JPH10155827A - Heating element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the generation of dust at the time of production of an exothermic compsn., to suppress the exothermic reaction of the exothermic compsn. and to prevent the loss by the exothermic reaction at the time of the production, the degradation in the quality of the exothennic compsn. 2 and the solidification of the exothemtic compsn. by forming the exothermic compsn. to an inky or creamy form. SOLUTION: The inky or creamy exothermic compsn. 2 are laminated and sealed into a sheet-like packaging material 10. Pulp powdery materials P or the mixtures composed of the pulp powdery materials and at least one kind selected from ceramic powder for radiating far IR rays, ceramic fibers radiating far IR rays, metallic powder, iron powder coated with carbon components or water absorbents are laminated on one or both surfaces of the inky or creamy exothermic compsn. 2, by which this heating element is constituted. The sheet- like packaging terminal at least partly has air permeability. The moisture of the inky or creamy exothermic compsn. is partly absorbed into the absorbers, such as pulp powdery materials.

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. In addition, the exothermic composition can be distributed in the packaging material at a uniform thickness, and a part or all of the exothermic composition can be fixed in the packaging material to prevent its movement. Further, a part of the water content of the ink-like or cream-like heat-generating composition is absorbed by a water-absorbing body such as a pulp powder, and the pulp powder or a mixture thereof is patterned. Is extremely easy,
Further, the pulp powder or the mixture thereof has good water absorption, and also has a high water absorption. Further, even after the water is absorbed, the heating element is flexible and elastic, and has a soft feeling. The present invention relates to a heating element having extremely excellent feeling as a result, for example, as a result, and to a method of manufacturing the heating element, which is extremely excellent in use feeling.

[0002]

2. Description of the Related Art In recent years, as a so-called disposable color trouser, a flat film or sheet-shaped base material having air permeability or non-air permeability and a film- or sheet-shaped covering material having air permeability have been used. A heating element in which a heating composition is enclosed in a packaging material is widely used.

[0003] As a method of manufacturing this 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.

The heating element thus manufactured is sealed in an air-impermeable outer bag to prevent an exothermic reaction until use, and stored or distributed.

Conventional heat-generating compositions include, in addition to metal powder and water, which are essential for the exothermic reaction, a carbon component such as graphite, carbon or activated carbon for promoting heat generation, and an oxide film on the surface of the metal powder to be destroyed. A powdery material containing a metal chloride which continuously generates an exothermic reaction and a water retention agent such as wood flour is used.

There are two methods for dropping the powdered exothermic composition: 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.

[0007]

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. In addition, since it is a powdery and porous body, it has a large surface area and extremely good contact with air, and an oxidation reaction occurs immediately upon contact with air.

[0008] Therefore, while the exothermic composition is being compounded at an appropriate compounding ratio, the exothermic composition is produced, and the exothermic composition is dropped onto a substrate and covered with a coating material to produce a heating element. In the meantime, before the obtained heating element is sealed in the air-impermeable packaging material, an oxidation reaction with air, that is, an exothermic reaction occurs, causing a loss due to the exothermic reaction of the exothermic composition, and causing the exothermic composition In addition to the deterioration of the quality, the product produced by the exothermic reaction solidifies and causes various adverse effects. Specifically, for example, reduced yield and difficulty in handling due to coagulation removal, the complexity of maintenance of 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 a powder form, as described above, a light-weight and thin heat-generating element is manufactured, and the obtained heat-generating element is sealed in a non-breathable outer bag. Oxidation reaction with air occurs, resulting in a fatal defect such as a decrease in the quality of the heating element and a decrease in its reliability.

In order to prevent such an oxidizing reaction of the exothermic composition, the mixing device is made airtight and the air in the mixing device is replaced with nitrogen, and then the components of the exothermic composition are uniformly mixed. Not only is the mixing apparatus complicated and expensive, but also there are problems such as the exothermic composition and the heating element becoming expensive.

At present, as a general manufacturing method, a method of dropping a heat-generating composition with a chute while creating a pocket with a packaging material, and then successively creating a next pocket while sealing is performed. However, the exothermic composition is provided with wettability by the addition of moisture, and is in a powder form and poor in fluidity, so that there is a large limit to the speed or lack of filling property of the exothermic composition. In addition, there are problems such that the filling amount of the exothermic composition varies, and the exothermic composition is biased in the packaging material, resulting in a lack of reliability.

The exothermic composition is in powder form, but is wettable by moisture, has poor fluidity, and is extremely difficult to be filled and distributed in a bag with a uniform thickness.

For this reason, after the filling and packaging, the distribution of the exothermic composition is equalized to some extent by a roller or the like.
In this method, the distribution of the exothermic composition tends to be biased in the direction of the source of the bag material.In order to increase the distribution amount of the exothermic composition in the direction of the destination of the bag material, the heating element is made thicker, for example, by hand during use. It is necessary to eliminate the deviation of the distribution amount by shaking.

[0014] When the entire heating element is thick, the touch is rough and the texture is poor, and the flexibility is reduced to make it difficult to conform to complicated unevenness and a curved surface having a small curvature on the body surface. There is a problem in that the ability to follow the surface of the body, which deteriorates and deforms or moves with the movement of the body, is poor, and that a feeling of tension or discomfort occurs.

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. Since it is not constant, fixing it to the same place and using it may cause low-temperature burns.

[0016] 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. However, the shift has not been completely prevented in the manufacturing process, the transportation stage, and the use stage. is the current situation.

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 during 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.

Therefore, recently, a heating element described below or a method of manufacturing the heating element has been proposed. That is, as a sheet-shaped heating element, a sheet-shaped heating element having a sheet-shaped support having a large number of voids, containing an oxidizable metal powder as a main component, and holding a heating composition that generates heat by contact with air. In addition, it has been proposed to use a nonwoven fabric obtained by blending superabsorbent fibers having a water absorption capacity of 50 ml / g or more as a support (Japanese Patent Application Laid-Open No. 7-59809).

In this case, a non-woven fabric containing water-absorbing fibers is used as a sheet-like support, and a mixed powder containing an oxidizable metal powder as a main component is uniformly spread on the support.
Then, the mixed powder is held inside the support by vibrating with a vibrator, and then water or an aqueous solution of sodium chloride is sprayed. However, in this method, the mixed powder is entangled due to fiber entanglement or partial bonding of the fibers. Difficult to enter, as a result of a small number of voids capable of holding the exothermic composition, there is a limit to the amount of the exothermic composition held, or required heat generation characteristics can not be obtained,
In addition to causing temperature unevenness and temperature variations, there is a problem in that the amount of the heat-generating composition held by the support greatly varies depending on the support, and it is difficult to obtain a sheet-like heating element having stable quality.

Further, as a method of manufacturing the sheet-like heating element, a nonwoven fabric b is superimposed on the lower surface of a nonwoven fabric a having a large number of voids using an adhesive, and a heat generating composition powder is sprayed on the upper surface of the nonwoven fabric a. It has been proposed that a non-woven fabric c is superposed on the upper surface of the non-woven fabric a, then heated and compressed by a mold compressor, and then impregnated with water or an aqueous inorganic electrolyte solution (Japanese Patent Laid-Open No. 8-112303). .

In this method, a nonwoven fabric b is superimposed on the lower surface of a nonwoven fabric a having a large number of voids using an adhesive,
The exothermic composition powder is scattered on the upper surface of the nonwoven fabric a so as to be held in the voids. Therefore, there is the same problem as in the case described above. As a result of poor contact, temperature unevenness and temperature variation are further increased, and reliability is lacking.

Further, as a sheet-like heating element, a sheet-like support having a large number of voids and holding a heat-generating composition containing an oxidizable metal powder as a main component and generating heat upon contact with air is held. A heating element using a nonwoven fabric which expands by heating and increases the porosity as a support has been proposed (Japanese Patent Publication No. 8-173471).

In this sheet-like heating element, a non-woven fabric which expands by heating to increase the porosity is used as a support, and this non-woven fabric is formed from two or more components having different melting temperatures. The fibers contain conjugated fibers and do not expand so much when heated by entanglement of fibers or partial joining of fibers. It is difficult for the body mixture to enter the inside, and as a result, there are few voids capable of holding the exothermic composition.As a result, the amount of the exothermic composition to be held is limited, and the required exothermic characteristics cannot be obtained. In addition, there is a problem that a large variation occurs in the holding amount of the exothermic composition due to the support, and it is difficult to obtain a sheet-shaped exothermic body of stable quality.

In the sheet-like heating element, the heating composition is decomposed and held in a state where the nonwoven fabric is heated and expanded at the time of manufacturing the heating element. However, in this case, the heating composition degrades due to heat and the quality is deteriorated. In this respect, there is a problem that reliability is lacking.

Therefore, in order to solve the above technical problem, the present inventor suppressed the exothermic reaction of the exothermic composition, and caused loss of the exothermic composition due to the exothermic reaction at the time of production, deterioration of the quality of the exothermic composition, and Prevent various adverse effects associated with solidification of the heat generating composition, can produce an ultra-thin heating element at high speed, and evenly distribute and fix the heat generating composition in the packaging material, thereby moving the heat generating composition, Extensive investigations have been made on a heating element that prevents bias and also minimizes excessive exothermic reaction of the exothermic composition.

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. In other words, it has been found that the exothermic reaction of this kind of exothermic composition depends not only on the amount of supplied oxygen but also on the amount of water, which greatly affects the reaction rate.

That is, in order to promote this oxidation reaction,
It is important that there is appropriate moisture, and the exothermic reaction is remarkably suppressed even if the water content is too much or too little. 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.

If the water content is too low, the air is sufficient but the water required for the reaction is insufficient. On the other hand, if the water content is too high, this water becomes a barrier layer covering the surface of the metal powder and forms a barrier layer on the metal powder. The reaction slows significantly due to the reduced air supply.

Therefore, the present inventor has proposed that when the exothermic composition is thickened to form an ink or a cream, lamination on a film or a sheet is extremely easy and can be performed at high speed by screen printing or coating. An ultra-thin heating element can be manufactured, and the heat-generating composition can be evenly distributed in the bag material. In addition, the ink-like or cream-like heat-generating composition has no excess water or free water therein. The water in the gel containing water (hereinafter, referred to as a water-containing gel) becomes an air barrier layer (hereinafter, referred to as a barrier layer),
It has been found that the reaction of exothermic substances such as metal powder is remarkably suppressed, and that the substance becomes stable in the air.

Further, the present inventor has reported that if the ink-like or cream-like exothermic composition is present in the packaging material as it is, the necessary exothermic reaction does not occur even if the barrier layer comes into contact with air. Knowledge was also obtained.

Further, the present inventor has found that in order to obtain a heating element capable of obtaining a required temperature, surplus water in an ink-like or cream-like heat-generating composition, or free water or a part of water in a hydrous gel is used. It is necessary to remove the barrier layer of the exothermic substance by absorbing it, and when the barrier layer is removed, a porous exothermic composition is formed and the contact with air is improved, so that excellent exothermic characteristics are obtained. Knowledge was also obtained. Accordingly, the present inventors have made intensive studies on an optimum material for removing the barrier layer of the exothermic substance.

As a result, in the heating element using the ink-like or cream-like heating composition, in removing the barrier layer of the heating substance, the pulp such as a pulp sheet or the like is pulverized while scraping or scraping. When the pulp powder or the mixture obtained by the above is dropped from the quantitative feeder and the pulp powder or the like is sucked through a breathable film or sheet, the pulp powder or the like is adsorbed only at the suction point. As a result of being laminated, patterning is extremely easy, and the pulp powder or the like has good water absorption, and has a high water absorption, and even after absorbing water, It has been found that extremely good results can be obtained, such as extremely excellent feeling, such as extremely excellent feeling in use as a result of the heating element being flexible and elastic and having a soft feeling.

According to this structure, the air-permeable film or sheet is formed of a heat-adhesive or heat-fusible material, and a heat-adhesive or heat-fusible foamed film or sheet is formed on one or both surfaces thereof. When a porous film / sheet, a nonwoven fabric or a woven fabric are laminated and thermally bonded, the two are firmly joined to each other, so that there is no delamination and the reliability is remarkably improved.

That is, a water-absorbing film or sheet coated with a water-absorbing agent is generally expensive and has low thermal adhesive force. When a nonwoven fabric or woven fabric is laminated on the film and thermally bonded, the adhesive force is low. It may be lowered to cause delamination. However, by using a pulp powder or the like, patterning is extremely easy and the pulp powder can be removed only at the heat-bonded portion, so that the adhesive force at the heat-bonded portion can be significantly improved.

Therefore, a breathable film or sheet
(Coating material) is formed of a heat-adhesive or heat-fusible material, and a pulp powder or the like is laminated on a predetermined area of the coating material. Laminate the exothermic composition on a substrate formed of a heat-adhesive or heat-fusible material so that the exothermic compositions overlap, and then, at the outer periphery of the ink-like or cream-like exothermic composition, It is most desirable to heat bond the front and back films or sheets, ie the substrate and the coating.

In this case, a heat-bonding or heat-fusing nonwoven fabric or woven fabric is bonded to at least the lamination side of the ink or cream-like heat-generating composition in the film or sheet. When the ink-like or cream-like heat-generating composition is laminated on a predetermined area of the heat-generating composition, and the pulp powder or the like is laminated only on the lamination portion of the heat-generating composition, the pulp powder with the ink-like or cream-like heat-generating composition, Alternatively, it has been found that as a result of the mixture being more easily fixed, its movement and bias are prevented.

The present invention has been completed on the basis of the above technical knowledge, and by making the exothermic composition ink-like or cream-like, it is possible to prevent the generation of dust during the production of the exothermic body and to produce the exothermic heat. It suppresses the exothermic reaction of the composition, prevents loss due to the exothermic reaction during production, reduces the quality of the exothermic composition and prevents solidification of the exothermic composition, and adopts printing and transfer methods such as screen printing and coating. Because
In addition to enabling uniform distribution of the exothermic composition and improving the quality of the product with high accuracy of thickness and distribution of the exothermic composition,
A thin heating element having a soft feeling can be manufactured at high speed and easily, and furthermore, the movement and offset of the heating composition can be prevented. It is an object of the present invention to provide a heating element which avoids a reaction as much as possible and has excellent heat generation characteristics and a method for producing the heating element.

The present invention has been completed on the basis of the above technical knowledge, and in particular, absorbs a part of the water content of an ink-like or cream-like heat generating composition into a water-absorbing material such as pulp powder. In addition, the pulp powder is extremely easy to pattern, and the water absorbent such as the pulp powder has good water absorption and high water absorption. Further, even after absorbing moisture, the heating element is flexible and resilient, and has a soft feeling. For example, the present invention provides a heating element that is extremely excellent in use feeling as a result, and provides a method of manufacturing this heating element. The purpose is to:

[0039]

A heating element according to the present invention comprises:
In order to achieve the above object, an ink-like or cream-like heat-generating composition is laminated and sealed in a sheet-like packaging material, and one or both sides of the ink-like or cream-like heat-generating composition are in the form of pulp powder. Laminated body or pulp powder and at least one mixture selected from ceramic powder that emits far-infrared ray, fiber that emits far-infrared ray, metal powder, iron powder coated with carbon component or water-absorbing agent And at least a portion of the sheet-like packaging material has air permeability, and a part of the water content of the ink-like or cream-like heat-generating composition is converted into a water-absorbent material such as the pulp powder-like material. It is characterized by being absorbed.

Hereinafter, the present invention will be described in detail. In the present invention, first, as a heat-generating composition, one feature is that a heat-generating composition which is thickened into an ink or a cream is used instead of using a powder-like heat-generating composition as in the related art. Have

The exothermic composition in the form of an ink or a cream is not particularly limited as long as it is composed 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. It is not something to be done.

Specifically, for example, it can be obtained by adjusting the mixing ratio of an exothermic substance which causes an exothermic reaction upon contact with air, water, a water-absorbing polymer and / or a thickener, and other components.

Since the exothermic composition used in the present invention is formed in the form of an ink or a cream, various advantages described below occur.

That is, since the exothermic composition is formed 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, or the like. It can be transferred and laminated very easily by coating and coating with a head coater, roller, applicator, etc. In addition to being able to manufacture ultra-thin heating elements at high speed, and evenly distributing the heating composition to bag material Can be.

When the exothermic composition is formed in the form of an ink or a cream, the surface area becomes significantly smaller than that of a conventional exothermic composition which is powdery and porous, and is not in contact with air. Is extremely restricted, and the oxidation reaction with air is remarkably suppressed.

Further, in the case of an exothermic composition in the form of an ink or a cream, excess moisture or free water or a hydrous gel wraps exothermic substances such as metal powder and functions as a barrier layer. Is 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 water content like a cream-like heat-generating composition. The free water or hydrogel wraps the exothermic substance and functions as a barrier layer, so that it is stable in the air.

Accordingly, while the exothermic composition is being compounded, an ink-like or cream-like exothermic composition is produced, and this ink-like or cream-like exothermic composition is prepared on a film-like or sheet-like substrate. After laminating in a predetermined area, oxidizing reaction with air, that is, exothermic reaction hardly occurs until pulp powder, or a mixture thereof is coated with a laminated covering material to produce a heating element, Loss due to the exothermic reaction of the exothermic composition and quality deterioration of the exothermic composition are prevented, and solidification of the exothermic composition is prevented. For this reason, the yield and the 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 time of the worker.

When the exothermic composition is in the form of an ink or a cream, as described above, a heating element is manufactured, and the heating element is air-sealed until it is sealed in a non-breathable outer bag. There is almost no oxidation reaction with the heating element, so that advantages such as stabilization of the quality of the heating element and an increase in its reliability occur.

Furthermore, since the ink-like or cream-like exothermic composition is stable in air, there is no need to make the mixing device airtight, and it is not necessary to replace the air in the mixing device with nitrogen. A simple mixing device is sufficient, so that the exothermic composition and the exothermic body can be manufactured at low cost.

In the case of an exothermic composition in the form of an ink or a cream, when excess moisture, or free water or a part of the moisture in a hydrogel is absorbed into a pulp powder or the like described later, the barrier layer is lost. Then, the exothermic composition becomes porous, the contact with the air is good, the exothermic reaction is smoothly performed, and the exothermic characteristics are improved.

Further, as described above, the use of the heat-generating composition in the form of an ink or a cream makes it possible to extremely easily transfer and laminate by screen printing or coating, and to produce a super-thin heating element at high speed. Yes, if the heating element is thin,
Excessive exothermic reaction due to heat storage in the exothermic composition is prevented,
The safety is improved, the exothermic composition can be evenly distributed in the bag material, and the movement and bias of the exothermic composition during use or handling can be prevented.

Further, when the exothermic composition in the form of an ink or cream is transferred and laminated on a foamed film / sheet, paper, a nonwoven fabric, a woven fabric or a porous film / sheet, the exothermic composition becomes an ink-like composition. Since it is creamy, it has high penetrating and anchoring properties, penetrates into the pores of these films or sheets together with the pulp powder or a mixture thereof, and further prevents its movement and deviation.

The exothermic composition used in the present invention includes:
It is not particularly limited as long as it has an ink-like or cream-like shape and a required temperature characteristic is obtained. Specifically, for example, a heat-generating substance essential for an exothermic reaction, a water-absorbing polymer and / or A thickener, a carbon component such as graphite, carbon or activated carbon for promoting heat generation, and / or a metal chloride and water as essential components, and further, an inorganic or organic water retention agent, pH adjuster, and dispersion At least one selected from a surfactant or an antifoaming agent that enhances the properties is blended, and is formed as an ink or cream as a whole.

The proportion of the heat-generating composition in the form of an ink or cream varies depending on the type of the water-absorbing polymer and the thickener used, the type of the heat-generating substance, the type of the carbon component, the type of the metal chloride, and the like. However, in general, the water-absorbing polymer 0.1 to 10 parts by weight based on 100 parts by weight
0.1 to 10 parts by weight of a thickener and / or 1.5 to 20 parts by weight of a carbon component and / or 1 to 15 parts of a metal chloride
Parts by weight, and for 100 parts by weight of the heating substance,
0.5-10 parts by weight of inorganic or organic water retention agent, pH
It is preferable that at least one selected from 0.1 to 5 parts by weight of a modifier, 0.1 to 5 parts by weight of a surfactant for enhancing dispersibility, and 0.1 to 5 parts by weight of an antifoaming agent is blended, In particular, water is added to this 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 may be charged into a mixer or kneader, and these components may be uniformly mixed to obtain an ink-like or cream-like exothermic composition.

The apparatus for mixing these components is not particularly limited as long as the apparatus is capable of mixing uniformly when the amount of water is excessive, particularly in the case of an exothermic composition in the form of an ink. 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.

In the present invention, the ink-like or cream-like heat-generating composition means an ink-like or cream-like viscous body which can be transferred by printing such as screen printing. There is no particular limitation as long as it is such an exothermic composition.

As the water-absorbing polymer, commercially available ones may be used, such as KI gel 201-K and KI gel 201-F2 manufactured by Kuraray Co., Ltd., and Sun Fresh ST-500MPS manufactured by Sanyo Chemical Industries, Ltd. Is mentioned as an example.

Among these commercially available water-absorbing polymers, in particular, KI gel 201K, K.K.
I-gel 201-KF2 and the like are more preferable because they absorb a large amount of a chloride aqueous solution and are stable.

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 property. Examples of the thickener include bentonite, activated clay, and stearin. Acid salt, polyacrylate such as sodium polyacrylate, gelatin,
Polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, acacia, tragacanth,
Alginate salts such as locust bean gum, guar gum, arabic gum, sodium alginate, pectin, carboxyvinyl polymer, dextrin, starch starch such as pregelatinized starch, starch for processing, and polysaccharide thickeners such as carrageenan and agar , CMC, ethyl acetate, hydroxyethyl cellulose, cellulose derivative thickeners such as methyl cellulose or hydroxypropyl cellulose,
One or a mixture of two or more selected from water-soluble cellulose ethers, N-vinylacetamide, etc. may be mentioned. Further, these may be treated with a surfactant or may be combined with a surfactant to obtain hydrophilicity. May be improved. These thickeners mainly have a function of absorbing water or an aqueous solution of a metal chloride to increase the consistency or impart thixotropy.

As the water-soluble cellulose ether,
For example, methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metrolose SM4000, etc., manufactured by Daiichi Kogyo Seiyaku Co., Ltd .:
Esca MC, etc.), hydroxymethylcellulose (CM
C) (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Cellogen EP), hydroxypropyl methylcellulose (Shin-Etsu Chemical Co., Ltd., trade name: Metroze 60SM-4000, 90SH)
-4000 etc.).

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 starts to thicken depends on 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.

The cream-like exothermic composition N-vinylacetamide is obtained by radical polymerization of N-vinylacetamide, and has a water-soluble linear structure and a water-insoluble crosslinked structure. The insoluble cream-like exothermic composition N-vinylacetamide includes a microgel that acts as a gelling agent due to the difference in the crosslink density, and specifically, for example, N-vinylacetamide Vinylacetamide-sodium acrylate copolymer (product name GE-1 manufactured by Showa Denko KK)
67), N-vinylacetamide homopolymer (trade name GE-191, manufactured by Showa Denko KK) or N-vinylacetamide crosslinked product (microgel) (manufactured by Showa Denko KK)
One or a mixture of two or more selected from trade names GX-205). Further, these may be treated with a surfactant or may be combined with a surfactant to improve hydrophilicity. You can. These thickeners mainly have a function of absorbing water or an aqueous solution of a metal chloride to increase the consistency or impart thixotropy.

As the exothermic substance used in the present invention, an organic substance can be used, but a metal powder which does not generate an off-odor due to the reaction, particularly an iron powder, a zinc powder, an aluminum powder or a magnesium powder, or a powder thereof. Powders of alloys composed of two or more types of metals, and mixed metal powders obtained by mixing two or more of these are used. Particularly, among these metal powders, safety, handling, cost, It is desirable to use iron powder which is the most excellent in view of storage stability and stability.

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, charcoal, activated clay, silica stone, diatomaceous earth, alumite such as alumina, mica powder, Examples include alum siliceous substances such as clay, formic siliceous substances such as talc, silica powder and wood powder.

Examples of the above-mentioned pH adjuster, surfactant and defoamer include those used in this field in addition to ordinary pH adjusters such as sodium polyphosphate.

In the ink-like or cream-like heat-generating composition used in the present invention, a part of water is absorbed by a water-absorbing material such as pulp powder, which will be described later, thereby removing the barrier layer of the heat-generating substance. At the same time, the exothermic composition is made porous, so that the exothermic composition is formed so as to be in good contact with air.

In the present invention, the above-mentioned ink-like or cream-like heat-generating composition is laminated and enclosed in a sheet-like packaging material having at least a part of air permeability.
One or both surfaces of this ink-like or cream-like heat-generating composition are coated with pulp powder, or pulp powder, ceramic powder that emits far-infrared rays, fiber, metal powder, or carbon component that emits far-infrared rays. At least one mixture (hereinafter abbreviated as pulp powder or a mixture thereof) selected from iron powder or a water-absorbing agent, and the ink-like or cream-like exothermic composition Is characterized in that a part of the water is absorbed by a water absorbing body such as a pulp powder.

In the present invention, the water-absorbing material such as pulp powder refers to pulp powder or pulp powder, ceramic powder that emits far-infrared rays, fiber or metal powder that emits far-infrared rays. In addition to those comprising at least one mixture selected from iron powder or a water-absorbing agent coated with a carbon component, a water-absorbing substrate and / or a coating material,
Alternatively, it refers to a substrate and / or a coating material to which water absorption has been imparted.

When a water-absorbing layer or a water-absorbing material is laminated or applied to a substrate and / or a coating material, the water-absorbing body such as pulp powder includes a combination of these and pulp powder.

The pulp powder refers to pulp in the form of powder, particles or fine fibers. The method for pulverizing pulp such as pulp sheet is not particularly limited, but specific examples include, for example, JP-A-56-89839, JP-A-58-8175, and JP-A-4-18085.
1 and JP-A-8-24697.

In the present invention, the ceramic powder emitting far-infrared rays is not particularly limited as long as it is a ceramic powder having a particle size of 50 μm or less and emitting far-infrared rays. The radiating fiber is not particularly limited as long as it radiates far-infrared rays.Specifically, for example, a material that radiates far-infrared rays on the surface of a ceramic fiber or an organic fiber that radiates far-infrared rays (E.g., paint), and generally, the aspect ratio (length / thickness value) is 1.5 to
It refers to one having a length of 50 μm to 15 mm within a range of 2000.

Examples of the water-absorbing agent include the above-described water-absorbing polymer and / or thickener, and the method of mixing the pulp powder with the water-absorbing agent is not particularly limited. Mixing the two with a mixer or spraying the water absorbing agent while dropping the pulp powder,
A mixture of the pulp powder and a water-absorbing agent is also preferably used, and in the present invention, this mixture is also included in the water-absorbent such as the pulp powder.

As another mixing method of the pulp powder and the water-absorbing agent, a jet-type injection nozzle having an air blowing port is used, and the water-absorbing agent is sprayed by jetting air to mix the pulp powder with the water-absorbing agent. And the like.
At this time, the pressure of air is 0.1 to 10 kg / cm ^2.
And the mixing ratio of the water-absorbing agent may be arbitrarily determined. However, the flexibility and elasticity should be 50% by weight or less, especially 30% by weight or less of the whole pulp powder and the water-absorbing agent. It is desirable because it has good properties, softness and feel, and excellent usability.

The iron powder coated with the carbon component is
It is formed by coating 0.1 to 10 parts by weight of a carbon component with respect to 100 parts by weight of iron powder.

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.

The mixing ratio of the pulp powder and the iron powder is such that the iron powder is mixed with 100 parts by weight of the pulp powder in terms of water absorption, flexibility and feeling of use such as softness.
The range is preferably from 100 to 100 parts by weight, preferably from 5 to 50 parts by weight, particularly preferably from 7.5 to 30 parts by weight. What is necessary is to mix the iron powder which coats the body and the carbon component.

The mixing ratio of the pulp powder (A), the iron powder (B) and the iron powder (C) coated with the carbon component is (B) to 100 parts by weight of (A). The total amount of (C) is 1
The range is preferably from 100 to 100 parts by weight, preferably from 5 to 50 parts by weight, particularly preferably from 7.5 to 30 parts by weight. In this case, the blending of (B) and (C) is preferred. The ratio may be mixed at an arbitrary ratio.

In the present invention, when an ink-like or cream-like exothermic composition is interposed between the substrate and the coating material, the ink-like or cream-like heat generation on the inner surface of the substrate and / or the coating material is performed. A water-absorbing body such as a pulp powder is suctioned and fixed in advance to the lamination region of the composition, whereby the water-absorbing body is brought into contact with one or both surfaces of the ink-like or cream-like heat-generating composition. Part of the moisture is absorbed by the water absorbing body from the composition to remove the barrier layer of the exothermic substance and to make the exothermic composition porous, so that good contact with air is formed.

In this case, the amount of the water-absorbing material such as pulp powder laminated on the inner surface of the base material and / or the coating material is generally 2 from the viewpoints of water absorption, flexibility, and soft feeling. range to 250 g / m ^2, preferably 5 to 200
g / m ² , particularly preferably 7.5 to 150 g / m ²
It is desirable to be within the range.

That is, simply enclosing the ink-like or cream-like heat-generating composition in a sheet-like packaging material as it is does not provide the required heat-generating properties due to the presence of the barrier layer. For this purpose, it is necessary to remove the exothermic substance barrier layer by absorbing free water and / or excess water in the ink-like or cream-like exothermic composition and a part of the moisture in the hydrogel. It is desirable that the pulp be absorbed by a pulp powder or a water absorbent mainly containing the pulp powder for the reasons described below.

That is, in a heating element using an ink-like or cream-like heat-generating composition, the pulp powder used for removing the barrier layer of the heat-generating substance is obtained by regenerating a roll-shaped pulp sheet, old newspaper, or the like. It is obtained by shaping pulp or the like while being crushed, and when the pulp powder is sucked through a breathable film or sheet onto a screen of a shape to be laminated while dropping from a quantitative feeder, the suction point As a result of adsorbing and laminating the pulp powder only on the pulp, patterning is extremely easy, and a low-cost, low-bulk, high-water-absorbing layer is obtained. Furthermore,
Even after absorbing moisture, the heating element is flexible and resilient, and has a soft feeling, such as a soft feeling.As a result, when used on the inside of underwear, the feeling of use is extremely excellent, and low-temperature burns can be prevented. Very good results can be obtained.

Further, in this case, the air-permeable film or sheet is formed from a heat-adhesive or heat-fusible material, and the heat-adhesive or heat-fusible foamed film / sheet is formed on one or both sides thereof. When a porous film / sheet, a non-woven fabric or a woven fabric is laminated and thermally bonded, the two are firmly joined to each other, so that there is no delamination and the reliability is remarkably improved.

That is, the water-absorbing film or sheet is
In general, the cost is high, the thermal adhesive strength is low, and the adhesive strength is low, so that delamination may occur. However,
The patterning is extremely easy by using the pulp powder or the mixture thereof, and the heat bonding portion can remove the pulp powder or the mixture thereof, so that the adhesive force of the heat bonding portion can be remarkably improved. The temperature control is also improved because the seal can be completely sealed. In other words, in the outer peripheral portion of the ink-like or cream-like heat-generating composition, the base material and the coating material are completely or partially sealed by heat bonding or heat fusion, so that the peeling of the sealed portion does not occur. It is surely prevented.

Therefore, the air-permeable film or sheet is formed of a heat-adhesive or heat-fusible material, and the air-permeable film or sheet, that is, the pulp powder or a mixture thereof is applied to a predetermined region of the substrate. Laminating, laminating the ink-like or cream-like heat-generating composition only on the laminating portion of the pulp powder or the mixture thereof, and then forming a film or thermo-adhesive material on top of it. It is most desirable to cover the sheet, that is, the coating material, and thermally bond the front and back films or sheets, that is, the base material, to the coating material at the outer periphery of the ink-like or cream-like heat generating composition.

In the present invention, as described above, the patterning can be carried out not only in the case of the pulp powder, but also in the case of the pulp powder and a mixture thereof. Since heat is transmitted through the body, low-temperature burns are more easily prevented, and the pulp powder does not necessarily have to absorb water because the pulp powder absorbs a large amount of moisture.

In the present invention, 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 is Has air permeability.

In the present invention, the pulp powder or a mixture thereof is formed in advance in the lamination region of the ink-like or cream-like heat-generating composition in the base material and / or the coating material. As the substrate and the coating material, those formed of a polymer material having no water absorption, such as synthetic resin or rubber, can be used.

In this case, the substrate and the coating material are not particularly limited as long as they are in the form of a film or sheet having air permeability or non-air permeability. Film or sheet made of breathable polymer material, foamed film or sheet, porous film
Examples include sheets, nonwoven fabrics and woven fabrics.

On the other hand, when the base material and the coating material have a heat bonding property or a heat fusing property, the base material and the coating material may be formed on the entire periphery or in the outer periphery of the ink-like or cream-like heat generating composition. By the thermal sealing, the peeling of the sealing portion is reliably prevented, and the sealing property of the thermal bonding portion is completed, so that air and moisture can completely enter and exit from the thermal bonding portion. And the temperature control with only a breathable film or sheet can be performed more reliably,
In addition, since the release of moisture can be prevented, the duration can be improved.

The base material and the coating material may be a single-layer film or sheet, or a plurality of layers of a film or sheet. It is necessary to consider the structure so that it does not occur.

The base material and the coating material formed of a film or sheet having a plurality of layers include, for example, one or both surfaces of a gas or gas permeable film or sheet formed of a polymer material. , Foam film / sheet,
Examples thereof include those obtained by laminating a porous film / sheet, a nonwoven fabric or a woven fabric.

In the present invention, as described above, the base material and / or the coating material do not need to have water absorption because the water-absorbing pulp powder or a mixture thereof is laminated. If desired, the base material and / or the coating material may be formed of a water-absorbing film- or sheet-shaped water-absorbing material. In this case, the water-absorbing material may be a water-absorbing film- or sheet-shaped water-absorbing material. If so, there is no particular limitation.

The water-absorbing material is air-permeable or non-air-permeable, regardless of whether the material itself has water-absorbing property or not. If there is, it is not particularly limited.

Specific examples of the water-absorbing material include foamed films and sheets having water-absorbing properties (foams such as water-absorbing foamed polyurethane), papers such as tissue paper and household thin paper such as towel paper, cardboard paper and cardboard. Cardboard or other thick paper (hereinafter, referred to as papers), nonwoven fabric or woven fabric formed of water-absorbing fiber, or nonwoven fabric or woven fabric containing water-absorbing fiber, or water-absorbing non-porous or In addition to porous films and sheets, regardless of whether the material itself has water absorption, foamed film sheets, nonwoven fabrics, woven fabrics or porous film sheets contain a water absorbing agent, impregnated, kneaded, Transfer or carried to impart or increase water absorption.

Further, a pulp powder or a mixture thereof is laminated on the lamination region of the ink-like or cream-like heat-generating composition on the substrate and / or the coating material, and then the pulp powder or the mixture thereof is mixed. The cut water absorbing material is applied only to the lamination point, whereby the cut water absorbing material may be in contact with one or both surfaces of the ink-like or cream-like heat generating composition, or Instead, the water absorbing material such as pulp powder and the water absorbing material may be exchanged.

In the present invention, since the exothermic composition is prevented from moving in the bag, it is possible to prevent the exothermic composition from being unevenly distributed in the exothermic temperature or generating heat to an abnormally high temperature.

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

In this case, laminating means that the layers are entirely or partially joined together by heat setting, adhesion, adhesion, lamination, or the like, or the layers are simply overlapped with each other, for example, at the periphery or center. It means that the layers are locally bonded by heat sealing, hot melt adhesive or pressure sensitive adhesive.

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

In this case, the ink-like or cream-like heat-generating composition is laminated on at least one predetermined area on the substrate with high precision and uniformity, and further, the film thickness is reduced uniformly over the whole. As a result,
As a whole, it is possible to produce a heating element that is safe and has a good feel against a low-temperature burn of about 0.5 mm to 5 mm.

In the present invention, a pulp powder or a mixture thereof is laminated on a predetermined region on a substrate,
An ink-like or cream-like heat-generating composition is laminated thereon, and the ink-like or cream-like heat-generating composition is coated with a coating material. What is cut into a laminated shape of the exothermic composition of the above, in particular, such as household thin tissue paper such as blotting paper or tissue paper, a highly water-absorbing film or sheet cut into a laminated shape of the ink-like or cream-like exothermic composition. Used, placed on one side of the ink-like or cream-like exothermic composition, or sandwiched both sides of the ink-like or cream-like exothermic composition,
Then, it may be sealed with a covering material.

The base material and the coating material need to have necessary mechanical strength such as tensile strength.
In order to increase conformability to the body surface, it is preferable that the entirety be flexible.

That is, in the present invention, the base material and the covering material are more preferably applied to a curved portion, a stretchable portion, and a bendable portion of the human body. That is, it is desirable that the packaging material of the heating element is formed of an extensible film or sheet, particularly an elastic film or sheet.

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, 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.

In this case, since a pulp powder or a mixture thereof is used in the present invention, a heating element excellent in extensibility and elasticity can be easily obtained.

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, necessary mechanical strength cannot be obtained, and it is 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 base material 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 polymer material include polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, saponified ethylene-vinyl acetate copolymer or ethylene-vinyl acetate copolymer, and natural polymers. Rubber or synthetic rubber can be used.

In the case of forming a laminated base material or coating material, at least 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.

As a method of imparting air permeability to the film or sheet made of the non-foamed polymer material, a method of forming a film or sheet by stretching to form air holes, and further 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.

In 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.

When 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 breathable 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.

When the water vapor transmission rate is less than 50 g / m ² · 24 hr, the calorific value is 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 6,000 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 Lissi method (Lyssy method) is a method based on industrial standards in 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 of which the transmittance is known in advance, thereby transmitting the light. This is a method for obtaining degrees.

In the present invention, the adhesive layer is formed on at least a part of the exposed surface of either one of the base material and 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 permeability, because the heating element can be stuck and fixed directly on 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.

Although the thickness of the pressure-sensitive adhesive layer is not particularly limited, it is 5 to 1000 μm, particularly 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 type polymer used in the present invention include, specifically, ABA type block copolymer, saturated polyester type polymer, polyamide type polymer, and acrylic high polymer. Examples include a molecular substance, a urethane-based polymer substance, a polyolefin-based polymer substance, a polyolefin-based copolymer, a modified product thereof, or a mixture of two or more thereof.

[0130] The modified product refers to a property of the hot-melt type polymer substance, for example, improvement of the adhesive property and stability of the hot-melt type polymer substance by replacing a part of the component of the hot melt type polymer substance with another component. It means something with different gender.

In the present invention, the pressure-sensitive adhesive layer on the exposed surface of the base material and / or the coating material is a compressive layer containing a compressive agent or a drug-containing layer containing or carrying a transdermally absorbable drug. These are desirable because they provide a compressing effect, a drug treatment or a pharmacological effect in addition to the heating effect.

In the present invention, a percutaneously absorbable drug is added to the pressure-sensitive adhesive layer to improve the effect of local treatment, the effect of systemic treatment, or to increase the circulation of blood by the heat effect. For example, the drug can be more effectively circulated to various parts of the living body by absorbing the drug, which is extremely preferable for further enhancing 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 include skin irritants, analgesics and anti-inflammatory agents, central nervous system active agents (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 viewpoints of pharmacological effect, economy, and adhesive strength, the content of the transdermally absorbable drug is reduced. 0.01 to 25 parts by weight per 100 parts by weight of the adhesive
It is appropriately determined in the range of parts by weight, particularly in the range of 0.5 to 15 parts by weight.

[0135]

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.

The heating element 1 according to the first embodiment of the present invention has a length of 130 mm and a width of 95 m as shown in the schematic sectional view of FIG.
m, a pulp powder or a mixture thereof, in this case, a pulp powder P, is interposed in the rectangular flat bag (packaging material) 10 to enclose the ink-like or cream-like heat generating composition 2; In this case, the bag body 10 is
An adhesive layer 5 made of a non-permeable base material 3 and a permeable covering material 4 and having a thickness of 100 μm is formed on an exposed surface of the base material 3. Reference numeral 7 denotes a release paper covering the exposed surface of the pressure-sensitive adhesive layer 5.

The base material 3 is a polyethylene film 3 having a thickness of 40 μm so that sufficient flexibility can be obtained.
b) Polyethylene / polypropylene heat-adhesive nonwoven fabric (ES fiber) 3 having a thickness of 40 g / m ² (about 340 μm) on one side
a was used.

In order to increase the mechanical strength and obtain sufficient flexibility, the coating material 4 is, for example, a 150 μm-thick polypropylene nonwoven fabric 4 b on one side of a 100 μm-thick polyethylene porous film 4 a. Are laminated. The moisture permeability of the coating material 4 was adjusted so that the moisture permeability was 450 g / m ² · 24 hr by the Lissi method.

By the way, an ink-like or cream-like exothermic composition 2 to be described later is laminated on the upper surface of the polyethylene / polypropylene heat-adhesive nonwoven fabric 3a on the substrate 3, while
After laminating the pulp powder P on the base 3 at a position corresponding to the lamination region of the ink-like or cream-like heat-generating composition 2 by the following method, the ink-like is formed only on the pulp powder P. Or the heat-generating composition 2 in the form of cream is laminated, that is, the pulp powder P is interposed between the porous film 4b made of polyethylene in the coating material 4 and the heat-generating composition 2 in the form of ink or cream. It becomes.

That is, while the heat-generating composition 2 in the form of an ink or a cream is laminated on the polyethylene-polypropylene heat-bonding nonwoven fabric (ES fiber) 3a on the substrate 3, the roll pulp is pulverized and the pulverized pulp powder is pulverized. The pulp powder P is sucked or sprayed and laminated on a predetermined area of the upper surface of the nonwoven fabric 4b made of polypropylene in the air-permeable covering material 4 while dropping the powder P by the quantitative feeder, and the heat generating composition 2 and the pulp powder are laminated. P, and the outer peripheral portion S of the exothermic composition 2
, The coating material 4 and the base material 3 are thermally bonded.

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

The exothermic composition 2 in the form of an ink or a cream was produced by the following method. That is, 100 parts by weight of iron powder (DKP manufactured by Dowa Iron Powder Co., Ltd.) as an active ingredient was added to activated carbon as a carbon component (SA-
1) 14 parts by weight, 5 parts by weight of salt (sodium chloride) as a metal chloride, CMC (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a thickener
1 part by weight of Cellogen EP (trade name), 1 part by weight of KI gel (201K) manufactured by Kuraray Co. as a water retention agent, 2 parts by weight of bentonite (200), and 0.2 part by weight of sodium tripolyphosphate as a pH adjuster were mixed. And the iron powder 10
The cream was prepared by adding 46 parts by weight of water to 0 parts by weight.

That is, the activated carbon, the thickener, the water retention agent, the pH adjuster, the salt and the iron powder were arranged in this order, and at the above-mentioned mixing ratio, a mixer (TK Hibis Mix 2P-100 manufactured by Tokushu Kika Kogyo KK). After stirring for 5 minutes, water was further added with stirring,
Knead for 15 minutes.

Thereafter, the blades and the deposits in the container are cleaned, kneading is performed again for 20 minutes, the viscosity is measured, the specific gravity is measured, and the water content is adjusted. The water content was 46 parts by weight based on 100 parts by weight of iron powder (DKP manufactured by Dowa Iron Powder Co., Ltd.).
The rotation speed of the blade is 10 rpm from start to end.
m.

The exothermic composition 2 is in the form of an ink or a cream and has a remarkably small surface area. The contact area with air is limited. In addition, free water or a hydrated gel suppresses the contact between iron powder and air. As a result, the amount of the oxidation reaction per unit time is remarkably limited. As a result, the film-like or sheet-like coating material 4 is laminated on the heat-generating composition 3 and the oxidation reaction until the heating element 1 is obtained is almost prevented. It is done.

As described above, since the exothermic composition 2 is formed in an ink-like or cream-like viscous body, it can be laminated on the upper surface of the base material 3 by screen printing, and the control of the lamination area can be improved. It can be performed with high precision and the film thickness can be controlled to be very thin and uniform. In addition, the bonding force between the pulp powder P and the ink-like or cream-like heat-generating composition 2 in the coating material 4 can be used. The exothermic composition 2 is prevented from moving in the bag 10. In addition, the heating element 1 can be made ultra-thin by reducing the film thickness of the ink-like or cream-like heating composition 2 in this manner.

In this embodiment, the pulp powder P is suctioned while dropping the pulp powder P onto a predetermined region on the upper surface of the polypropylene nonwoven fabric 4b while feeding the rolled coating material 4 having a width of 140 mm horizontally at a speed of 180 m / min. , laminated (basis weight 35 g / m ^2), further as the pulp powder-like bodies P is in contact with the ink-like or creamy exothermic composition 2 on the substrate 3, covered the coating material 4, followed by The outer peripheral portion S of the printing area is sealed by heat sealing, and cut one after another at the center of the heat sealing area in the width direction, so that the sealing width around each heating element 1 is 7 mm, and is ultra-thin. Heating element 1 was manufactured.

Each of the cut heating elements 1 is subsequently sent to a packaging step and sealed in an airtight outer bag (not shown).

Ink-like or cream-like exothermic composition 2
Is screen-printed on the upper surface of the base material 3 and then covered with a coating material 4 from above, and a part of the moisture of the heat generating composition 2 is gradually absorbed by the pulp powder P in the coating material 4. However, the time from when the ink-like or cream-like heat-generating composition 2 is screen-printed on the pulp powder P to when it is enclosed in the outer bag is extremely short, during which the exothermic reaction becomes possible. In addition, since the water of the ink-like or cream-like exothermic composition 2 is hardly absorbed by the pulp powder P on the coating material 4, the exothermic reaction hardly occurs.

Accordingly, there is almost no possibility that the ink-like or cream-like heat-generating composition 2 generates heat in the production process, and there is no risk of loss due to the exothermic reaction or deterioration of the heat-generating composition. In addition, there is almost no possibility that the ink-like or cream-like heat-generating composition solidifies in the process from the mixing of the ink-like or cream-like heat-generating composition 2 to the screen printing on the base material 3, thereby lowering the yield due to the solidification and reducing the operation. It is possible to prevent various problems such as interruption, restrictions on operation time, difficulty and danger of cleaning of the manufacturing apparatus, frequent cleaning of the manufacturing apparatus, and difficulty of coagulation processing.

Further, after 24 hours had passed after enclosing in the outer bag, the outer bag was broken and allowed to adhere to the body surface of the person, and when used normally, the exothermic temperature was about 38 ° C. in about 1 to 2 minutes. , And then exothermed at 38-41 ° C. for 8.5 hours or more. During this use, the exothermic composition 2 did not move in the bag 10 at all, and average heat generation was observed over the entire surface.

The heating element 1 according to the second embodiment of the present invention has a length of 130 mm and a width of 95 m, as shown in the schematic sectional view of FIG.
An ink-like or cream-like heat-generating composition 2 is sealed and laminated in a rectangular flat bag (wrapping material) 10 of m in length with a pulp powder P interposed therebetween. ,
It is composed of a non-permeable base material 3 and a permeable covering material 4.

In this case, the heat-generating composition 2 in the form of an ink or a cream is encapsulated on the polyethylene-polypropylene heat-bonding nonwoven fabric (ES fiber) 3a in the base material 3 with the pulp powder P interposed therebetween. A laminated styrene-isoprene-styrene block copolymer-based pressure-sensitive adhesive layer 5 having a thickness of 100 μm is formed on the exposed surface of the substrate 3. Reference numeral 7 denotes a release paper for covering the adhesive layer 5.

As the base material 3, the coating material 4, the pulp powder P, the ink-like or cream-like heat-generating composition 2, and the pressure-sensitive adhesive layer 5, the same as those in the first embodiment were used. In this case, the basis weight of the pulp powder P was 35 g / m ² .

Then, the pulp powder P is laminated on a predetermined area of the base material 3, and the ink-like or cream-like heat generating composition 2 is laminated only on the pulp powder P by screen printing. Or creamy exothermic composition 2
The outer peripheral portion S is sealed by heat sealing with the covering material 4 covered from the upper surface of the heating element 1 so that the sealing width around each heating element 1 is 7 mm, and the ultra-thin heating element 1 according to the present invention.
Was manufactured.

In short, in the second embodiment, instead of laminating the pulp powder P on the covering material 4, the pulp powder P is laminated on the base material 3, and the pulp powder P Except that a part of the water of the ink-like or cream-like exothermic composition 2 is absorbed by P, the other configuration of the exothermic body 1 is the same as that of the first embodiment, and therefore, Since their operations and effects are the same as those of the first embodiment, their description is omitted to avoid duplication.

[0157] Also, after 24 hours had passed after enclosing in the outer bag, the outer bag was broken and allowed to adhere to the body surface of a human, and when used normally, the exothermic temperature was about 38 ° C in about 1 to 2 minutes. The temperature was raised to 38 to 41 ° C. for 8 hours or more. During use, the exothermic composition 2 in the form of an ink or a cream did not move in the bag 10 at all, and an average exotherm was observed over the entire surface.

The heating element 1 according to the third embodiment of the present invention has an ink-like or cream-like heat-generating composition 2 sandwiched between pulp powders P from both sides as shown in a schematic sectional view of FIG. The configuration is the same as that of the first embodiment except that the layers are stacked.

In other words, the heating element 1 is provided on the upper surface of the heat-bondable polyethylene / polypropylene non-woven fabric (ES fiber) 3a on the base material 3 with an ink-like or cream-like heating composition 2 similar to that used in Example 1. Before laminating the pulp powder P on the lamination region of the ink-like or cream-like exothermic composition 2 on the base material 3 so that the basis weight is 20 g / m ² , The ink-like or cream-like heat-generating composition 2 is laminated on the pulp powder P, and then, as in Example 1, a coating material 4 is placed on the heat-generating composition 2, and then the outer peripheral portion S of the printing area is formed.
Was sealed by heat sealing, and cut one after another at the center of the heat sealing region in the width direction, thereby producing an ultra-thin heating element 1 having a sealing width around each heating element 1 of 7 mm. In this case, the pulp powder P laminated on the coating material 4 was adjusted so that its basis weight was 20 g / m ² .

In short, the heating element 1 of the present invention, its manufacturing method and other constitutions are the same as those of the first embodiment.
Therefore, these descriptions are omitted to avoid duplication.

Also, after enclosing in the outer bag, 24 hours later, the outer bag was broken and adhered to the body surface of the person. When the device was used normally, the heat generation temperature was about 38 ° C. in about 1 to 2 minutes. The temperature was raised to 38 to 41 ° C. for 8 hours or more. During this use, the exothermic composition 2 did not move in the bag 1 at all, and average heat generation was observed over the entire surface.

When the heating element according to the present invention is applied, since the heating element is formed to be ultra-thin, it becomes flexible as a whole, and as a result, the feel to the shoulder is softened or the shoulder is curved. It easily deforms along, deforms 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, Excellent 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 according to the present invention is uniform, there is no low-temperature burn, and safety is enhanced.

In particular, in the heating element according to the present invention, a pulp powder or a mixture thereof is used. The pulp powder has a good water absorption and a high water absorption. In addition, even after absorbing moisture,
The heating element is extremely flexible and elastic, and has a soft feeling.

[0165]

As described above, in the present invention, the ink-like or cream-like heat-generating composition is laminated and enclosed in a sheet-like packaging material. One or both sides of pulp powder, or pulp powder, ceramic powder that emits far-infrared rays, fiber that emits far-infrared rays, iron powder, iron powder coated with carbon component, or water absorbent At least one mixture is laminated, and at least a part of the sheet-like packaging material has air permeability,
Moreover, a part of the water content of the ink-like or cream-like heat-generating composition is absorbed by a water-absorbing body such as the pulp powder.

That is, in the present invention, an ink-like or cream-like heat-generating composition is used, excess water in an ink-like or cream-like heat-generating composition, or free water or a part of water in a water-containing gel, The most significant feature is that the barrier layer is removed by absorbing the water into a water absorbent such as pulp powder, and as a result of having such a configuration, the following remarkable effects are exhibited.

First, in the present invention, since the heat-generating composition used is an ink-like or cream-like thickened heat-generating composition, this ink-like or cream-like heat-generating composition is printed or coated. , A pulp powder laminated on a predetermined region of the upper surface of the substrate, or a predetermined region on the upper surface of the substrate, or can be laminated on a mixture thereof, and an ink-like or cream-like exothermic composition, The lamination area can be controlled with high precision, and can be laminated on the pulp powder or the mixture thereof with a very thin film thickness, and as a result, it is possible to produce an ultra-thin heating element of the present invention at high speed. Can be

In the present invention, since an exothermic composition in the form of an ink or a cream is used, excess moisture or free water or a hydrogel in the exothermic composition forms a barrier layer, and During the production of the composition, there is almost no exothermic reaction of the ink-like or cream-like exothermic composition, and loss due to the exothermic reaction at the time of production, quality deterioration and coagulation of the exothermic composition are prevented.

On the other hand, in the heating element according to the present invention, the water-absorbing body such as pulp powder,
Excess water in the ink-like or cream-like exothermic composition,
Alternatively, as a result of absorbing free water or a part of the water in the hydrogel, the barrier layer is lost, and when used, the mixing ratio of the water in the exothermic composition becomes a state suitable for the exothermic reaction,
Porous, good contact with air, and can obtain a desired exothermic temperature during use, such as extremely high quality,
The effect is that the reliability is extremely high.

Further, as described above, the heat-generating composition in the form of an ink or cream is laminated on a pulp powder or a mixture thereof in a predetermined region on the upper surface of the substrate by printing or coating. Since the heat-generating composition in the form of an ink or a cream has tackiness, the heat-generating composition is adhered and fixed to a water-absorbing body such as a pulp powder, and therefore, the heat-generating composition in the bag body is not used. As a result, the movement of the heat-generating composition is prevented from fluctuating, and the heat-generating composition is prevented from being biased in the bag to generate high-temperature spots, thereby reliably preventing low-temperature burns. Therefore, the effect of significantly improving safety can be obtained.

By the way, in the heating element of the present invention, as described above, if the ink-like or cream-like heat-generating composition is simply encapsulated in a sheet-like packaging material, required heat-generating characteristics can be obtained due to the presence of the barrier layer. In order to obtain a heating element having the required heating characteristics, it is necessary to absorb excess water in the ink-like or cream-like heat-generating composition, or free water or a part of the water in the water-containing gel to remove the heating substance. It is necessary to remove the barrier layer.

In the heating element according to the present invention,
The removal of the barrier layer can be realized by absorbing the water into a water-absorbing material such as pulp powder, so that the following remarkable effects can be obtained.

That is, in the heating element using the ink-like or cream-like heat-generating composition, the pulp powder or the mixture thereof is passed through a gas-permeable film or sheet when the barrier layer of the heating substance is removed. Suction, or laying a screen and spraying, as a result of the pulp powder, or a mixture thereof being laminated only at the predetermined location,
Patterning is extremely easy, and this pulp powder,
Alternatively, the mixture has good water absorption, and has a high water absorption, and even after absorbing water,
As a result, the heating element is extremely flexible and elastic, and has a soft feeling.

Of course, in the present invention, since the exothermic composition thickened into an ink or a cream is used, the exothermic composition is super-thin and uniformly laminated by printing or coating. As a result, the heating element is ultra-thin, highly flexible, has excellent followability to curved or bent parts such as shoulders, and has excellent usability. By using a powder or a mixture thereof, the powder can be used more comfortably.

In the present invention, in particular, a heat-adhesive or heat-fusible foam film sheet, porous film sheet, A non-woven fabric or a woven fabric is joined, and a pulp powder or a mixture thereof is laminated on a predetermined area of the foamed film sheet, the porous film sheet, the non-woven fabric or the woven fabric, and the pulp powder or a mixture thereof is mixed. When the ink-like or cream-like heat-generating composition is laminated only on the lamination point, the foamed film / sheet, the porous film / sheet, the nonwoven fabric or the woven fabric, together with the pulp powder, or the mixture thereof, becomes ink-like or cream-like. As a result, the exothermic composition is more easily fixed, so that its movement and bias are prevented.

In the heating element according to the present invention, if the base material and the covering material have extensibility, in particular, elasticity, it becomes easier to train the heating element in a complicated uneven shape at the application site, and it is difficult to use the heating element. The ability to follow changes in the uneven shape due to the movement of the user is enhanced, the peeling of the heating element or lifting from the application site is reliably prevented, and the close contact with the living body is improved, resulting in an excellent warming effect and blood circulation promoting effect Is obtained.

In the heating element according to the present invention, the water evaporating from the exothermic composition with the progress of the exothermic reaction can be replenished by discharging water from a water-absorbing body such as a pulp powder that retains the water, and can be used for a long time. The required heat generation temperature can be maintained over the range.

[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.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Heating element 2 Ink-like or cream-like heat-generating composition 3 Substrate 3a Polyethylene / polypropylene heat-adhesive nonwoven fabric
(ES fiber) 3b Polyethylene film 4 Coating material 4a Polypropylene nonwoven fabric 4b Polyethylene porous film 5 Adhesive layer 7 Release paper 10 Packaging material (bag) P Pulp powder

Claims (10)

[Claims] An ink-like or cream-like heat-generating composition is laminated and enclosed in a sheet-like packaging material, and one or both sides of the ink-like or cream-like heat-generating composition is a pulp powder or Pulp powder, ceramic powder that emits far-infrared rays, fiber that emits far-infrared rays, metal powder,
At least one mixture selected from iron powder or a water absorbing agent coated with a carbon component is laminated, and at least a part of the sheet-like packaging material has air permeability, and the ink-like A heating element characterized in that a part of the water content of the cream-like heating composition is absorbed by a water-absorbing body such as the pulp powder. 2. 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. The heating element according to claim 1. 3. The base material and the coating material are entirely or partially sealed by adhesion, heat bonding, or heat fusion at an outer peripheral portion of the ink-like or cream-like heat generating composition. Or the heating element according to 2. 4. The heating element according to claim 1, wherein the base material and / or the coating material is formed of a film- or sheet-shaped water-absorbing material having a water-absorbing property. 5. The heat generation according to claim 1, wherein a water-absorbing layer is laminated on at least a portion of the base material and / or the coating material which is in contact with the ink-like or cream-like heat generation composition. body. 6. The heating element according to claim 5, wherein the water-absorbing layer is formed of a film-shaped or sheet-shaped water-absorbing material. 7. The heating element according to claim 4, wherein the water-absorbing material is a water-absorbing foamed film / sheet, paper, nonwoven fabric, woven fabric, or porous film / sheet. 8. The heating element according to claim 1, wherein the base material and the covering material are formed of an extensible material. 9. The heating element according to claim 1, wherein in the packaging material, at least one side or at least one of the base material and the coating material has air permeability. 10. The heating element according to claim 1, wherein the pressure-sensitive adhesive layer is laminated on at least a part of one of the exposed surfaces of the base material or the coating material.