothermic composition is placed inside the exothermic body bag. It is almost impossible to adhere to the surface, and even if it can be done, the adhesive strength is weak and it is impossible to completely fix it, causing peeling during use, or a poor flexibility because it becomes a plate-like material with poor flexibility In addition, if the adhesive is mixed, the contact between the heat-generating composition and air deteriorates, resulting in temperature unevenness and temperature variation, and lacks practicality.

In order to solve the above-mentioned technical problems, the present inventor has suppressed the exothermic reaction of the exothermic composition, resulting in loss of the exothermic composition due to the exothermic reaction during production, deterioration of the exothermic composition quality, and Various adverse effects associated with solidification of the heat-generating composition can be prevented, an ultra-thin heating element can be manufactured at a high speed, and the heat-generating composition can be uniformly distributed and fixed in the bag body, thereby moving and moving the heat-generating composition. In addition to the prevention of the deviation, the heating element that minimizes the excessive exothermic reaction of the exothermic composition has been intensively studied.

As a result, the heat generation principle of a disposable body warmer or the like utilizes the heat generated when metal powder is oxidized.
It has been found that the speed is greatly affected.

That is, in order to accelerate this oxidation reaction,
The reaction is extremely slow with too much or too little water and it is important that there is adequate moisture. In this state of moderate humidity, the supply of moisture and air (oxygen) to the metal powder is balanced, and the rate of the oxidation reaction, that is, the rate of the exothermic reaction is maximized.

When the water content is too small, the air is sufficient but the water required for the reaction is insufficient. On the other hand, when the water content is too large, this water becomes a barrier layer and the amount of air supplied to the metal powder decreases. Reaction slows down.

Therefore, the present inventor has proposed that when the exothermic composition is thickened into an ink or a cream, lamination by screen printing or coating is extremely easy, and a super-thin heating element can be manufactured at high speed. In addition to being able to distribute the exothermic composition evenly in the bag material, the exothermic composition in the form of an ink or a cream can be used as a foam film /
Paper such as thin paper for home use such as sheets, tissue paper and towel paper, as well as cardboard such as corrugated cardboard and cardboard core
(Hereinafter referred to as paper), non-woven fabric, woven fabric, or porous film / sheet, the ink-like or cream-like heat-generating composition has a high penetration and anchoring property, and the fineness of these films or sheets is small. It has been found that they can bite into holes and prevent their movement and bias.

In this case, in particular, these films or sheets have water absorbency, and an ink-like or cream-like heat-generating composition is laminated on the films or sheets.
Alternatively, when a water-absorbing layer is further formed on the above-mentioned film or sheet, and an ink-like or cream-like heat-generating composition is laminated on the water-absorbent layer, all or a part of the heat-generating composition becomes the foamed film / sheet. , Papers, non-woven fabrics, woven fabrics or porous films and sheets, or a water-absorbing layer formed on them as a result of being more easily fixed,
We have also learned that bias is prevented.

In addition, the present inventor has found that when the exothermic composition is formed into an ink or a cream, the surface area is significantly reduced as compared with a powder exothermic composition, and contact with air is extremely limited. It was found that the oxidation reaction with air was significantly suppressed.

[0030] Further, the present inventors have found that in an ink-like or creamy exothermic composition, excess water, or free water and / or water-containing gel, since that function as an air blocking layer wrapped metal powder From this point, it was found that it was extremely stable in air.

In this case, if the exothermic composition contains an excessive amount of water, that is, if the moisture is excessively incorporated as in the case of an ink-like exothermic composition, the excess moisture is used as a barrier layer. It exhibits a function, further suppresses an exothermic reaction (oxidation reaction) with air, and further improves stability.

On the other hand, the ink-like or cream-like heat-generating composition does not necessarily need to contain an excessive amount of water, and may have a relatively low moisture like a cream-like heat-generating composition. The free water and / or hydrated gel wraps the metal powder and functions as an air barrier layer (barrier layer), so that it is stable in the air.

When an excess of water is blended, such as an ink-based oxygen absorber, the excess water is removed from one or both surfaces of a support, a coating material, or an ink- or cream-like heat-generating composition. The water-absorbing material applied to at least one of them, or even a part of the water in the cream-like exothermic composition, free water and / or water-containing gel, to a support, a coating material or an ink. Or at least one of the water-absorbing materials applied to one or both sides of the exothermic composition in the form of a cream, the barrier layer is lost, the exothermic composition becomes porous, It was also found that the contact was good and the exothermic reaction was performed smoothly.

Accordingly, while the exothermic composition is being compounded, and an ink-like or cream-like exothermic composition is produced, this is laminated on a substrate by printing or coating, and then coated with a coating material. Oxidation reaction with air, that is, exothermic reaction hardly occurs until the heating element is manufactured, and loss due to the exothermic reaction of the exothermic composition and deterioration of the quality of the exothermic composition are prevented. Solidification of the object is prevented. For this reason, it has been found that the yield and handleability are improved, the maintenance of the manufacturing apparatus is easy, and there is no restriction on the operation time of the manufacturing apparatus or the working hours of the worker.

When the exothermic composition is in the form of an ink or a cream, as described above, the exothermic body is manufactured, and the exothermic body is exposed to air during the time until the obtained exothermic body is sealed in an airtight outer bag. Of the heating element is stable,
It has been found that advantages such as higher reliability occur.

Furthermore, the inventor of the present invention has concluded that, since the ink-like or cream-like heat-generating composition is stable in the air, it is not necessary to make the mixing device airtight, and furthermore, the air in the mixing device is removed. Since it is not necessary to replace with nitrogen, it has been found that a simple mixing apparatus can be used, and that the exothermic composition and the exothermic body can be manufactured at low cost.

Further, as described above, the present inventor has found that when an exothermic composition in the form of an ink or cream is used, transfer and lamination by screen printing or coating are extremely easy.
In addition, it is possible to produce an ultra-thin heating element at high speed, and evenly distribute the exothermic composition in the bag material, and furthermore, when the exothermic composition is prevented from moving or biasing during use or handling. Was also obtained.

Further, the present inventor has found that this heating element can be made extremely thin by a lamination method using printing such as screen printing or coating, and if the heating element is thin, heat generation per unit time can be achieved. As a result of the decrease in the reaction amount,
It has also been discovered that excessive exothermic reactions of the exothermic composition are prevented.

In addition, the present inventor impregnated, sprayed, kneaded, printed, or printed a viscous aqueous solution of a water-absorbing agent on a packaging material such as a foamed film / sheet, paper, nonwoven fabric, woven fabric or porous film / sheet. After laminating and drying by coating, etc., containing or absorbing a water absorbing agent by pressing or kneading, and imparting water absorption to the packaging material, an ink-like or cream-like exothermic composition is formed thereon. It was also found that transfer and lamination by screen printing, coating, etc. would eliminate the powder input process and would make it easier to manage factories that meet GMP standards in the manufacture of future medical devices and pharmaceuticals.

By the way, the inventor of the present invention has proposed a method of absorbing excess water, free water, or a part of the water contained in a hydrogel onto one or both surfaces of a base material, a coating material, or an ink-like or cream-like heat-generating composition. When absorbed by at least one of the materials, the barrier layer is lost, and when used, becomes a porous heat-generating composition and becomes in good contact with air, resulting in excellent heat-generating properties. The knowledge was obtained.

The present invention has been completed on the basis of the above technical knowledge, and prevents the generation of dust during the production of a heating element and suppresses the exothermic reaction of the exothermic composition to produce heat during the production. It prevents loss due to the reaction, deterioration of the quality of the exothermic composition and solidification of the exothermic composition, and adopts printing and transfer methods such as screen printing and coating, so that an even distribution of the exothermic composition is possible. In addition, the thickness and distribution of the exothermic composition are high in accuracy and the quality of the product is improved, so that an ultra-thin heating element can be easily manufactured at a high speed. The heat-generating composition can be evenly distributed and fixed on the bag material by transferring and laminating on the water-absorbing layer formed thereon or the coating material, or these, so that the movement of the heat-generating composition and the displacement are offset. To prevent and in addition to fever It is an object to provide a method for producing an excessive exothermic reaction. Avoid ink-like or creamy exothermic composition and the heating element and the heating element using the same heat-generating composition by thinner.

In the present invention, the viscous aqueous solution of the water-absorbing agent is laminated on the packaging material by spraying, spraying, kneading, coating, coating or the like, and dried, or the water-absorbing agent is contained by pressing or kneading. If the heat-generating composition in the form of an ink or cream is transferred and laminated by screen printing or coating, etc., after it has been carried, that is, after imparting water absorption to the packaging material, the powder transfer process will be eliminated, and future medical treatment will be carried out. An object of the present invention is to provide an ink-like or cream-like heat-generating composition, a heat-generating element using the composition, and a method for producing the heat-generating element, which enable easy factory management that satisfies GMP standards in the manufacture of tools and pharmaceuticals. is there.

[0043]

The ink-like or cream-like heat-generating composition (hereinafter referred to as the present invention) according to the present invention has a heat-generating substance, a water-absorbing polymer and / or Or a thickener, a carbon component and / or a metal chloride and water as essential components, and an exothermic composition formed as an ink or cream as a whole ,
Moreover, excess water or free water in this exothermic composition
And / or hydrated gel expresses function as barrier layer
And the reaction with air is suppressed .

The heating element according to the present invention (hereinafter referred to as the heating element of the present invention) is obtained by laminating and enclosing the product of the present invention in a sheet-like packaging material in order to achieve the above object. It is characterized in that at least a part of the sheet-shaped packaging material has air permeability, and a part of the moisture of the present invention is absorbed by the sheet-like packaging material.

In order to achieve the above object, the first method for producing a heating element according to the present invention (hereinafter referred to as the first method of the present invention) forms the present invention and converts the present invention into a film. After laminating at least one predetermined region on the upper surface of the sheet-like base material, a film-like or sheet-like covering material is covered so as to cover the present invention, and at least one of the above-described base material and the covering material Or a part having air permeability , and the ink or cream
Part of the water content of the exothermic composition according to the above-mentioned substrate and / or coating material
It is characterized by being made to be absorbed .

In order to achieve the above object, the second method for producing a heating element according to the present invention (hereinafter referred to as the second method of the present invention) forms the present invention, and this present invention is formed into a film. After laminating at least one predetermined region on the upper surface of the sheet-like substrate, at least one selected from iron powder, carbon component or water absorbing agent is laminated or sprayed on the upper surface of the present invention, A film-like or sheet-like covering material is covered so as to cover at least one selected from the invention and iron powder, a carbon component, or a water absorbing agent, and at least one or a part of the base material and the covering material is ventilated. It has characteristics.

According to a third method of manufacturing a heating element according to the present invention (hereinafter referred to as the third method of the present invention), in order to achieve the above object, a product of the present invention is laminated on a film-like or sheet-like base material. Then, a film-like or sheet-like covering material is put thereon, and the base material and the covering material are attached to each other due to the viscosity of the present invention. It is characterized in that at least one or a part of the base material or the coating material has air permeability.

Hereinafter, the present invention, the heating element, and the first to third methods of the present invention will be described in detail.

The heat-generating composition of the present invention is not a powdery substance as in the prior art, but is a heat-generating composition which is thickened in the form of an ink or a cream.
Excess water or free water and / or hydrous gel
Layer so that it functions as a layer
It is characterized in that the exothermic reaction is controlled .

The product of the present invention is not particularly limited as long as it is made of a component which reacts with oxygen in the air to cause an exothermic reaction, and has a property of flowing when an external force is applied.

Specifically, for example, it can be obtained by adjusting the mixing ratio of water, a water-absorbing polymer and / or a thickener, and other components in each component constituting the present invention.

Since the present invention is formed in the form of an ink or a cream, it has the following various advantages.

That is, since the product of the present invention is in the form of an ink or a cream, it can be printed using a known printing technique such as thick coating printing, gravure printing, offset printing, screen printing, spraying, etc. Transfer and lamination can be extremely easily performed by coating or coating with a roller, an applicator, or the like, and an ultra-thin heating element can be manufactured at high speed, and the present invention can be evenly distributed in bag materials.

Further, the present invention is characterized in that a foamed film / sheet,
When transferred and laminated on paper, non-woven fabric, woven fabric or porous film / sheet, the present invention is ink-like or cream-like, so it has high penetration and anchoring properties, and the pores of these films or sheets are high. In addition, the movement and the deviation are prevented, and the contact area with the air is remarkably small, the supply amount of the air is reduced, and the oxidation reaction hardly occurs.

In this case, in particular, these films or sheets have water absorbency, and the present invention is laminated on this film or sheet, or a water-absorbing layer is further formed on the film or sheet, When the product of the present invention was laminated on this water absorbing layer, all or a part of the exothermic composition was formed on the foamed film sheet, paper, nonwoven fabric, woven fabric or porous film sheet, or on these. As a result of being more easily fixed to the water absorbing layer, its movement and bias are further prevented.

Further, according to the laminating method such as screen printing or coating, the heating element can be made extremely thin. When the heating element is thin, the amount of exothermic reaction per unit time decreases, resulting in heat generation. Excessive exothermic reaction of the composition is prevented, but since the present invention is in the form of an ink or a cream and has a thin layer thickness, movement and bias of the exothermic composition are prevented.

In addition, the viscous aqueous solution of the water-absorbing agent is mixed with a foamed film / sheet, paper, non-woven fabric, woven fabric or porous film.
The sheet-like packaging material such as a sheet is laminated and dried by impregnation, spraying, printing or coating or the like, or contains and carries a water-absorbing agent by pressing or kneading, that is, the sheet-like packaging material absorbs water. After imparting the properties, transfer the present invention thereon by screen printing or coating, etc.
By laminating the powder, there is no need for a process of charging powder, and factory management that satisfies GMP standards in the production of future medical devices and pharmaceuticals can be easily performed. In addition, as the water absorbing agent, a water absorbing polymer and a thickener described below are mainly used.

Further, since the product of the present invention is made into an ink or cream by mixing and adjusting the mixing ratio of water in the exothermic composition, and further, a water absorbing polymer and / or a thickener, It is extremely easy to transfer and laminate by printing or coating, and it is possible to manufacture an ultra-thin heating element at high speed. In addition, since excess water becomes a barrier layer, the amount of air supply decreases and the exothermic reaction is substantially reduced. As a result, the exothermic reaction is more stable in the air, and loss due to an exothermic reaction at the time of production, quality deterioration of the exothermic composition and solidification of the exothermic composition are further prevented, which is desirable.

That is, in the conventional powdered heat-generating composition, the various serious harms described above occur. However, when the heat-generating composition is thickened into an ink or a cream as in the present invention, An ultra-thin heating element that can be easily transferred and laminated by screen printing or coating can be manufactured at a high speed, and the excess water or free water or hydrogel becomes a barrier layer. And the exothermic reaction hardly occurs.

In this case, when excess water or free water or a part of the water in the hydrogel is absorbed by a bag material such as a base material and / or a coating material, the barrier layer is lost and the water is lost. As a result of the present invention being porous, the contact with air is improved, and a heat generating element of the present invention having good heat generation characteristics is obtained.

According to the present invention, the heat-generating substance, the water-absorbing polymer and / or the thickener, the carbon component and / or the metal chloride and water are essential components, and they are formed in ink or cream form as a whole. That is,
The mixing ratio is 0.1 to 7.5 parts by weight of a water-absorbing polymer and / or 0.1 to 0.1 parts by weight of a thickener with respect to 100 parts by weight of a heating substance.
10 parts by weight, 1.5 to 20 parts by weight of a carbon component and / or 1 to 10 parts by weight of a metal chloride are essential components, and water is blended to form an ink or cream as a whole. Things.

In this case, in producing the product of the present invention,
First, only the solid components are put into a mixing device, and after these components are uniformly mixed, an aqueous solution or dispersion of water or a metal chloride may be added thereto to form an ink or cream. Alternatively, all the components of the exothermic composition may be charged into a mixing device, and these components may be mixed to form an ink or cream.

The mixing device of these components is not particularly limited as long as it is a device capable of uniformly mixing when the water content is excessive, particularly in the case of an ink-like heat-generating composition. In the case of a small cream-like exothermic composition, a kneading device such as a kneader or a mixer is preferable because the exothermic composition is easily formed into a creamy form and the surface of the exothermic substance is easily covered with free water or a hydrogel.

The product of the present invention is formed into an ink or a cream as described above, and its viscosity (at a temperature of 20 ° C.) is generally 1,000 to 7,000 by the following method.
If the viscosity of the heat-generating composition is too low, such as less than 1,000 cps, the transferability of the heat-generating composition by printing or coating becomes poor, or the water content becomes extremely excessive. The transfer amount of other components is insufficient, the heat generation time is short, or the heat generation composition oozes out of a predetermined region on the base material, and it is necessary to absorb a large amount of moisture into the base material after transfer, It is not preferable because it is necessary to use a substrate having a special structure or to complicate the structure of the heating element. On the other hand, if it exceeds 7,500,000 cps, the transferability deteriorates and the transfer amount varies,
It is not preferable because an exothermic reaction may occur on the surface.
Therefore, for these reasons, 10,000 to 6,50
In the range of 0000 cps, particularly preferably 50,000
It is desirable to be in the range of 5,500,000 cps.

The viscosity is 2,000,000 cps.
If less than TOKIMECINC. (VISC
OMETER BH-type viscometer), using a # 7 rotor, rotating at 2 rpm, and beaker inner diameter (85φ).
mm) at a measurement temperature of 20 ° C. using a beaker. If the measured value exceeds 2,000,000 cps, a product manufactured by Toki Sangyo Co., Ltd. (R110 type viscometer, RE11
0U system, detection head RE100U, controller RC100A) and using an SPP rotor at a rotation speed of 0.2 rpm (D = 0.4 (1 / S)) at a measurement temperature of 20 ° C. This viscosity is a value at the time of transfer and lamination.

The components of the present invention include, in addition to water and a water-absorbing polymer and / or a thickener, and other components, that is, exothermic substances essential for an exothermic reaction, carbon and activated carbon for promoting exothermic reaction. And / or a metal component which breaks down the oxide film on the surface of the metal powder and continuously generates an exothermic reaction. A water retention agent, a pH adjuster, a surfactant for improving dispersibility, an antifoaming agent, and the like are blended, and are formed into an ink or cream as a whole.

The proportion of the compound of the present invention varies depending on the kind of the water-absorbing polymer and the thickener used, the kind of the exothermic substance, the kind of the carbon component, the kind of the metal chloride and the like. Parts by weight, 0.1 to 7.5 parts by weight of a water-absorbing polymer, 0.1 to 10 parts by weight of a thickener, 1.5 to 20 parts by weight of a carbon component, and 1 to 10 parts by weight of a metal chloride. Preferably, water is added to the mixture to form an ink or cream as a whole. In this case, a predetermined amount of the metal chloride is dissolved or dispersed in water, and this is added to a mixture of a water-absorbing polymer and / or a thickener and a carbon component and / or a metal chloride, and the ink as a whole is added. It may be formed into a shape or a cream.

In this case, after uniformly mixing only the solid components as described above, instead of mixing an aqueous solution or dispersion of water or a metal chloride, an appropriate amount of water is added to the solid components. The components of the present invention may be obtained by mixing the components uniformly.

Also in this case, as in the above case, the present invention has a viscosity (temperature of 20 ° C.).
Is generally 1,000 to 7,500,
It is desirable to be in the range of 000 cps.

In the present invention, as described above,
Moisture and water-absorbing polymer and / or thickener, and other components,
In other words, a desired exothermic characteristic can be obtained even with a substance composed of a heating substance, a carbon component, and a metal chloride. In addition, in order to further improve the stability of temperature and further improve the heat generation time, If desired, an inorganic or organic water retention agent, a pH adjuster, a surfactant for improving dispersibility, an antifoaming agent, and the like are blended, and those formed as an ink or cream as a whole are also useful.

That is, based on 100 parts by weight of the heating substance, 0.1 to 7.5 parts by weight of the water-absorbing polymer, 0.1 to 10 parts by weight of the thickener.
Parts by weight, 1.5 to 20 parts by weight of a carbon component and 1 to 10 parts by weight of a metal chloride. The heat-generating composition further contains an inorganic or organic water retention agent for 100 parts by weight of the heat-generating substance. 0.5 to 10 parts by weight, pH adjuster 0.1 to 5 parts by weight,
At least one selected from 0.1 to 5 parts by weight of a surfactant that enhances dispersibility and 0.1 to 5 parts by weight of an antifoaming agent is blended. In the present invention, water is particularly added to this mixture. In addition, it is formed as an ink or cream as a whole. In this case, it is desirable to dissolve or disperse a predetermined amount of the metal chloride in water and add this to the mixture to form an ink or cream as a whole, since particularly excellent heat generation characteristics can be obtained. By the way, after uniformly mixing only the solid components in this manner, instead of mixing an aqueous solution or dispersion of water or a metal chloride, an appropriate amount of water is added to the solid components, and all the components are uniformly mixed. The present invention may be obtained by mixing.

Also in this case, as in the case described above, the viscosity of the product of the present invention (at a temperature of 20 ° C.) is generally from 1,000 to 7,500,000 by the method described above.
It is desirable to be in the range of cps.

In the present invention, the water-absorbing polymer is mainly a polymer material which absorbs water and an aqueous solution of a metal chloride smoothly and in large quantities. No. 43395, a starch-polyacrylonitrile copolymer disclosed in
No. 1-39672, a cross-linked polyalkylene oxide disclosed in JP-B-53-13495, and a saponified vinyl ester-ethylenically unsaturated carboxylic acid copolymer disclosed in JP-B-53-13495, and JP-B-54-30710. Self-crosslinking polyacrylic acid salts obtained by the disclosed reversed-phase suspension polymerization method, reaction products of polyvinyl alcohol-based polymers and cyclic anhydrides disclosed in JP-A-54-20093, One or two selected from cross-linked polyacrylates, cross-linked N-vinylacetamide (water-absorbing agent) (trade name NA-010, manufactured by Showa Denko KK) and the like disclosed in JP-A-59-84305. The above-mentioned mixtures are mentioned, and further, these may be treated with a surfactant, or a surfactant may be combined with these to improve the hydrophilicity. It is. Among these water-absorbing polymers, there are those which absorb water or a metal chloride aqueous solution to increase viscosity, but mainly have a function of smoothly absorbing a large amount of water or a metal chloride aqueous solution. Things.

As the water-absorbing polymer, a commercially available polymer may be used, for example, Sunwet I manufactured by Sanyo Chemical Co., Ltd.
M-300, Sunwet IM-300MPS, Sunwet IM-1000, Sunwet IM-1000M
PS, Sunwet IM-5000, Sunwet IM
-5000MPS, Aquakeep 4S and Aquakeep 4SH manufactured by Iron and Steel Chemical Co., Ltd., Sumikagel NP manufactured by Sumitomo Chemical Co., Ltd.
1020, Sumikagel NP-1040, Sumikagel SP
-520, Sumikagel N-1040, KI manufactured by Kuraray Co., Ltd.
Gel 201-K, KI Gel 201K-F2, Nippon Shokubai's Aquaclick CS-6, Aquaclick CS-
7. Arasoap 800, Arasoap 80 manufactured by Arakawa Chemical Co., Ltd.
OF is mentioned as an example.

Among these commercially available water-absorbing polymers, Sanwet IM-30 manufactured by Sanyo Chemical Co., Ltd., which rapidly absorbs water or an aqueous solution of metal chloride and has a high absorption amount.
0MPS, Sunwet IM-1000MPS, Sunwet IM-5000MPS, Sumikagel NP-1020 and Sumikagel NP-1040 manufactured by Sumitomo Chemical Co., Ltd., KI Gel 201-K and KI Gel 201-F2 manufactured by Kuraray Co., Ltd., manufactured by Arakawa Chemical Co. Arasorp 800F is particularly preferred.

In the present invention, examples of the thickener include substances which absorb water or an aqueous solution of a metal chloride to increase the consistency or impart thixotropic properties. Examples of the thickener include bentonite and stearic acid salts. , Polyacrylates such as sodium polyacrylate, gelatin, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, tragacanth, locust bean gum, guar gum, gum arabic, alginates such as sodium alginate, pectin, carboxyvinyl polymer , Dextrin, pregelatinized starch, starch-based water-absorbing agents such as processing starch, carrageenan, polysaccharide-based thickeners such as agar, CMC, ethyl acetate, hydroxyethyl cellulose, methyl cellulose or hydroxypropyl cellulose. Cellulose derivatives thickener, an acrylic acid polymer material (e.g., Nippon Shokubai Co., Ltd., trade name: CS-6HS), selected from water-soluble cellulose ethers or poly-N- vinylacetamide, etc. 1
Species or a mixture of two or more species.
These may be treated with a surfactant or may be combined with a surfactant to improve the hydrophilicity. These thickeners mainly have a function of absorbing water or an aqueous solution of a metal chloride to increase the consistency or impart thixotropy.

The water-soluble cellulose ethers include
Specifically, for example, methyl cellulose obtained by etherifying cellulose with a methoxyl group (manufactured by Shin-Etsu Chemical Co., Ltd.
Product name: Metroze SM15, Metroze SM25, Metroze SM400, Metroze SM4000, etc.),
Hydroxypropyl methylcellulose obtained by etherifying cellulose with a hydroxypropoxyl group (trade names: Metrolose 60SH-50, Metrolose 60SH-4000, Metrolose 90SH-40, manufactured by Shin-Etsu Chemical Co., Ltd.)
00, Metros 90 SH-30000, Metros 9
Water-soluble cellulose ethers such as hydroxyethyl methylcellulose obtained by etherifying cellulose with a hydroxyethoxyl group (Shin-Etsu Chemical Co., Ltd., trade name: Metroose 60SH-50,
Metroose 60SH-4000, Metroose 90SH-
4000, Metrolose 90SH-30000, Metrolose 90SH-100000), water-soluble cellulose ethers such as Cellogen EP, Cellogen BSH-12, Cesca MC, Cesca MHEC, and Cesca MHPC manufactured by Daiichi Kogyo Seiyaku.

When the aqueous solution of the water-soluble cellulose ether is heated, the viscosity decreases, for example, up to a predetermined temperature (the temperature at which thickening starts). (Hereinafter, this phenomenon is referred to as a thermal gelation phenomenon), and this free water acts as a barrier layer to reduce the exothermic reaction. On the other hand, when this gel is cooled, it absorbs water and returns to its original state. Has properties.

The temperature at which the water-soluble cellulose ether thickens is determined by the type of etherifying agent, the substitution rate, the cellulose molecular weight,
When it is added as a solution, its concentration, and when other additives are added, it is affected by the rate of temperature rise and cooling, in addition to the type and amount (concentration) of the additive. Therefore, when using a water-soluble cellulose ether as a thickener,
The type of the etherifying agent, the substitution rate, the molecular weight of the cellulose, the concentration of the solution, the type and the amount (concentration) of the other additives, and the like are appropriately selected, and the composition and the amount of the heating element composition are appropriately selected. By controlling the heating rate and the cooling rate, the maximum heat generation temperature can be determined as appropriate.

For example, in the case of a 2% by weight aqueous solution of the water-soluble cellulose ether (for example, trade name: Metroose SM4000 manufactured by Shin-Etsu Chemical Co., Ltd.), the thickening start temperature is 55.degree. sodium chloride (NaCl), or sodium carbonate (Na ₂ CO ₃ · 1
When 0% H ₂ O) is added at 5% by weight, the thickening start temperature is 40 ° C., and when applied directly to the human body, Metroose SM4000 releases adsorbed moisture below the safe temperature (43 ° C.). To suppress the exothermic reaction.

The thickening start temperature of this Metroze SM4000 is 45 ° C. even when 5% by weight of Al ₂ (SO ₄ ) ₃ .18H ₂ O is added.
00 releases the adsorbed moisture to the periphery of the metal powder to suppress the exothermic reaction.

Further, for example, a water-soluble cellulose ether (for example, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metroose 6)
In the case of a 2% by weight aqueous solution (0SH-4000), when there is no additive, the thickening start temperature is 75 ° C., but when 5% by weight of sodium chloride (NaCl) is added, the thickening start temperature is 70 ° C. And sodium carbonate (Na ₂ CO ₃
For example, when 5% by weight of 10H ₂ O) is added, the thickening start temperature is 45 ° C.
SH-4000 releases adsorbed moisture to the surroundings to suppress the exothermic reaction.

Further, the thickening start temperature of Metrolose 60SH-4000 becomes 50 ° C. even when 5% by weight of Al ₂ (SO ₄ ) ₃ .18H ₂ O is added. To increase the amount of free water around the metal powder to suppress the exothermic reaction.

Examples of additives for adjusting the thickening start temperature of the thickener include the above-mentioned sodium chloride, sodium carbonate, inorganic substances such as aluminum sulfate and hydrates, lower alcohols such as ethanol, polyethylene glycol and glycerin. Examples thereof include polyhydric alcohols, the above-mentioned water-absorbing polymers and thickeners.

The poly-N-vinylacetamide is obtained by radical polymerization of N-vinylacetamide, and includes a water-soluble linear structure and a water-insoluble crosslinked structure. The insoluble poly-N-vinylacetamide includes a microgel that acts as a gelling agent due to the difference in crosslink density. Specifically, for example, an N-vinylacetamide-sodium acrylate copolymer ( Showa Denko KK product name GE-167), N-vinylacetamide homopolymer (Showa Denko KK product name GE-19)
1) or crosslinked N-vinylacetamide (microgel)
(Manufactured by Showa Denko KK, trade name: GX-205), and one or more mixtures thereof. Further, these may be treated with a surfactant or a surfactant may be added thereto. The hydrophilicity may be improved in combination. These thickeners mainly have a function of absorbing water or an aqueous solution of a metal chloride to increase the consistency or impart thixotropy.

In the present invention, an organic substance can be used as a heat generating substance, but it is composed of iron powder, zinc powder, aluminum powder, magnesium powder, or two or more of these metals, which does not generate an off-odor due to the reaction. Alloy powders, furthermore, mixed metal powders obtained by mixing two or more of these are used. In particular, among these metal powders, safety, handleability, cost, storage stability and stability etc. It is desirable to have iron powder which is the best in terms of viewpoints.

Examples of the carbon component include carbon black, graphite, and activated carbon. Examples of the metal chloride include alkali metal chlorides such as sodium chloride and potassium chloride and alkali chlorides such as calcium chloride and magnesium chloride. An example thereof is chloride of earth metal.

As the inorganic or organic water retention agent, water is retained, and when the water content in the exothermic composition becomes insufficient and the exothermic reaction slows down, not only is water released, but also the porosity in the exothermic composition is reduced. To improve the contact between air and the exothermic composition.

Specifically, for example, pearlite, cristobalite, vermiculite, silica-based porous materials, silicates such as calcium silicate, silica stone, diatomaceous earth, alum earth such as alumina, and mica powder and clay such as clay Siliceous,
For example, formic acid siliceous substances such as talc, silica powder, wood powder, pulp powder and the like can be mentioned.

As the above-mentioned pH adjusting agent, surfactant and defoaming agent, those used in this field can be used in addition to ordinary pH adjusting agents such as sodium polyphosphate.

In the present invention, a part of the moisture is absorbed by the base material and / or the coating material, so that the contact with the air can be improved in use.

Next, the heating element of the present invention will be described in detail. The feature of the heating element of the present invention lies in that the present invention is formed by laminating and enclosing the present invention at least partially in a sheet-like packaging material having air permeability.

The present invention includes the aforementioned ones, and furthermore, the present invention is configured so that a part of the moisture of the present invention is absorbed by the sheet-like packaging material.

In the heating element of the present invention, the sheet-like packaging material is
It consists of a film-like or sheet-like base material and a film-like or sheet-like covering material, and at least one or a part of the base material and the covering material preferably has air permeability and water absorbency.

In the heating element of the present invention, an ultra-thin heating element is formed by printing, coating, or the like. However, when the heating element is formed thin, the consumption of oxygen in the air by the heating composition in the bag body is reduced. If the heating element is further reduced in thickness (about 1 mm or less in thickness) and lightweight, the amount of exothermic reaction per unit time is reduced only by reducing the pressure based on the pressure, so that the movement of the heating composition and the displacement can be prevented. May not be maintained.

In such a case, it is preferable to fix all or a part of the heat-generating composition to a base material and / or a coating material to prevent its movement and deviation.

More specifically, for example, at least a portion of the base material and / or the coating material which is in contact with the present invention has irregularities formed on the surface thereof, or
Alternatively, the coating material is formed of a film-shaped or sheet-shaped water-absorbing material having a water-absorbing property.
Or by forming irregularities in the contact portion with the present invention in the coating material, to enhance the adhesion due to water absorption from the present invention and the bonding with the present invention by these irregularities to move, shift It is desirable to prevent it.

In the heating element of the present invention, the substrate and / or
Alternatively, the coating material is formed by laminating a water-absorbing material having water absorption on one or both surfaces of a non-breathable or breathable film or sheet. By forming the irregularities, it is desirable to increase the adhesion due to the absorption of water from the present invention and the binding to the present invention by these irregularities to prevent the movement and the offset.

That is, it is desirable that the substrate and / or the coating material be formed of a water-absorbing material having a water-absorbing property. It is not limited.

The water-absorbing material is not particularly limited, regardless of whether or not the material itself has water absorption, as long as it has water absorption as a result.

Specifically, for example, water-absorbent foamed films and sheets (foams such as water-absorbent foamed polyurethane) and papers, nonwoven fabrics and woven fabrics formed of water-absorbent fibers,
Or, in addition to a water-absorbing material such as a nonwoven fabric or a woven fabric containing a water-absorbing fiber, or a water-absorbing porous film or sheet, with or without water absorption, a foamed film or sheet, a nonwoven fabric, a woven fabric or a porous film The sheet contains a water absorbing agent, impregnated, kneaded, transferred or carried to impart or increase water absorption, regardless of the presence or absence of water absorption, foamed film
Water absorption of sheets, papers, non-woven fabrics, woven fabrics or porous film sheets, water-absorbent foam film sheets, papers, non-woven fabrics, woven fabrics or porous film sheets cut into the planar shape of the present invention A material to which water-absorbing properties are imparted by applying a water-soluble material to one or both surfaces of the product of the present invention.

In the heating element of the present invention, it is particularly preferable that a water-absorbing layer is formed on at least a portion of the base material and / or the coating material which is in contact with the present invention. In this case, the base material and / or the coating material are provided with a water-absorbing layer at the contact portion with the present invention. This is desirable because it becomes easy to perform heat fusion.

In the heating element of the present invention, all or a part of the present invention is embedded or joined to the unevenness of the surface of the base material and / or the coating material and / or the water absorbing layer, whereby the movement of the present invention is improved. It is desirable to further prevent bias.

As described above, since the product of the present invention is prevented from moving in the bag, it is possible to prevent the exothermic composition from being unevenly distributed and the exothermic temperature fluctuating or generating an abnormally high temperature.

Incidentally, examples of the water-absorbing layer include a layer formed of the above-described water-absorbing polymer and / or thickener, or the above-mentioned film-shaped or sheet-shaped water-absorbing material.

The surface of the base material and / or the coating material may be smooth, but in order to ensure the bonding with the present invention, at least 38 dynes or more, preferably 40 dynes or more. It preferably has an index. Therefore, when the substrate and / or the coating material is formed of a film or sheet having a smooth surface, the surface is roughened (irregularized) by a physical treatment such as a corona treatment, and thereby a wetting index is obtained. Is preferably increased.

When a water-absorbing layer is formed on the base material and / or the coating material at the contact portion of the present invention, the water-absorbing power of the heat-generating composition causes the water-absorbing layer to absorb water other than water in the heat-generating composition. No special surface roughening treatment is required, as other components are attracted to the substrate and / or the coating, a portion of which infiltrates the water-absorbing layer and creates a strong anchoring effect.

As described above, the base material and / or the coating material used in the heating element of the present invention is obtained by using the heat-generating composition which generates heat by contact with air as a heat source. It is necessary that at least one or a part of the material has air permeability, and the base material and / or the coating material include a single-layer material and a material obtained by laminating a plurality of layers in the thickness direction. .

In this case, lamination means that the layers are entirely or partially joined by heat setting, adhesion, adhesion, lamination, or the like, or the respective layers are simply overlapped with each other, for example, in the peripheral portion or the central portion. It means that the layers are locally bonded by heat sealing, hot melt adhesive or pressure sensitive adhesive.

In the present invention, the exothermic composition can be laminated by high-speed printing, coating, or the like since it is formed in an ink or cream form. By deep gravure printing, spraying, coating or the like, for example, the feed rate of the substrate is 160 to 200 m / min.
At a high speed of about a minute, at least in one predetermined area, for example, to a thin film thickness of about 0.02 to 1.5 mm, and
It is possible to make the layers with a uniform thickness.

In this case, the product of the present invention is precisely and uniformly laminated on at least one predetermined region on the base material, and the film thickness is uniformly set to, for example, 0.0% over the entirety.
As a result, it is possible to manufacture an ultra-thin heating element having a thickness of about 0.5 to 2 mm as a whole as a result of being thinned to about 2 to 1.5 mm, preferably about 0.1 to 0.5 mm. .

In this case, in order to increase the processing speed, to control the adhesion area more precisely, to reduce the wall thickness, and to make the film thickness uniform, a roll film or roll sheet substrate is moved at a constant speed, for example, every minute. The product of the present invention may be laminated on the substrate while feeding at a high speed of about 160 to 200 m / min, and a roll film or roll sheet covering material may be further placed thereon. At this time, since the present invention plays the same role as the adhesive and joins the base material and the covering material,
It is desirable to seal around the material of the exothermic composition.

The heating element of the present invention is formed by laminating a thin film of the present invention on at least one predetermined region on the upper surface of a film-like or sheet-like substrate, and covering the heat-generating composition. A film-like or sheet-like covering material is covered, and the base material and the covering material are bonded together via the present invention.
That is, the present invention plays the same role as the pressure-sensitive adhesive.
Of course, in order to further improve the quality and reliability, it is desirable to seal the base material and the coating material around the periphery of the present invention by adhesion, heat bonding or heat fusion.

When the base material and / or the coating material are a single layer (single film or sheet), as described above, in order to prevent the present invention from moving and offsetting, it is preferable to use a film having a smooth surface. It is preferable that the sheet has a rough surface (uneven surface) or a foamed film / sheet, paper, non-woven fabric, woven fabric or porous film / sheet is used. When they are formed by using a water-absorbing agent, they may contain, impregnate, transfer or carry a water-absorbing agent to exhibit water-absorbing properties. In this case, foam film such as sponge
When a sheet, paper, nonwoven fabric, woven fabric, or the like is used, the adhesiveness to the pressure-sensitive adhesive layer described later is improved. Also, the base material has multiple layers,
That is, the above-mentioned thing is mentioned as what laminated two or more types of films or sheets.

In addition, when the present invention is interposed between the substrate and the coating material, at least one selected from iron powder, carbon component and water absorbing agent is provided on the present invention laminated on the upper surface of the substrate. May be laminated or sprayed to quickly raise the heat generation temperature during use or to change the temperature characteristics during use. In this case, the amount of lamination or spraying may be within a range that does not deteriorate the temperature characteristics. Although it is not particularly limited as long as it is, specifically, it is generally desirable to be in the range of 1 to 250 g / m ² . Examples of the water absorbing agent include the above water absorbing polymers and thickeners.

In the heating element of the present invention, the amount of iron powder coated on the upper surface of the present invention with a carbon component, or the total amount of iron powder (A), carbon component (B), and (A) and (B) On the other hand, a mixture containing 5% by weight or less of water is laminated,
Thus, scattering of dust at the time of lamination can be prevented, the rise of the heat generation temperature during use can be made faster, or the temperature characteristics during use can be changed.

In this case, as a method of coating iron powder with a carbon component, a pressing type mixer, for example, AM-15F manufactured by Hosokawa Micron Co., Ltd. is used. 10 to 10 parts by weight, the number of rotations is 500 to 1500 rpm, and 1
It is obtained by kneading for 0 to 80 minutes.

As a method for obtaining a mixture of iron powder (A), carbon component (B) and water of 5% by weight or less based on the total amount of (A) and (B), a method manufactured by Hosokawa Micron Corp.
Using AM-15F, the proportion of carbon component is 0.1 to 10 parts by weight, water is 0.3 to 5 parts by weight, especially water is 0.5 to 3 parts by weight with respect to 100 parts by weight of iron powder. 500
It is obtained by kneading at 〜1500 rpm and for 10 to 80 minutes. By adding such a small amount of water, scattering of dust can be further prevented.

Further, in the heating element of the present invention, when the present invention is laminated on a base material, and the present invention is coated with a coating material, a film-shaped or sheet-shaped water-absorbing material is used. What was cut into a laminated shape, in particular, such as household thin paper such as blotting paper or tissue paper, using a high water-absorbing film or sheet cut into a laminated shape of the present invention,
This may be placed on one side of the present invention, or both sides of the present invention may be sandwiched between them, and then sealed with a covering material.

In the present invention, as a method of supporting a water-absorbing agent on a film or sheet, the film or sheet is impregnated with a solution of the water-absorbing agent, and the solvent is steamed, or the film or sheet is coated with the water-absorbing agent. Examples include spraying, coating, kneading, pressing, laminating or blending, or weaving a water-absorbing fiber into a nonwoven fabric or woven fabric, or mixing.

It is necessary that the base material and / or the coating material have a necessary mechanical strength such as tensile strength, and it is preferable that the base material and / or the coating material be flexible as a whole in order to increase conformability to the body surface. .

That is, in the heating element of the present invention, it is more suitably applied to a curved portion, a stretchable portion, and a bent portion of a human body.
Moreover, in order to more easily follow the stretched portion and the bent portion, the base material and the covering material, that is, the wrapping material of the heating element, are formed of an extensible film or sheet, particularly, an stretchable film or sheet. Things are desirable.

That is, when the sheet-like wrapping material is formed of an extensible material, particularly an elastic material, it is extremely easy to expand and contract extremely, and joints such as elbows and knees as well as curved parts of the human body such as shoulders and arms. It has excellent adhesiveness by following the expansion and contraction part and bending part more, and it has no feeling of tension or discomfort during use, so it has a better feeling of use and also reliably prevents peeling during use. It is most desirable because a more excellent thermal effect is exhibited.

The extensible base material and the covering material include, for example, those formed of a synthetic resin such as polyethylene or polypropylene having high extensibility.

The stretchable substrate and covering material, that is, stretchable films or sheets are not particularly limited as long as they are formed of stretchable materials.
Particularly, stretchable foamed film / sheet, nonwoven fabric, woven fabric, porous film / sheet, etc., which are stretchable and have a high binding property with the present invention, are mentioned, and these themselves have water absorbency. With or without water-absorbing agents, they themselves contain, impregnate, adhere, knead, transfer, laminate, or carry a water-absorbing agent to impart or improve the water-absorbing property in the present invention. It is desirable that the barrier layer be removed by absorbing the water of the present invention so that the present invention is porous and in a state suitable for contact with air.

As the material of the stretchable film or sheet, for example, natural rubber, synthetic rubber or thermoplastic elastomer can be used. However, since the stretchability is large and the handleability is high, and the thermoplastic elastomer has heat fusion property, It is desirable because the production of the heating element of the present invention is extremely easy.

Of course, in the heating element of the present invention, it does not matter whether the base material and the coating material have adhesiveness, heat-sealing property or heat-bonding property, but the quality and reliability are further improved. For this purpose, it is desirable to seal the base material and the coating material over the periphery of the exothermic composition by adhesion, heat bonding or heat fusion.

Specific examples of the synthetic rubber include butadiene rubber, isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, isobutylene-isoprene rubber, polyalkylene sulfide, silicone rubber, and poly (chloro) rubber.・
Trifluoroethylene), vinylidene fluoride-6-propylene copolymer, urethane rubber, propylene oxide rubber, epichlorohuman phosphorus rubber, acrylate-acrylonitrile copolymer or acrylate-2-chloroethyl vinyl ether copolymer, etc. No.

The thermoplastic elastomer includes:
Specific examples include olefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, and the like.

As the olefin-based elastomer,
Specific examples include ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, chlorosulfonated polyethylene, chlorinated polyethylene, and ethylene-vinyl acetate copolymer.

The thicknesses of the base material and the coating material vary greatly depending on the application and are not particularly limited. Specifically, in the case of foot use, 10 to 5000 μm
m, 10 to 500 when directly attached to human body
μm, more preferably 12 to 250 μm, generally 10 to 2500 μm, particularly 12 to 1 μm.
It is desirable that the thickness be 000 μm.

When the film thickness of the base material and the coating material is less than 10 μm, the required mechanical strength cannot be obtained, and it may be difficult to make the film thickness uniform.

On the other hand, when the thickness of the base material exceeds 5000 μm, even if it is a foam such as a sponge, the flexibility is reduced, the conformability to the body surface is significantly reduced, and the deformation or movement of the body surface is reduced. In addition, the followability of the heating element is reduced, and the feeling is stiff and the feeling becomes poor, and the thickness of the entire heating element is undesirably increased.

Therefore, in particular, the thickness of the substrate should be 10 to 2500.
μm, especially 12 to 1000 μm,
It is desirable because the required mechanical strength is obtained and the required flexibility is obtained.

Examples of the base material and / or the coating material include foamed or non-foamed films or sheets made of a polymer material. Can be further prevented.

Examples of the polymer material include polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, saponified ethylene-vinyl acetate copolymer and ethylene-vinyl acetate copolymer. Can be

In the case of forming a laminated base material or a covering material, a part thereof can be formed of a film or sheet having air permeability. Examples of the film or sheet having air permeability include foamed or non-foamed films or sheets, papers, nonwoven fabrics, woven fabrics or porous film sheets, cloths, and the like. A nonwoven fabric or the like can be used.

Examples of a method for imparting air permeability to the film or sheet made of the non-foamed polymer material include a method of forming a film or sheet by stretching to form air holes, and a method of adding a specific component from the film or sheet. In addition to the method of extracting and forming air holes, there is a method of mechanically forming air holes by punching or punching with a fine needle after forming the film, and the like, whereby a porous film or sheet is formed. Is obtained.

In the foamed film or sheet made of a polymer material, closed cells or open cells open on both front and back sides are formed by foaming, and after foaming, the film or sheet is pressed to form inside. The closed cells or open cells that have been ruptured and communicated on both the front and back surfaces are provided with air permeability, and foamed airtight materials that do not have air permeability.

Fabrics such as papers, woven fabrics, knitted fabrics, and non-woven fabrics have air permeability because they have air holes or air passages communicating with the front and back surfaces of the fabric. As the fibers constituting the cloth, there can be used regenerated fibers, semi-synthetic fibers, synthetic fibers using natural materials such as natural fibers and viscose fibers, and mixtures of two or more of these.

Examples of natural fibers include vegetable fibers such as cotton and hemp, and animal fibers such as silk and animal hair.
Examples of the polymer material constituting the synthetic fiber include polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, saponified ethylene-vinyl acetate copolymer or ethylene-vinyl acetate copolymer. And the like.

In the heating element of the present invention, in the packaging material,
It is necessary that at least one or a part of the side or the base material and the coating material has air permeability.

In the case where at least one or a part of the base material and the coating material has air permeability, the air permeability greatly affects the control of the reaction rate or the heat generation temperature of the exothermic composition. In order to obtain an effect and to prevent low-temperature burns and ensure safety, it is preferable to manage the air permeability. Further, in order to control the air permeability with high accuracy, it is preferable to control the air permeability of the film or sheet with the moisture permeability.
(Lyssy method L80-4000H type) 50 ~ 10,
It should be within the range of 000 g / m ² · 24 hr, particularly preferably within the range of 200 to 6,000 g / m ² · 24 hr.

When the base material and / or the covering material are composed of a plurality of layers of a gas permeable film, the moisture permeability as a whole is determined to be 50 to 10,000 g / m ² by the Lissy method.
-It is preferable to set the range to 24 hours.

If the water vapor transmission rate is less than 50 g / m ² · 24 hr, the calorific value becomes small and a sufficient heating effect cannot be obtained, which is not preferable. On the other hand, 10,000 g / m ² · 2.
Exceeding 4 hours is not preferable because the heat generation temperature becomes high to cause a problem in safety and a possibility that heat generation time may be shortened. Therefore, the moisture permeability of the breathable film is 100 to
A range of 1,000 g / m ² · 24 hr is particularly preferable because a safe and sufficient heating effect can be obtained for a long time.

By the way, the Lyssy method (Lyssy method) is a method based on industrial standards of various countries around the world.
In SZ0208, a temperature of 40 ° C. and a relative humidity difference of 90% R
H, it is set to 10
A measurement sample is inserted into the boundary between the lower chamber in a state of 0% relative humidity and the upper chamber in which a highly sensitive humidity sensor is installed, and the relative humidity of the upper chamber with the humidity sensor is adjusted to 10% RH (100% -90). %), And about ± 1% width (△ RH)
That is, the time required for the humidity to increase from about 9% to about 11% (several seconds) is measured and compared with the result of calibration performed under the same conditions using a standard sample whose transmittance is known in advance, thereby transmitting the light. This is a method for obtaining degrees.

In the heating element of the present invention, the adhesive layer is formed on at least a part of at least one of the exposed surfaces of the base material or the coating material at any time before being sealed in the airtight outer bag material. In this case, it is preferable that one of them has air permeability because the heating element can be stuck and fixed directly to the body surface or clothing.

The pressure-sensitive adhesive layer is not particularly limited as long as it is a layer capable of adhering to the outer skin, and specific examples include a layer formed of a poultice or a pressure-sensitive adhesive.

Examples of the pressure-sensitive adhesive layer include a layer formed of a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, or a hot-melt-type pressure-sensitive adhesive.

Specific examples of the adhesive layer include a rubber adhesive, a vinyl acetate adhesive, an ethylene-vinyl acetate adhesive, a polyvinyl alcohol adhesive, a polyvinyl acetal adhesive, and a vinyl chloride adhesive. Acrylic pressure-sensitive adhesive, polyamide-based pressure-sensitive adhesive, polyethylene-based pressure-sensitive adhesive, cellulose-based pressure-sensitive adhesive, a polysulfide pressure-sensitive adhesive or a layer formed of a pressure-sensitive adhesive containing a hot melt type polymer substance, among these, Contains rubber-based adhesives, acrylic-based adhesives or hot-melt type polymer substances, because they have good skin adhesion properties and have little skin irritation and little decrease in adhesive strength even when heated. A layer formed of a pressure-sensitive adhesive is desirable. In particular, a layer of a pressure-sensitive adhesive containing a hot-melt type polymer substance has a strong initial tack force and a high tackiness when heated. Always excellent.

Although the thickness of the pressure-sensitive adhesive layer is not particularly limited, it is 5 to 1000 μm, especially 10 to 5 μm.
If the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the required adhesive strength may not be obtained, while the thickness of the pressure-sensitive adhesive layer may be 1000 μm.
If it exceeds, not only is it bulky and the feeling of use deteriorates, but also the economic efficiency deteriorates, which is not preferable.

Examples of the hot melt polymer used in the heating element of the present invention include, for example, an ABA block copolymer, a saturated polyester polymer, a polyamide polymer, and an acrylic polymer. Or a mixture of two or more of these materials, such as a polymer-based material, a urethane-based polymer, a polyolefin-based polymer, or a polyolefin-based copolymer or a modified product thereof.

[0153] This modified product refers to a component of the hot melt type polymer substance which is partially replaced with another component to improve the properties of the hot melt type polymer substance, for example, to improve the adhesiveness and stabilization of the hot melt type polymer substance. It means something with different gender.

In the ABA type block copolymer, the A block is a monovinyl-substituted aromatic compound A such as styrene and methylstyrene, and is an inelastic polymer block, and the B block is a conjugate such as butadiene and isoprene. Diene is an elastic polymer block, specifically, for example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and the like. Is also good.

Examples of commercial products of the ABA type block copolymer include, specifically, Kariflex TR-110.
1, Califflex TR-1107, Califflex T
R-1111 (manufactured by Shell Chemical Co., Ltd.), or Solprene 418 manufactured by Philippe Petroleum, and the like.

By the way, if desired, this pressure-sensitive adhesive is
Other components, such as other adhesives, adhesive additives, antioxidants, fillers, adhesive modifiers, adhesion improvers, coloring agents, defoamers, thickeners, modifiers, fungicides, antibacterial An appropriate amount of an agent, a bactericide, a deodorant, a deodorant, or the like may be appropriately added.

In this pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be formed directly on the exposed surface of either the base material or the coating material. In this case, the pressure-sensitive adhesive layer is applied to the base material or the coating material. To increase the bonding strength, roughen the exposed surface of the base material or coating material, or roughen the exposed surface of the base material or coating material such as paper, woven fabric, knitted fabric, nonwoven fabric, foam film, etc. Alternatively, it is preferable to form the sheet.

In the heating element of the present invention, the pressure-sensitive adhesive layer on the exposed surface of the base material and / or the coating material may be a compress layer containing a compress or a drug-containing layer containing or carrying a transdermally absorbable drug. Is preferred because, in addition to the heating effect, a compressing effect or a therapeutic or pharmacological effect with a drug can be obtained.

In the heating element of the present invention, by incorporating a transdermally absorbable drug into the pressure-sensitive adhesive layer, the local therapeutic effect, the systemic therapeutic effect can be improved, and the circulation can be activated by the thermal effect. The drug can be absorbed into blood and the like, and the drug can be circulated to each part in the living body more effectively. Therefore, it is extremely preferable to further enhance the administration effect of each part.

The transdermally absorbable drug is not particularly limited as long as it is a transdermally absorbable drug. Specific examples thereof include a skin irritant, an analgesic anti-inflammatory agent, a central nervous system active agent (sleep Sedatives, antiepileptic agents, agents for psychiatric nerves), diuretics, antihypertensive agents, coronary vasodilators, antitussive expectorants, antihistamines, agents for arrhythmias, inotropic agents, corticosteroids, local anesthetics and the like. These drugs are used alone or in combination of two or more as needed.

The content of this drug is not particularly limited as long as it is within the range in which the medicinal effect can be expected. However, from the viewpoint of pharmacological effect, economic efficiency, adhesive strength, etc., the content of the transdermally absorbable drug is reduced. It is appropriately determined within the range of 0.01 to 25 parts by weight, particularly 0.5 to 15 parts by weight, based on 100 parts by weight of the adhesive.

In the heating element of the present invention, if desired, in order to exert the far-infrared effect, a ceramic powder or a molded body which emits far-infrared rays may be provided in the heating composition and / or on the adhesive layer side of the heating element. It is desirable to provide.

That is, ceramics that emit far-infrared rays can be used together with or in place of the heating element composition of the present invention. The ceramics can also be carried on an adhesive layer.

When a transdermally absorbable drug is used in the production of the heating element of the present invention, the above-mentioned heating element or ceramics that emit far-infrared rays are used in combination to enhance the systemic effects such as blood circulation by the heat effect. Thereby, the transdermal absorbability of the drug can be increased, and the systemic therapeutic effect and the local therapeutic effect can be further enhanced.

In the winter season, the heating element thus obtained can not only comfortably survive the cold by supplying heat to the human body, but also cause symptoms such as local dust, pain and coldness. For example, stiff shoulders, muscle pain, muscle stiffness, back pain, cold limbs, neuralgia, rheumatism, bruising,
It is used for diseases such as sprains and can be expected to have a sufficient therapeutic effect by heat.

In the heating element according to the present invention, the base material and / or the coating material may be a non-breathable or breathable film or sheet laminated on one or both sides of a foamed film or sheet, a nonwoven fabric, a woven fabric or a porous fabric. It is desirable that the exothermic composition be formed of a high quality film or sheet, since an ink-like or cream-like heat-generating composition can be laminated on one side to prevent the movement of the heat-generating composition and offset, particularly in this case, on the other side. It is particularly preferable to use a nonwoven fabric or a woven fabric, since the feeling is improved and the usability is improved.

Next, the first method of the present invention will be described in detail. In the first method of the present invention, first, the step (A) of producing the exothermic composition thickened into an ink or a cream, that is, the present invention is carried out.

Examples of the present invention include the same as those described above. By the way, in producing the product of the present invention, all the components may be charged into a mixer and then uniformly mixed, or alternatively, only the solid component of the all components may be charged into the mixer. After that, these components are uniformly mixed with this mixer, and then water or an aqueous solution or dispersion of metal chloride is added and mixed, thereby obtaining the above-mentioned present invention. Is also good. In this case, it is desirable that the solid components are put into a mixer, then mixed uniformly, and then water is added and mixed to stabilize the quality of the obtained product of the present invention.

The mixer used in the first method of the present invention is not particularly limited as long as it can uniformly mix the components constituting the present invention. Specific examples include a ribbon mixer and a spartan. A mixer, a screw blender, a roll mixer, a Banbury mixer, a kneader, or the like can be used.

By the way, in producing the product of the present invention,
When the water content is excessive, for example, in the case of an exothermic composition in the form of an ink, any mixing device may be used. On the other hand, when the exothermic composition is in the form of a cream, the proportion of moisture is relatively small, and therefore, an apparatus such as a mixer or a kneader that kneads the components while pressing the components is easy to make the exothermic composition creamy, In addition, the water squeezed out becomes free water, or after the cream-like exothermic composition is produced, the free water is absorbed by the gel around the exothermic substance. As a result, the free water or the hydrous gel forms a barrier layer (air blocking layer). )
It is desirable because the exothermic composition is stabilized.

In the present invention, the step (B) of transferring and laminating the product of the present invention obtained in the step (A) to at least one predetermined region on the upper surface of a film or sheet substrate.
Is carried out.

The base material used here is the same as that described for the heating element of the present invention, and therefore is omitted to avoid redundant description.

In this step (B), the present invention is transferred and laminated in an arbitrary shape by printing or coating such as screen printing on the upper surface of the base material. One or more places may be laminated in the width direction, or may be laminated in a staggered manner in the longitudinal direction of the base material.

In the present invention, a step (C) of covering a film-like or sheet-like covering material so as to cover the present invention is carried out.

The covering material used here is the same as that described for the heating element of the present invention, and therefore is omitted to avoid redundant description.

[0176] In this case, the base material and the covering material are bonded together via the present invention. In other words, since the present invention plays a role similar to that of the pressure-sensitive adhesive, it is not always necessary to seal the substrate and the covering material around the present invention, but in order to further improve the quality and reliability. Preferably, the base material and the coating material are sealed at the peripheral portion of the present invention by adhesion, heat bonding, or heat fusion.

[0177] In the first method of the invention, organic since it is to obtain a present invention the heating element which generates heat by contact with air, at least one or some of the coating material and the base material is breathable And a part of the water of the present invention
Is configured to be absorbed by the base material and / or the coating material.
Need to be

In the first method of the present invention, a film-shaped or sheet-shaped water-absorbing material may be applied to one or both surfaces of the material of the present invention, and the water-absorbing material may absorb a part of the moisture of the material of the present invention. is there. Examples of the water absorbing material include those described above.

In the first method of the present invention, since it is formed in the form of an ink or a cream, various advantages described below occur.

That is, in the first method of the present invention, when the ink-like or cream-like heat-generating composition, that is, the present invention is used, lamination by printing or coating such as screen printing is extremely easy. In addition to being capable of producing an ultra-thin heating element at high speed, the heating composition can be evenly distributed in the bag material, and the present invention can be applied to a foamed film / sheet, paper, nonwoven fabric, woven fabric or When sandwiched between a base material or a coating material formed of a porous film or sheet,
This product of the present invention has high penetration and anchoring properties, penetrates into the pores of these base materials and coating materials, and prevents its movement and deviation.

In this case, particularly, the base material and / or the coating material has water absorbency, and the present invention is laminated on this base material, or a water absorbing layer is further laminated on the base material, above,
When the product of the present invention is laminated and coated with a coating material, all or a part of the exothermic composition is a water-absorbing substrate and / or coating material,
Alternatively, as a result of being more easily fixed to the water-absorbing layer formed thereon, movement and bias are prevented.

Further, according to the laminating method by printing, coating or the like, the heating element can be made extremely thin. When the heating element is thin, the amount of exothermic reaction per unit time is reduced, and as a result, the exothermic composition is reduced. Excessive exothermic reaction of the object is prevented, and the material is flexible and easily follows the expansion and contraction of the outer skin, so that the usability is improved.

In addition, in the first method of the present invention, a viscous aqueous solution of a water absorbing agent is impregnated and sprayed on a sheet-like packaging material such as a foamed film / sheet, paper, nonwoven fabric, woven fabric or porous film / sheet. Laminating and drying by kneading, printing or coating, etc., containing and carrying a water absorbing agent by pressing or kneading, that is, after imparting water absorption to the sheet-like packaging material, Transferring and laminating the invention by screen printing or coating, etc., eliminates the step of charging the powder and makes it possible to easily manage the factory that satisfies GMP standards in the production of future medical devices and pharmaceuticals. Examples of the water-absorbing agent used here include the aforementioned water-absorbing polymer and thickener.

Further, in the first method of the present invention, the present invention is formed in the form of an ink or a cream, and therefore has various advantages as described above. It is extremely easy to transfer and laminate by heating, etc., and can produce an ultra-thin heating element at high speed. In addition, the surface area is significantly smaller than that of a powdered heating composition, and the amount of air supply is reduced to generate heat. As a result of substantially stopping the reaction, loss due to an exothermic reaction during production, deterioration of the quality of the exothermic composition, and solidification of the exothermic composition are prevented.

By the way, in the first method of the present invention, excess water and free water and a part of the water in the hydrogel are converted to the base material and / or free water.
Alternatively, when absorbed in a bag material such as a coating material, the barrier layer is lost, the exothermic composition becomes porous, and good contact with air is obtained. As a result, the temperature characteristics during use are improved.

Next, the second method of the present invention will be described in detail. In the second method of the present invention, the present invention is formed, and the present invention is laminated on at least one predetermined region on the upper surface of the film-like or sheet-like base material. Laminating or spraying at least one selected from a carbon component or a water-absorbing agent;
And a coating material in the form of a film or sheet so as to cover at least one selected from iron powder, a carbon component and a water absorbing agent, and at least one or a part of the base material and the coating material has air permeability. It is characterized by having.

In the second method of the present invention, a film-shaped or sheet-shaped water-absorbing material may be applied to one or both surfaces of the material of the present invention, and a part of the moisture of the material of the present invention may be absorbed by the water-absorbing material. is there. Examples of the water absorbing material include those described above. In this case, one or both surfaces of the present invention means one or both surfaces of at least one selected from iron powder, a carbon component, and a water absorbing agent in a state of being laminated or sprayed on the upper surface of the present invention.

Accordingly, the covering material is applied so as to cover at least one selected from the present invention, iron powder, carbon component or water absorbing agent and the water absorbing material.

In the second method of the present invention, the heating element of the present invention which generates heat by contact with air is obtained.
Since at least a part of the packaging material composed of the base material and the coating material has air permeability, and the base material and the coating material are the same as those described in the heating element of the present invention, the description will not be repeated. Omitted.

That is, in the second method of the present invention, in the first method of the present invention, at least one selected from the group consisting of iron powder, a carbon component and a water absorbing agent is laminated or sprayed on the upper surface of the product of the present invention. And a coating material in the form of a film or sheet so as to cover at least one selected from the group consisting of iron powder, a carbon component and a water-absorbing agent. Since it is the same as that of FIG.

Next, the third method of the present invention will be described in detail. In the third method of the present invention, first, the present invention is laminated on a film-like or sheet-like base material, and then a film-like or sheet-like covering material is placed thereon, and the viscosity of the present invention-like substance is increased. Thus, the base material and the covering material are laminated to obtain a laminate. In this case, a film-shaped or sheet-shaped water-absorbing material may be applied to one or both surfaces of the present invention.

In the third method of the present invention, examples of the present invention used include those similar to those described above, and a detailed description thereof will be omitted to avoid redundant description.

[0193] In the third method of the present invention, as in the above-mentioned case, until a part of the water content of the present invention is absorbed by the water-absorbing base material and / or the coating material, even if it comes into contact with air. Since the oxidation reaction of the product of the present invention, that is, the exothermic reaction is suppressed, loss of the exothermic composition due to the exothermic reaction during production, deterioration of the quality of the exothermic composition and solidification of the exothermic composition are surely prevented. Since the product is formed in an ink or cream form, it can be laminated to a uniform thickness. In addition, the present invention is viscous and adheres to the packaging material, so that the movement of the exothermic composition and displacement are prevented. In addition, excessive exothermic reaction of the exothermic composition can be avoided as much as possible.

In the third method of the present invention, the method of laminating the product of the present invention on a substrate is not particularly limited, but specifically, for example, a coater such as a head coater,
Coating and coating with a roller, an applicator or the like can be mentioned.

In the third method of the present invention, the heating element of the present invention which generates heat by contact with air is obtained.
At least one or a part of the base material and the coating material has air permeability, and the base material and the coating material are the same as those described in the heating element of the present invention. Omitted.

In the third method of the present invention, the obtained laminate is then punched into an arbitrary shape to obtain a heating element. Therefore, it is preferable that the base material and the coating material are easily punched out. From this viewpoint, it is preferable that the base material and the coating material are formed of paper.

The step of punching the laminate into a predetermined shape may be performed while the laminate is stationary. In this case, a plurality of laminates arranged at the same time in the feed direction of the laminate and in the width direction perpendicular thereto. Can be formed at the same time by punching out a large number of heating elements at the same time, so that the cost can be reduced.

However, in this method, as described above, the present invention is laminated on a roll film-shaped or roll-sheet-shaped substrate while feeding it at, for example, 160 to 200 m / min. To cover the coating material of the present invention by a method of guiding a coating material in the form of a roll film or a roll sheet thereon with a roll, and thereby obtain a laminate, in order to stop the laminate in the punching step First, it is necessary to wind the laminate into a roll shape and punch out while intermittently feeding out this roll.
The manufacturing process becomes complicated and the manufacturing time becomes longer.
Since the punching operation is performed intermittently, there is a limit in improving the operation efficiency.

Therefore, in the third method of the present invention, in order to simplify the manufacturing process and shorten the manufacturing time,
The feed rate at the time of manufacturing the laminate is, for example, 160 to 2 per minute.
It is preferable that the heating element of the present invention is obtained by punching into an arbitrary shape using a roll press while feeding at a speed of 00 m / min.

As described above, when the roll press is used, the laminated body can be continuously punched, and the production and the punching of the laminated body can be performed continuously and continuously. As a result, the cost can be significantly reduced as compared with a method in which the stacked body is stopped and punched.

In this case, by punching continuously at one or two or more places in the width direction of the laminate or by continuously punching a plurality of pieces in the laminate in a staggered manner in the longitudinal direction, a larger amount can be obtained in a short time. By manufacturing the heating element of the present invention, it is possible to further reduce the cost.

[0202] The punched shape of the laminated material is punched in a shape to cover an arbitrary portion according to the use of the obtained heating element. That is, in the third method of the present invention, the obtained laminate is punched into a desired arbitrary shape, and the heating element of the present invention obtained by punching is, for example, for feet, for shoulders,
It is not particularly limited, such as for a waist, and may be of any shape.

By the way, in the third method of the present invention, the base material and the coating material are bonded together due to the viscosity of the product of the present invention. After this bonding, a part of water is absorbed by the base material and the coating material. As a result of the heating element being enclosed in a non-breathable outer packaging material and provided for distribution, it may be sold as it is or as a commercial product.

However, the punched-out heating element of the present invention is interposed between two films or sheets, and at the same time as or after this interposition, the two films or sheets are separated from the heating element of the present invention or more. It is preferable that the two films or sheets are sealed at the periphery of the heating element of the present invention at the same time as or after the punching.

In this case, a film having at least one or a part of the two films or sheets having air permeability is used, and thus a more reliable heating element of the present invention can be obtained.

That is, the heating element of the present invention having an arbitrary shape is obtained by this step, and the amount of air supplied to the heating composition inside the heating element is controlled by the air permeability of the two films. The management of the air permeability to the product of the present invention is managed on the basis of the moisture permeability in the same manner as the management of the air permeability of the base material and / or the coating material in the heating element of the present invention. Since the moisture permeability of the laminated film or sheet of one of the films and the substrate or the covering material is the same as that of the product of the present invention and the heating element of the present invention, detailed description thereof will be omitted to avoid redundant description.

The two films or sheets include a non-breathable one and a breathable one.
This includes not only those having tackiness, but also those having heat adhesion or heat fusion.

As the adhesive film or sheet, a base film or base sheet may be formed by forming a gas-permeable pressure-sensitive adhesive layer on the entire surface thereof with a hot-melt type pressure-sensitive adhesive, or may be partially gas-permeable over the entire surface. Alternatively, the base film or the base sheet having a non-breathable pressure-sensitive adhesive layer formed thereon may be mentioned, and it does not matter whether the base film or the base sheet itself has a heat adhesive property or a heat fusible property.

In the third method of the present invention, after the formation of the long heating element, before or after the punching of the long heating element, or after the formation of the long heating element. Alternatively, after punching out a long heating element, two films or sheets are sealed at the peripheral edge of the heating element.

Here, the punching into a larger size than the heating element is not particularly limited as long as it is at least the size of the heating element. In particular, the punching is performed in a shape similar or substantially similar to the shape of the heating element. Therefore, it is preferable to form a large shape extending over the entire circumference by about several mm to 20 mm from the shape.

Then, in the third method of the present invention, the extended portion is sealed, that is, the two films or sheets are sealed at the peripheral edge of the heating element by adhesion, heat bonding or heat fusion. Because

In the first to third methods of the present invention, the pressure-sensitive adhesive layer is formed on the whole or a part of the exposed surface of any one of the heating elements of the present invention, and at least a part of the other is provided. However, those having air permeability are desirable.

The pressure-sensitive adhesive layer may be a compressing layer containing a compressing agent, or a drug-containing layer containing or carrying a transdermally absorbable drug. Omitted to avoid.

This pressure-sensitive adhesive layer may contain or carry at least one of a far-infrared radiator and a magnetic material.

In the above-mentioned first to third methods of the present invention, the obtained heating element may have a part of the water content in the present invention between the production and use thereof, which may be a substrate and / or a coating material or a coating material. or it is taken to the present invention was one side or the water absorbent material which the covering was cracking on both sides of, part of the moisture of free water or water-containing gel of the present invention was in
Is absorbed by the substrate and / or coating material or the water-absorbing material applied to one or both surfaces of the product of the present invention, resulting in a porous and good contact with air, and a rapid exothermic reaction upon contact with air. The resulting heating element is obtained.

[0216]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below with reference to the drawings, but the present invention is not limited thereto.

As shown in the schematic sectional view of FIG. 1, the heating element of the present invention according to the first embodiment of the present invention has an ink-like shape in a rectangular flat bag body (packaging material) 1 having a length of 130 mm and a width of 95 mm. Or a cream-like heat-generating composition, that is, one in which the present invention 2 is enclosed. In this case, the bag 1 is composed of a non-breathable base material 3 and a breathable coating material 4, In addition, an adhesive layer 5 having a thickness of 100 μm is formed on the exposed surface of the substrate 3.

The substrate 3 is made of a non-breathable polyethylene film 3 having a thickness of 40 μm so that sufficient flexibility can be obtained.
b) On one surface thereof, a polyester nonwoven fabric containing a water-absorbing polymer (thickness: 210 μm, Sunwet IM-5000MPS, 10 g / m ² ) 3a, and on the other surface, rayon with a rayon fiber content of 60% by weight.
Polyester mixed nonwoven fabric (thickness: 140 μm) 3c was used.

In order to increase the mechanical strength and to obtain sufficient flexibility, the coating material 4 is, for example, a nylon nonwoven fabric 4b having a thickness of 150 μm on one side of a polyethylene porous film 4a having a thickness of 100 μm. Are laminated. The moisture permeability of the coating material 4 was adjusted so that the moisture permeability was 400 g / m ² · 24 hr by the Lissi method.

Further, the pressure-sensitive adhesive layer 5 is for sticking to the outer skin, and this pressure-sensitive adhesive layer 5 is formed of a styrene-isoprene-styrene block copolymer-based pressure-sensitive adhesive.

The present invention 2 was manufactured by the following method. That is, iron powder as an active ingredient (manufactured by Dowa Iron Powder Co., Ltd.)
DKP) (70 parts by weight), activated carbon (GL-50, manufactured by Norit) 10 parts by weight as a carbon component, salt (sodium chloride) 2 parts by weight as a metal chloride, and a thickener (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) Metroose 60SH-4000) 0.
7 parts by weight, 0.2 parts by weight of a surfactant (trade name: DEMOL EP, manufactured by Kao Corporation) and 0.1 part by weight of sodium tripolyphosphate as a pH adjuster were mixed, and water was added to the mixture. It is adjusted so that the viscosity at a temperature of about 250,000 cps.

That is, activated carbon, thickener, surfactant, P
The H adjuster, salt and iron powder were added in this order to a mixer (TK Hibis Mix 2P-100, 100 liter capacity, manufactured by Tokushu Kika Kogyo Co., Ltd.) at the above mixing ratio, and after stirring for 5 minutes, Add water while stirring,
Knead for 15 minutes.

Thereafter, the blades and the deposits in the container are cleaned, kneaded again for 20 minutes, and the viscosity and specific gravity are measured. The water content is adjusted so that the viscosity is around 250,000 cps by the following method. The water content is iron powder (DK
P) was 40 parts by weight with respect to 100 parts by weight. The obtained product of the present invention had a viscosity of 230,000 cps. The rotation speed of the blade was 10 rpm from the start to the end.

When the composition of the present invention was stored at 10 ° C. for 1 hour, the viscosity increased. However, when the composition was kneaded again, the viscosity was 250,000 cps by the following method, and this was laminated on the substrate 3 by screen printing. . Also in this case, the rotation speed of the blade was 10 rpm from the start to the end.

The viscosity is determined by TOKIMEC IN
C. (VISCOMTER BH type viscometer), using a # 7 rotor, a rotation speed of 2 rpm, and a measurement temperature of 20 using a beaker having a beaker inner diameter (85 mm).
It is a value measured at ° C.

The product 2 of the present invention is in the form of an ink or a cream, has a small surface area, has a limited contact area with air, and has a gel containing free water or water that suppresses contact between iron powder and air. As a result, the amount of oxidation per unit time is remarkably limited, and as a result, the oxidation reaction until the heating element is obtained, which is laminated with a film-like or sheet-like coating material, is almost prevented. .

As described above, the present invention 2 is an ink-like or cream-like viscous body. The present invention 2 can be laminated on the upper surface of the water-absorbing polymer-containing polyester nonwoven fabric 3a on the substrate 3 by screen printing. become,
The lamination area can be controlled with high precision, and the film thickness can be controlled very thinly and uniformly, and the bonding force between the water-absorbent polymer-containing polyester mixed nonwoven fabric 3a on the base material 3 and the present invention 2 Thereby, the present invention 2 is prevented from moving in the bag 1. Further, by making the film thickness of the present invention 2 thin, the heating element can be made ultra-thin.

In this example, the present invention 2 was screen-printed to a film thickness of about 0.5 mm on the upper surface thereof while horizontally feeding a roll film-like substrate 3 having a width of 130 mm at a speed of 180 m / min. Immediately after the screen printing, the coating material 4 is put on, and the periphery of the printing area is subsequently sealed by heat sealing, and cut one after another at the center of the heat sealing area in the width direction. A heating element of the present invention having a width L of 7 mm and an ultra-thin shape was manufactured.

[0229] Each of the cut heating elements of the present invention is subsequently sent to a packaging step and sealed in an airtight outer bag (not shown).

In the present invention 2, after screen printing is performed on the upper surface of the base material 3, a part of the water is gradually absorbed by the base material 3, and the coating material 4 is coated thereon. . However, the time from when the present invention 2 is screen-printed on the base material 3 until it is sealed in the outer bag is extremely short,
During this time, the moisture of the product 2 of the present invention is hardly absorbed by the substrate 3 to such an extent that an exothermic reaction becomes possible.

Therefore, there is almost no possibility that heat generation of the product 2 of the present invention occurs in the production process, and there is no risk of loss due to the exothermic reaction or deterioration of the quality of the heat generating composition. Further, in the process from the blending of the present invention 2 to the screen printing on the substrate 3, there is almost no risk of the present invention being solidified, the yield is reduced by the solidification, the operation is interrupted, the operation time is restricted, and the cleaning of the manufacturing apparatus is reduced. Various adverse effects such as difficulty and danger, frequent cleaning of the manufacturing apparatus, and difficulty in coagulation treatment can be prevented.

Also, after 24 hours have passed after enclosing in the outer bag, the outer bag was broken and adhered to the human body surface. The temperature was raised, and thereafter, heat was generated at 38 to 41 ° C for 9 hours or more. During this use, the present invention 2 did not move in the bag 1 at all, and an average heat generation was observed over the entire surface.

The heating element of the present invention according to the second embodiment of the present invention is provided in a rectangular flat bag (packaging material) 1 having a length of 130 mm and a width of 95 mm as shown in the schematic sectional view of FIG. The bag 1 is made up of a non-breathable base material 3 and a breathable covering material 4. In this case, the exposed surface of the base material 3 has a thickness of A pressure-sensitive adhesive layer 5 of 100 μm styrene-isoprene-styrene block copolymer system is formed.

The base material 3 was coated on both sides of a 40 μm-thick polyethylene film 3b with a thickness of 140 μm and a rayon / polyester mixed nonwoven fabric 3a having a rayon fiber content of 60% by weight so that sufficient flexibility was obtained. · 3c is laminated.

The coating material 4, the present invention 2 and the pressure-sensitive adhesive layer 5 were the same as those in the first embodiment.

Then, the present invention 2 is laminated on the upper surface of the substrate 3 by screen printing, and thereafter, a water absorbing agent (Nippon Shokubai high water absorbing resin Aquaclick CS-6HS) is manually applied on the upper surface of the present invention 2. Spray to absorb water (weight 20g / m
² ) After forming 6, the covering material 4 is covered, and the periphery is heat-sealed. The periphery of each heating element is sealed by heat sealing, so that the sealing width L around each heating element is 7 mm, and the present invention is ultra-thin. A heating element was manufactured.

In short, in the second embodiment, except that a part of the water content of the present invention 2 is also absorbed by the water absorbing layer 6, the heating element of the present invention, its manufacturing method and other constitutions are different. Since the operation and effects are the same as those of the first embodiment and the previous example, and their operations and effects are also the same as those of the first embodiment, their description will be omitted to avoid duplication.

The heating element of the present invention according to the third embodiment of the present invention is different from that of FIG. 3 in that the vertical relationship between the water absorbing layer 6 and the present invention 2 is reversed. For example, the configuration is the same as in the previous example.

That is, in the heating element of the present invention, the water-absorbing layer 6 having a basis weight of 20 g / m ² was formed on the substrate 3 by the following method. That is, using a water absorbing agent (manufactured by Nippon Shokubai, high water-absorbing resin Aquaclick CS-6HS), a 4% by weight aqueous solution was printed by screen printing to a thickness of 500 μm, and dried to obtain a basis weight of 20 g / m ² . The water absorbing layer 6 was formed.

The heating element of the present invention according to the third embodiment is manufactured in the same manner as in the preceding example except that the heating element of the present invention 2 is manufactured by screen-printing the surface of the water-absorbing layer 6 on the substrate 3. Manufactured in.

In short, the heating element of the present invention, its manufacturing method and other constitutions are the same as those of the first embodiment and the previous example. Therefore, their operations and effects are the same as those of the previous example. These descriptions will be omitted to avoid this.

Next, a method of manufacturing a heating element of the present invention for heating a shoulder portion according to a fourth embodiment of the present invention and an example of the heating element of the present invention for shoulder temperature manufactured by this method will be described. FIG. 4 is a perspective view of the heating element of the present invention for shoulder temperature.

The heating element prints the present invention 2 on the substrate 3 in a gourd-like shape in a plan view while feeding out the base material 3 having water absorbency, and then exposes the surroundings of the present invention 2. An adhesive is applied to the surface, and the coating material 4 is guided and laminated on the surface by a roller, whereby the base material 3 and the coating material 4 are bonded to each other by sandwiching the exothermic composition 2 with the base material. A pressure-sensitive adhesive layer 5 having a thickness of 50 μm is formed on the exposed surface of No. 1 and the long heating element thus obtained is expanded by about 7 mm from the present invention 2 by a roll press. In this embodiment, the cover is manufactured by punching it into a gourd shape in plan view.

With this configuration, the base material 3 and the coating material 4
Are bonded by the present invention 2.

As shown in the sectional view of the main part of FIG.
Is a laminate of a water-absorbent rayon nonwoven fabric 3a having a basis weight of about 80 g / m ² and a non-breathable polyethylene sheet 3b having a thickness of about 50 μm. The object 2 is printed so as to make direct contact.

The coating material 4 is formed by laminating a breathable polyethylene sheet 4b having a thickness of about 50 μm on a water-absorbent rayon nonwoven fabric 4a having a basis weight of about 80 g / m ² and having a moisture permeability of 300 g. / m ² · 24h
In this coating material 4, the coating material 4 is laminated on the rayon nonwoven fabric 4a such that the present invention 2 comes into direct contact with the nonwoven fabric 4a.

For the pressure-sensitive adhesive layer 5, a styrene-isoprene-styrene block copolymer system is used. In order to increase the adhesion of the pressure-sensitive adhesive layer 5 to the substrate 3, the pressure-sensitive adhesive The exposed surface of the polyethylene sheet 3b is roughened to have a wetting index of 40 dynes or more by corona treatment.

The present invention 2 is characterized in that iron powder which is a heating substance is used.
(DKP manufactured by Dowa Tekko Co., Ltd.) 100 parts by weight as a water-absorbing polymer (Sunwet IM, manufactured by Sanyo Chemical Co., Ltd.)
-5000MPS) 0.21 part by weight, as a thickener (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen EP) 1.4 parts by weight, activated carbon (Norit SA-SUPER) 4.21 parts by weight,
4.87 parts by weight of sodium chloride as a metal chloride and 0.25 parts by weight of sodium tripolyphosphate as a pH adjuster are mixed, and water is added to the mixture so that the viscosity at a temperature of 20 ° C. becomes about 3 million cps. It has been prepared to be.

That is, the activated carbon, the thickener, the water-absorbing polymer, the pH adjuster, the salt and the iron powder were arranged in this order, and in the mixing ratio described above (TK Hibis Mix 2P- manufactured by Tokushu Kika Kogyo Co., Ltd.). 100 type capacity 100 liter)
After stirring for 5 minutes, water is further added while stirring, and kneading is performed for 15 minutes.

Thereafter, the blades and the deposits in the container are cleaned, kneaded again for 20 minutes, and the viscosity and specific gravity are measured. The water content is adjusted so that the viscosity is around 3,000,000 cps by the following method. In this case, the water content was 29.79 parts by weight based on 100 parts by weight of iron powder (DKP manufactured by Dowa Iron Powder Co., Ltd.). The obtained product of the present invention had a viscosity of 3.03 million cps. The rotation speed of the blade was 10 rpm from the start to the end.

When the product of the present invention was stored at 10 ° C. for 1 hour, the viscosity increased. However, when it was kneaded again, the viscosity was 3.05 million cps by the following method, and this was laminated on the substrate 3 by screen printing. . Also in this case, the rotation speed of the blade was 10 rpm from the start to the end.

The viscosity was measured by using Toki Sangyo Co., Ltd. (R
110 type viscometer, RE110U system, detection head R
E100U, controller RC100A) and S
Using a PP rotor, the number of rotations was 0.2 rpm (D = 0.4
(1 / S)) and a value measured at a measurement temperature of 20 ° C.

Therefore, it was confirmed that the gel of the present invention 2 functions as a barrier layer in which the gel containing free water or water prevents contact between iron powder and air, and as a result, almost no exothermic reaction occurs.

On the base material 3, the present invention product 2 was coated with a thickness of 820.
When screen printing is performed so as to have a thickness of μm, the water in the gel containing free water or water in the product of the present invention becomes
Of the heat-generating composition 2 was set after the water-absorbent rayon nonwoven fabric 3a began to be absorbed by the water-absorbent rayon nonwoven fabric 3a, and was covered by the rayon nonwoven fabric 4a in the coating material 4 It is in an optimal state for generating an exothermic temperature.

However, the water in the gel containing the free water or water is absorbed by the base material 3 and the coating material 4,
While it takes a considerable amount of time to reach the predetermined blending ratio, the time required for the obtained heating element of the present invention to be sealed in the air-impermeable bag is extremely short. The water mixing ratio of the product 2 does not become the optimum mixing ratio for generating a predetermined heat generation temperature.

As described above, the present invention 2 does not generate heat until the heating element of the present invention is sealed in the air-impermeable bag.
The product of the exothermic reaction solidifies and causes various adverse effects, such as reduced yield, difficulty in handling, complicated maintenance of the manufacturing equipment, restrictions on the operating time of the manufacturing equipment or the working hours of workers, and difficulty in coagulated material processing. There is no risk of adverse effects such as the nature.

By the way, the heating element of the present invention is sealed in a non-air-permeable bag and reaches the user's hand through distribution.
Excess water in the present invention 2 is absorbed by the water-absorbent rayon nonwoven fabric 3a in the base material 3 and the water-absorbent rayon nonwoven fabric 4a in the coating material 4, and the moisture content becomes suitable for obtaining a predetermined heat generation temperature. Therefore, the quality of the exothermic composition 2 does not deteriorate before the non-breathable bag is broken and comes into contact with air, and the quality of the heat-generating composition 2 can be maintained at a high level. As soon as the heating element of the present invention is taken out, an exothermic reaction is started and the temperature is quickly raised to a predetermined exothermic temperature.

In addition, since the product 2 of the present invention has a high fluidity, it can be laminated on the substrate 3 by a technique of printing or coating. As a result, the conventional powdery heat-generating composition having no fluidity is simply placed on the substrate 3. Compared to the case of dropping, it is possible to stack the layers accurately and at high speed in a predetermined range and at a uniform thickness.

The heating element of the present invention is sealed in an air-impermeable bag,
After leaving it for 10 days, the heat-generating body of the present invention was taken out by breaking the air-impermeable bag, and then used by directly adhering to the shoulder using the pressure-sensitive adhesive layer 5, which was excellent for more than 6 hours. A warming effect was obtained.

When the heating element of the present invention is applied, since the heating element is formed to be ultra-thin, it becomes flexible as a whole, so that the feel to the shoulder is softened and the shoulder is easily bent. It is deformed along, deformed following the movement of the shoulder very well, has good adhesion to the application site, and the heating element of the present invention does not peel off from the application site during use, and is excellent A warming effect was obtained, and it was recognized that the shoulder was effectively warmed.

Furthermore, in this use, the exothermic composition 2 does not move, the exothermic temperature distribution of the exothermic body of the present invention is uniform, there is no low-temperature burn, and the safety is enhanced.

Next, although not shown, the heating element of the present invention for heating the back as a fifth embodiment according to the present invention is shown in FIG.
It was manufactured in the same manner as in the example.

The present invention 2 is characterized in that iron powder which is a heating substance is used.
Activated carbon (SA-SUPER manufactured by Norit) 7.0 parts by weight, diatomaceous earth (obright) 2.0 parts by weight as a water retention agent, and a thickener as 100 parts by weight (DKP manufactured by Dowa Iron Powder Co., Ltd.)
1.4 parts by weight (trade name, Cellogen EP, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.3 parts by weight as a water-absorbing polymer (trade name, Sunwet IM-5000MPS, manufactured by Sanyo Chemical Co., Ltd.), and sodium chloride as a metal chloride. 0 parts by weight and 0.3 parts by weight of sodium tripolyphosphate as a pH adjuster were mixed, and water was added to the mixture to give a viscosity at 20 ° C. of 2 parts.
It was prepared to be about 500,000 cps.

That is, a mixing machine (manufactured by Tokushu Kika Kogyo Co., Ltd.) in the order of activated carbon, diatomaceous earth, a thickener, a water-absorbing polymer, a pH adjuster, and sodium chloride in the stated order.
T. K. Hibismix 2P-100 type capacity 1
00 liters), and after closing the lid in a sealed state, while stirring at a rotation speed of 10 rpm, iron powder is thrown in from an inlet and stirred for 3 minutes, and water is thrown in while further stirring, and the rotation speed is increased to 15 rpm. After rising and mixing for 5 minutes, stop once.

Next, after cleaning the deposits on the blades and casing of the mixer, they are mixed again at a rotation speed of 1 rpm for 5 minutes, and the viscosity and specific gravity are measured. The viscosity is 2
The water content is adjusted to be around 500,000 cps. In this case, the water content was 42.0 parts by weight based on 100 parts by weight of iron powder (DKP manufactured by Dowa Iron Powder Co., Ltd.). The specific gravity of the obtained product of the present invention is 2.428 g / ml, and the viscosity is 2.52 million cp.
s.

When the product of the present invention was stored at 10 ° C. for 1 hour, the viscosity increased. However, when the material was kneaded again, the viscosity was 2.55 million cps by the following method, and this was laminated on the base material 3 by screen printing. . In this case, the rotation speed of the blade was set at 10 rpm.

The viscosity was measured by using Toki Sangyo Co., Ltd. (R
110 type viscometer, RE110U system, detection head R
E100U, controller RC100A) and S
Using a PP rotor, the number of rotations was 0.2 rpm (D = 0.4
(1 / S)) and a value measured at a measurement temperature of 20 ° C.

Therefore, it was confirmed that the present invention 2 functions as a barrier layer in which the gel containing free water or water prevents contact between iron powder and air, and as a result, almost no exothermic reaction occurs.

The obtained heating element of the present invention was sealed in a non-permeable bag, and after leaving it for 10 days, the non-permeable bag was broken to take out the heating element of the present invention. When used by directly adhering to the back, an excellent thermal effect was obtained for 6 hours or more.

When the heating element of the present invention is applied, since the heating element is formed to be ultra-thin, it becomes flexible as a whole, so that the feel to the back becomes soft and the back moves very well. The heating element of the present invention is not deformed following, has good adhesion to the application site, and does not peel off from the application site during use, provides an excellent heating effect, and effectively heats the shoulder. Was observed.

Further, upon use, it was confirmed that the exothermic composition 2 did not move, the exothermic temperature distribution of the exothermic body of the present invention was uniform, there was no low-temperature burn, and safety was high.

Next, an exothermic experiment was performed by the following method. 70 parts by weight of iron powder (DKP manufactured by Dowa Iron Powder), 10 parts by weight of activated carbon as a carbon component (Activated Carbon GL-50 manufactured by Norit), 2 parts by weight of sodium chloride as a metal chloride, thickener (Metroze manufactured by Shin-Etsu Chemical Co., Ltd.) 60SH-4000) 0.7 parts by weight, a surfactant (manufactured by Kao Corporation, trade name: Demol EP) 0.2 parts by weight, and a PH adjuster (sodium tripolyphosphate) 0.1 part by weight, excess water is added. In addition, temperature 20 ℃
Thus, an ink-like or cream-like viscous liquid having a viscosity of 10,000 cps and 6.8 million cps was prepared.

A product of the present invention having a viscosity of 10,000 cps and a viscosity of 6
As shown in FIG. 6, the exothermic composition was put into a 200 ml beaker 10 using the 800,000 cps of the present invention, and the temperature sensors 11 were respectively inserted into positions D 10 mm below the surface and the center of the surface. The temperature change was measured.

As a result, in the exothermic composition having a viscosity of 10,000 cps, no temperature increase was observed at both the surface and the center in about 20 minutes, but in the exothermic composition having a viscosity of 6.8 million cps, 5 The temperature rises in about a minute,
In the center, almost no temperature rise was observed in about 5 minutes.

On the other hand, as comparative examples, 60 parts by weight of iron powder, 10 parts by weight
An exothermic composition consisting of 25 parts by weight of a saline solution, 13 parts by weight of activated carbon, and 14 parts by weight of wood flour was used. The same iron powder, salt and activated carbon as those used in the above-described example were used. In this case, it was impossible to measure the viscosity.

Using this exothermic composition, an exothermic experiment was conducted in the same manner as described above. As a result, it was found that the temperature rose immediately on both the surface and the center, and it exceeded 60 ° C. in about 2 minutes.

In the present invention, the above-mentioned Examples 1 to 3 may be combined, and a film- or sheet-like water-absorbing material, particularly a paper having a high water-absorbing property, is applied to one or both surfaces of the present invention. It is also possible to absorb a part of the water content of the invention and fix the invention to the paper more firmly.

[0278]

As described above, since the exothermic composition according to the present invention is thickened into an ink or a cream, the exothermic composition is laminated on a substrate by printing or coating. In addition, the lamination area can be controlled with high precision, and the present invention can be laminated on a substrate with a very thin film thickness and evenly. As a result, an ultra-thin heating element of the present invention can be formed at high speed. The effect that can be manufactured is obtained.

[0279] Further, the present invention was laminated on the substrate top surface, after being coated with a coating material thereon, the substrate and / or covering material further excess moisture, such as water-absorbing layer, or the free water or water-containing gel Since water is absorbed, there is almost no exothermic reaction of the present invention at the time of production, and loss due to the exothermic reaction at the time of production,
In addition to preventing quality deterioration of the present invention and solidification of the present invention,
By the time of use, a portion of the water in the present invention is partially
Or, as a result of being absorbed by the coating material and the water-absorbing layer, the mixing ratio of the water of the present invention at the time of use becomes a state suitable for the exothermic reaction, the contact with air becomes good, and the desired exothermic temperature is obtained. Has the effect of

Further, as described above, the present invention is laminated on a substrate by printing or coating. Since the present invention has adhesiveness, the present invention is applicable to a substrate, a coating material or a water-absorbing layer. It is adhered to and fixed to the like, so that the movement of the present invention in the bag is reliably prevented. As a result, the temperature variation of the exothermic composition is eliminated, and the exothermic composition is biased in the bag. The effect of reliably preventing the occurrence of high-temperature spots, reliably preventing the occurrence of low-temperature burns, and improving safety is also obtained.

In the heat generating element of the present invention, since the heat generating composition thickened in the form of an ink or cream, that is, the present invention is used, the heat generating composition can be made ultra-thin by printing or coating. In addition, the heating element can be laminated uniformly, so that the heating element is ultra-thin, highly flexible,
The ability to follow curved or bent parts such as shoulders is extremely good,
It has the effect of excellent feeling in use.

[0282] In the present invention heating elements, because by using a heat-generating composition was thickening in the ink-like or cream-like, excessive moisture, or free water or water-containing gel is a barrier layer, at the time of manufacture The occurrence of an exothermic reaction of the present invention is significantly reduced, and a loss due to an exothermic reaction during production;
While the quality deterioration and coagulation of the exothermic composition are prevented, the moisture in the exothermic composition is absorbed by the packaging material by the time of use, and the mixing ratio of the moisture of the exothermic composition during use is suitable for the exothermic reaction. As a result, the desired exothermic temperature can be obtained at the time of use, so that the quality is extremely high and the reliability is extremely high.

Further, in the heating element of the present invention, the movement of the heat-generating composition in the bag material can be reliably prevented by the bonding force between the packaging material and the present invention. It is possible to reliably prevent the exothermic composition from being partially offset and causing a high-temperature exothermic part to occur,
As a result, the effect of reliably preventing the occurrence of low-temperature burns and improving safety can be obtained.

[0284] Particularly, in the present invention the heating element, it places the present invention was to direct contact from those having water absorption, to absorb excess moisture present invention was in, or free water or water in the hydrogel As a result, the exothermic composition is attracted to the substrate and / or the coating material or the water-absorbing layer, and a part of the product of the present invention penetrates into the substrate and / or the coating material or the water-absorbing material to produce an anchor effect. Thereby, the effect of fixing the present invention to the substrate and / or the coating material or the water absorbing layer can be obtained.

In this case, if the contact portion between the substrate and / or the coating material and the present invention is formed of a water-absorbent foam film sheet, nonwoven fabric, woven fabric or porous film sheet, The effect of the present invention is that the bondability with the present invention is further improved, the movement and the offset of the present invention are more reliably prevented, and various adverse effects associated with the offset of the present invention are more reliably prevented.

In the heating element of the present invention, when the base material and the coating material have extensibility, in particular, elasticity, it becomes easier to imitate the heating element in a complex uneven shape at an arbitrary portion. The ability to follow the change in the irregular shape due to the movement is enhanced, the peeling of the heating element or the lifting from the application site is reliably prevented, and the close contact with the living body is improved, so that an excellent warming effect and a blood circulation promoting effect are obtained. It has the effect that it is.

In the heating element of the present invention, when the substrate and / or the coating material or the water-absorbing layer has water absorption, a part of the water in the present invention is absorbed by the time of use, and As a result, the heat generation can be started immediately by breaking the airtight bag at the time of use, and the required heat generation temperature can be obtained quickly. As a result, water evaporating from the exothermic composition with the progress of the exothermic reaction can be replenished by discharging water from the substrate and / or the coating material, and the required exothermic temperature can be maintained for a long time. can get.

In the heating element of the present invention, when a film- or sheet-shaped water-absorbing material, particularly paper having a high water-absorbing property, is applied to one or both surfaces of the present invention, a part of the water of the present invention is absorbed, The invention can be more firmly fixed to the paper.

In the heating element of the present invention, when the pressure-sensitive adhesive layer contains or carries at least one of a far-infrared radiator, a magnetic substance, and a transdermally absorbable drug, a far-infrared heating effect and a far-infrared therapeutic effect In addition to obtaining magnetic therapeutic effects, therapeutic effects by drugs, these effects are synergistically promoted with systemic and local actions such as blood circulation promotion by heat generation of the heating element, and the effects are further enhanced. The effect is obtained.

In the first method of the present invention, the heat-generating composition can be formed on a substrate by transfer, printing, etc., by forming the product of the present invention. As a result that the heat-generating composition can be uniformly laminated on the substrate with a very thin film thickness, the effect of producing an ultra-thin heating element of the present invention at a high speed can be obtained.

Further, in the first method of the present invention, the composition of the present invention is increased in water content to make it into a mucous form in the form of an ink or a cream and laminated on a substrate. Since the material or the water-absorbing layer absorbs moisture, there is almost no exothermic reaction of the present invention at the time of production, loss due to the exothermic reaction at the time of production, deterioration of the exothermic composition and solidification can be prevented, and the present invention can be used before use. A part of the moisture in the substrate and / or
Alternatively, by absorbing the moisture into the coating material or the water-absorbing layer, the mixing ratio of water becomes suitable for the exothermic reaction, and the highly reliable heating element of the present invention can be obtained.

In the first method of the present invention, the present invention to be used is formed in an ink or cream form, and can be accurately laminated on a substrate in a predetermined range without waste. The heating element of the present invention, which effectively heats the site, can be obtained. As a result, an excellent heating effect and blood circulation promotion can be effectively obtained, and the dust of the heating composition to the surroundings can be reduced as in the related art. There is a particularly remarkable effect that there is no emission and that factory management that fully satisfies GNP standards in future medical device and pharmaceutical manufacturing can be performed.

In the first method of the present invention, the heat generating composition of the present invention is formed by laminating an ink-like or cream-like heat generating composition on a substrate by printing or coating, and covering the material with a coating material. Furthermore, since the process up to packaging the heating element can be performed consistently and in a very short time, the heating composition does not become a condition capable of generating heat in the manufacturing process, and the present invention is used during the manufacturing process. Is prevented from generating heat.

As a result, quality reduction and solidification of the product of the present invention can be completely prevented during the production of the heating element. As a result, the yield is reduced, handling is difficult, the maintenance of the production equipment is complicated, and the operation time of the production equipment is reduced. In addition, it is possible to eliminate various adverse effects such as restrictions on the working hours of workers and difficulty in coagulation treatment, and obtain an effect that a high-quality and highly reliable heating element of the present invention can be obtained at lower cost. .

In the second method of the present invention, the heat-generating composition of the present invention, that is, an exothermic composition which is made into an ink or a cream by increasing the mixing ratio of water is formed.
After laminating at least one predetermined region on the upper surface of the film or sheet, at least one selected from iron powder, carbon component or water absorbing agent is laminated or sprayed on the upper surface of the present invention, and then After covering with a film-like or sheet-like covering material so as to cover them, the base material and the covering material are adhered with the present invention, and a part of the moisture of the present invention is used as the base material or the covering material. Or it is made to be absorbed in a water absorbing agent or the like, the lamination area is controlled with high precision, and also, with a very thin film thickness, and evenly laminated the present invention on the substrate,
The ultra-thin heating element of the present invention can be manufactured at a high speed, and effects such as good startup at the beginning of use and good temperature characteristics can be obtained by laminating or spraying iron powder or the like.

[0296] In the present invention the second method, pyrogens present invention was in is covered by the excess moisture, or free water or water-containing gel, the contact with oxygen in the air is suppressed by such excessive moisture As a result, the exothermic reaction of the exothermic composition is prevented, and the loss due to the exothermic reaction at the time of production, the deterioration of the quality of the present invention and the solidification are prevented. It is absorbed by the laminated or sprayed water-absorbing agent, base material and coating material. Therefore, after the heating element is manufactured, the mixing ratio of water in the heat-generating composition is suitable for the exothermic reaction between the time of use and the time of use. This has the effect that a heating element can be manufactured.

In the second method of the present invention, an ink-like or cream-like heat-generating composition is laminated on a base material by printing or coating, and a heating material is formed by covering the material with a coating material. Since the process up to packaging the heating element can be performed consistently within a very short time, the heating composition does not become a condition capable of generating heat in the manufacturing process, and the present invention generates heat during the manufacturing process. Is prevented.

As a result, quality reduction and solidification of the product of the present invention can be completely prevented during the production of the heating element. As a result, the yield is reduced, the handling is difficult, the maintenance of the production equipment is complicated, and the operation time of the production equipment is reduced. In addition, it is possible to eliminate various adverse effects such as restrictions on the working hours of the worker and difficulty in coagulation treatment, and obtain an effect that a high-quality and highly reliable heating element of the present invention can be obtained at lower cost.

In the third method of the present invention, the heat-generating composition of the present invention, that is, an ink-like or cream-like composition is laminated on a film-like or sheet-like substrate, and then the film-like or cream-like heat-generating composition is laminated on the substrate. A sheet-like covering material is covered, and the base material and the covering material are adhered to each other due to the viscosity of the present invention, and then the obtained laminate is punched into an arbitrary shape. At least one or a part thereof has air permeability.

Therefore, an ultra-thin heating element can be manufactured, and since the present invention, that is, an ink-like or cream-like heating composition is used, the exothermic reaction is caused by the formation of a barrier layer due to excess moisture and the like. In addition to suppressing heat generation loss during production, reducing the quality of the product of the present invention and various adverse effects associated with coagulation of the product of the present invention, the present invention can be evenly distributed and fixed in the bag. This prevents the exothermic composition from moving and biasing, thereby preventing excessive exothermic reaction of the exothermic composition as much as possible to prevent low-temperature burns, and has the effect of producing the heating element of the present invention that can be used safely. .

In the first to third methods of the present invention, when a film-like or sheet-like water-absorbing material, particularly paper having a high water-absorbing property, is applied to one or both surfaces of the present invention, a part of the water of the present invention is absorbed. In addition, the present invention can be more firmly fixed to the paper.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a heating element according to a first embodiment of the present invention.

FIG. 2 is a schematic sectional view of a heating element according to a second embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view of a heating element according to a third embodiment of the present invention.

FIG. 4 is a perspective view of a heating element according to a fourth embodiment of the present invention.

FIG. 5 is a sectional view of a main part of a heating element according to a fourth embodiment of the present invention.

FIG. 6 is an explanatory diagram showing a test method for examining the stability of the exothermic composition.

[Explanation of symbols]

Reference Signs List 1 bag material 2 present invention (ink-like or cream-like exothermic composition) 3 base material 3a PET wet nonwoven fabric 3b polyethylene laminated film 3c PET wet nonwoven fabric 4 coating material 4a polyethylene porous film 4b nylon nonwoven fabric 5 adhesive Agent layer 10 Beaker 11 Temperature sensor L Seal width

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A61F 7/08 334 C09K 5/16

Claims (23)

(57) [Claims] And 1. A pyrogen, the water-absorbing polymer and / or a thickener, a carbon component and / or a metal chloride and water as essential components, are formed in the ink-like or cream-like as a whole by the water Exothermic composition
Excess water or free water and / or in the exothermic composition
The hydrogel expresses the function as a barrier layer, and
An exothermic composition in the form of an ink or a cream, wherein an exothermic reaction is suppressed . 2. The exothermic composition according to claim 1, wherein at least one selected from an inorganic or organic water retention agent, a pH adjuster, a surfactant and an antifoaming agent is blended. Or a cream-like exothermic composition formed in the form of an ink or a cream. 3. The ink-like or cream-like heat-generating composition according to claim 1 or 2, which has a viscosity (at a temperature of 20 ° C.) of 1,
An ink-like or cream-like exothermic composition having a molecular weight of 000 to 7,500,000 cps. 4. An ink-like or cream-like heat-generating composition is laminated and enclosed in a sheet-like packaging material, and at least a part of the packaging material has air permeability, and the ink-like or cream-like heating composition A heating element characterized in that a part of the water content of the exothermic composition is absorbed by the sheet-like packaging material. 5. The sheet-like packaging material comprises a film-like or sheet-like base material and a film-like or sheet-like covering material, and at least one or a part of the base material and the covering material has air permeability. 5. It has water absorption as well as having
The heating element according to the above. 6. The heating element according to claim 4, wherein at least one selected from iron powder, a carbon component and a water absorbing agent is laminated or sprayed on the upper surface of the ink-like or cream-like heating composition. 7. Iron powder or iron powder in which an ink-like or cream-like heat-generating composition is coated on the upper surface with a carbon component.
5 to the total amount of (A), carbon component (B) and (A) and (B)
The heating element according to claim 4 or 5, wherein a mixture to which water is added in an amount of not more than weight% is laminated. 8. The ink composition according to claim 4, wherein the base material and the coating material are completely or partially sealed by adhesion, heat bonding or heat fusion at the periphery of the ink-like or cream-like heat generating composition. 8. The heating element according to any one of items 7 to 7. 9. The heating element according to claim 4, wherein the base material and / or the coating material are formed of a film- or sheet-like water-absorbing material having water absorbency. 10. The heat generation according to claim 4, wherein a water-absorbing layer is laminated on at least a portion of the base material and / or the coating material that is in contact with the ink-like or cream-like heat generation composition. body. 11. The heating element according to claim 10, wherein the water absorbing layer is formed of a film-shaped or sheet-shaped water absorbing material. 12. The method according to claim 12, wherein the base material and / or the coating material are provided on the inner surface or both surfaces of a non-breathable or breathable film or sheet.
The heating element according to any one of claims 4 to 11, wherein a film-shaped or sheet-shaped water-absorbing material is laminated. 13. The water-absorbing material is a water-absorbent foam film / sheet, paper, non-woven fabric, woven fabric or porous film.
The heating element according to claim 9, wherein the heating element is a sheet. 14. A water-absorbing material containing, impregnating, kneading, laminating, transferring or carrying a water-absorbing agent on a foamed film / sheet, paper, nonwoven fabric, woven fabric or porous film / sheet to impart water absorption. 14. The heating element according to claim 13, wherein the heating element is increased. 15. The heating element according to claim 4, wherein the base material and the covering material are formed of an extensible material. 16. The heating element according to claim 4, wherein at least one or a part of the side of the packaging material, or at least one of the base material and the coating material has air permeability. 17. The heating element according to claim 4, wherein an adhesive layer is laminated on at least a part of one of the exposed surfaces of the base material or the coating material. 18. The heating element according to claim 17, wherein the pressure-sensitive adhesive layer is a poultice layer containing a poultice, or a drug-containing layer containing or carrying a transdermally absorbable drug. 19. A heat-generating composition which is thickened into an ink or a cream is formed, and the heat-generating composition in the form of an ink or a cream is formed in at least one predetermined position on the upper surface of a film or sheet. After laminating to the area,
A film-like or sheet-like coating material is covered so as to cover the ink-like or cream-like heat-generating composition, and at least one or a part of the base material and the coating material has air permeability , and The ink or chestnut
A part of the water content of the exothermic composition in the form of a substrate and / or
A method for manufacturing a heating element, wherein the heating element is absorbed by a coating material . 20. A heat-generating composition which is thickened into an ink or a cream is formed, and the heat-generating composition in the form of an ink or cream is applied to at least one predetermined position on the upper surface of a film or sheet. After laminating to the area,
At least one selected from iron powder, a carbon component and a water absorbing agent is laminated or sprayed on the top surface of the ink-like or cream-like heat generating composition. A film-like or sheet-like covering material is covered so as to cover at least one selected from the group consisting of:
In addition, at least one or a part of the base material and the coating material has air permeability. 21. An ink-like or cream-like heat-generating composition is laminated on a film-like or sheet-like base material, and then a film-like or sheet-like coating material is put on the heat-generating composition. Due to the viscosity of the exothermic composition, the base material and the coating material are attached to each other, and then the obtained laminate is punched into an arbitrary shape, and at least one or a part of the base material or the coating material. Wherein the material has air permeability. 22. The heating element obtained in claim 21 is interposed between two films or sheets, and at the same time as or after this interposition, the two films or sheets are larger than the heating element. Punching into shape,
Or after punching, at the periphery of the heating element,
A method for producing a heating element for sealing the two films or sheets. 23. The heating element according to claim 19, wherein a film-like or sheet-like water-absorbing material is applied to one or both surfaces of the ink-like or cream-like heat-generating composition. Production method.