JPH1130579A - Method and apparatus for measuring oxygen diffusion amount, and heat-generating bag having gas permeation amount regulated by oxygen diffusion amount - Google Patents

Abstract

PROBLEM TO BE SOLVED: To speedily and accurately measure a gas permeation amount irrespective of the type of a wrapping material, by exposing one face of the gas-permeable wrapping material to the air, scavenging with a carrier gas not including oxygen to the other face, and measuring the concentration of oxygen in the carrier gas. SOLUTION: A gas-permeable wrapping material 4 to be measured is held between metallic frames 8, 9 and sheet packings 10, 11 of a lid part 3 where a part corresponding to a face 12 to be measured is removed. The interface between the lid part 3 and a chamber 2 is maintained hermetically by a ring sheet packing 13. A bottom frame 14 and the lid part 3 are fastened by a stud bolt 15 and a nut 16 and fixed. In this state, nitrogen gas of a constant flow rate is supplied into the chamber 2 from a nitrogen gas feed pipe 5. The concentration of oxygen in the gas coming out from a discharge pipe 6 is measured. The oxygen diffusion amount of the wrapping material 4 is detected. The gas permeability of the wrapping material 4 can be quickly and accurately measured irrespective of material, thickness, shape of a gas permeation hole, etc. At the same time, the obtained oxygen diffusion amount shows high correlation with heat generation characteristic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for measuring the air permeability of a gas-permeable packaging material, and to a heating bag using the gas-permeable packaging material defined by the oxygen diffusion amount. For more information,
The present invention relates to an oxygen diffusion amount measuring method and an oxygen diffusion amount measuring device for measuring the air permeability of a gas permeable packaging material used for a color filter and a deoxidizer, and a heat generating bag in which the amount of air is defined by the oxygen diffusion amount.

[0002]

2. Description of the Related Art Conventionally, a heat-generating composition mainly composed of an oxidizable metal powder which generates heat upon contact with oxygen in the air has been housed in a gas-permeable inner bag and further sealed in a non-gas-permeable outer bag. The heat-produced bag is used as a disposable color warmer for the human body or as a medical device. Further, examples of the heat generating bag used for keeping the human body warm include a heat generating bag for the body used for the waist and shoulders, a heat generating bag for the pocket used for pockets and gloves, and a heat generating bag for shoes inserted into shoes.

[0003] These heating bags are designed so that a desired maximum temperature, a time until the desired temperature is reached (rise time), a duration of heat generation, and the like are obtained according to the application.
The composition ratio of the exothermic composition, the amount of the exothermic composition, the ventilation rate of the inner bag, and the like are set.

Here, the exothermic composition is an oxidizable metal powder,
It is a mixture of activated carbon, inorganic electrolyte, water and the like, and iron powder is generally used as the oxidizable metal powder. The exothermic composition comes into contact with oxygen in the air and generates heat when the oxidizable metal powder turns into a metal oxide. The air-permeable packaging material used for the inner bag may be a non-air-permeable sheet having an equivalent diameter of 0.03 to 0.5 with a needle or electric discharge.
mm, a synthetic fiber such as polyethylene, polypropylene, etc. One in which the powder is dispersed, extruded into a film shape, stretched, and provided with a large number of fine pores having an equivalent diameter of 10 μm or less (a microporous film) is available. Further, there is a material obtained by laminating a non-woven fabric or the like to these ventilation packaging materials.

Here, there are two methods for controlling the heat generation characteristics of the heat generation bag, by controlling the composition ratio of the heat generation composition as described above, and adjusting the oxygen supply amount to the heat generation composition. Can do it. Furthermore, it can be carried out by adjusting both the preparation of the exothermic composition and the amount of ventilation of the breathable packaging material. However, in general, the setting of the heat generation characteristic is mainly performed by the air permeability of the air-permeable packaging material used for the inner bag.

As a method for measuring the air permeability of these air permeable packaging materials, a conventionally known method is diverted, and a method using a Gurley air permeability measurement method (JIS P 8117) (Japanese Patent Publication No. 7-90030). JP-A-8-80317
And a Frazier-type tester (JIS L
1018, JIS L 1096) (Japanese Unexamined Patent Publication No. 7-67907), and a moisture permeability measurement method (J
IS Z 0208) (JP-A-7-124)
192, JP-A-8-92075) and the like. These methods are used for design of heat generation characteristics of the heat generation bag, quality control, and the like.

[0007] As a method which is officially determined by a method for measuring the heat generation characteristics of a heat generation bag, Japanese Industrial Standard (JIS)
There is a test method specified in S4100). According to this, the heat generation characteristics were measured using a temperature measurement device specified in JIS S 4100, using an outside air temperature of 20 ° C. and a relative humidity of 65 ° C.
% In an atmosphere. The heat generation characteristics include the time from the start of the heat generation operation until the temperature reaches 40 ° C. (rise time), the maximum temperature reached (maximum temperature),
It is defined that the time is expressed by a time (duration) for maintaining the temperature of not less than ° C.

[0008]

The heat generated by the heat-producing bag is supplied by the infiltration of oxygen in the air for a long time through the fine holes of the air-permeable packaging material, and the oxygen and the oxidizable metal powder ( It is generated by an oxidation reaction upon contact with a typical metal powder (iron powder). However,
In the method for measuring air permeability, depending on the configuration, material, shape of the air hole, size of the air hole, and the like of the air permeable packaging material constituting the inner bag, there is a correlation between the measured value of the air flow and the temperature characteristic. Therefore, there was a problem that the design and quality control of the heat generating bag could not be sufficiently performed.

In other words, in the above-mentioned Gurley air permeability measurement method, the weight of the gas chamber of the measuring instrument is configured to act as a pressure difference between the front and back of the gas permeable packing material, so that a certain volume of gas passes through the gas permeable packing material. This is a method of measuring the time required. According to this measuring method, in the case of a packaging material provided with a needle or an electric discharge and having a relatively large vent such as an equivalent diameter of 0.03 to 0.5 mm, it can be measured in several seconds to several minutes. However, an air-permeable packaging material composed of a number of fine holes, for example, a fine powder such as calcium carbonate or barium sulfate dispersed in a synthetic resin, extruded into a film shape, and further stretched to form a fine hole having an equivalent diameter of 10 μm or less. In the case of a gas-permeable packaging material provided with a Grease, not only does it take a long time of several thousand to 10,000 seconds or more, but also the measurement is out of the measurement range (2 to 1800 seconds / 100 ml) of the Gurley air permeability test method itself. As a result of the measurement, there was an inconvenience that reproducibility could not be obtained. Furthermore, even when the Gurley air permeability measurement value is significantly different depending on the type of the air-permeable packaging material, the same heat generation characteristic may be exhibited when used for a heating bag, and the measured air permeability and the heat generation characteristic may be different. However, there was a disadvantage that no correlation could be obtained.

A method using a Frazier-type tester is a method for measuring air permeability of a woven fabric mainly, and a method of giving a pressure difference of 12.7 mmH ₂ O between the front and back of the air-permeable packaging material. . This method can be applied to measurement of a gas-permeable packaging material having a large air hole. However, in the case of a gas-permeable packaging material having fine pores of 5 μm or less, the air permeability is too small, and the measurement range of this measurement method itself (0.
3 to 400 cc / cm ² / sec), and the measurement could not be performed.

Further, in the case of the moisture permeability measurement method, a method is used in which a pressure difference is not applied between the front and back of the gas-permeable packaging material, and the moisture permeability is determined from the amount of water vapor diffused and transmitted under the condition of moisture saturation. Seems as if the way. However, depending on the type of air-permeable packaging material, especially in the case of a moisture-permeable air-permeable packaging material or a fine-pored air-permeable packaging material, there is a correlation between the measured value of the moisture permeability and the heat generation characteristics. There was a disadvantage that the property could not be obtained. For these reasons, it has been strongly desired to develop a method for measuring the amount of air that can measure the amount of air quickly and accurately regardless of the type of air-permeable packaging material, and that can obtain a correlation with the heat generation characteristics. .

Further, as described above, since there is no correlation between the air permeability and the heat generation characteristics of the air-permeable packaging material used for the inner bag, the heat generation bag for the body, the heat generation bag for the pocket, and the heat generation bag for the shoes are used. In this case, the heat generation characteristics could not be designed with high accuracy, and the quality control could not be performed. Therefore, development of a heat generating bag having desired heat generating characteristics and stable heat generating characteristics has been strongly desired. In particular, in the case of shoes, despite the high demands on the market, only the heating bag significantly deviated from the desired heating characteristics for the above-described reason was obtained, and thus the desired heating characteristics were obtained and stable. There has been a strong demand for the development of a heat generating bag having heat generating characteristics.

Accordingly, an object of the present invention is to provide a method for measuring the amount of air that allows quick and accurate measurement of the amount of air irrespective of the type of air-permeable packaging material and that can be selected for correlation with the heat generation characteristics. I do. Further, another object of the present invention is to provide a ventilation amount measuring device capable of measuring a ventilation amount quickly and accurately and irrespective of the type of a breathable packaging material, and obtaining a correlation with a heat generation characteristic. . Still another object of the present invention is to provide a heat generating bag for a body, a pocket, and shoes which has a desired heat generating characteristic and has a stable heat generating characteristic.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, have placed one side of the breathable wrapping material in the state of being exposed to the atmosphere, and placed the other side on the opposite side. By scavenging the carrier gas containing no oxygen, the amount of oxygen gas in the atmosphere diffused and transmitted into the carrier gas through the gas-permeable packaging material, that is, the oxygen diffusion amount is determined as a measure of gas permeability, so that the heating bag It has been found that a correlation can be obtained between the heat generation characteristic of and the oxygen diffusion amount. Furthermore, by using the air permeability defined by the oxygen diffusion amount as a scale, and by defining the ventilation rates suitable for each of the so-called body heating bag, pocket heating bag, and shoe heating bag, a heating bag with stable heating characteristics can be obtained. The inventors have found that the present invention has been achieved.

That is, according to the present invention, one side of the gas-permeable packing material is exposed to the atmosphere, and the other side is scavenged with a carrier gas containing no oxygen. This is a method for measuring the oxygen diffusion amount of a gas-permeable packaging material, which comprises measuring the gas permeability of the material.

Further, according to the present invention, one side of the gas-permeable packaging material is exposed to the atmosphere, and the other surface is brought into contact with a carrier gas containing no oxygen, so that oxygen gas in the air allows the gas-permeable packaging material to be removed from the carrier gas. An apparatus for measuring the amount of diffused oxygen in a gas-permeable packaging material, comprising a diffuser that diffuses and transmits light on the side.

Further, the present invention provides a method of the present invention, wherein the temperature is 20 ° C. and the relative humidity is 65%.
Under the conditions of, one side of the breathable packaging material is exposed to the atmosphere,
Oxygen diffusion amount measured by flowing a carrier gas containing no oxygen on the opposite surface at a flow rate of 0.193 Nl / cm ² h per unit area of the gas-permeable packaging material so as to scavenge the surface of the gas-permeable packaging material. The heat-generating composition that generates heat upon contact with oxygen in the air is stored in a gas-permeable inner bag using a gas-permeable packaging material corresponding to a range of 1100 ± 220 Nl / m ² 24 h (hereinafter the same) on one side. And a heat generating bag for a body characterized by being sealed in a non-breathable outer bag.

Furthermore, the present invention relates to a method of the present invention, wherein the temperature is 20 ° C. and the relative humidity is 6
Under a condition of 5%, one side of the gas-permeable packaging material is exposed to the atmosphere, and a carrier gas containing no oxygen is ventilated to the opposite surface at a flow rate of 0.193 Nl / cm ² h per unit area of the gas-permeable packaging material. Oxygen in the air is placed in a gas-permeable inner bag using a gas-permeable packing material on one side, which has an oxygen diffusion amount of 1600 ± 350 Nl / m ² 24h when measured by flowing the surface of the packing material so as to scavenge it. A heat generating composition for a pocket, wherein a heat generating composition which generates heat upon contact with the air bag is stored and further sealed in an air-impermeable outer bag.

In addition to the above, the present invention relates to a method in which the temperature of 20.degree.
% Of the gas-permeable packaging material, one side of the gas-permeable packaging material is exposed to the atmosphere, and a carrier gas containing no oxygen is supplied to the opposite surface at a flow rate of 0.193 Nl / cm ² h per unit area of the gas-permeable packaging material. Oxygen in the air is added to a gas-permeable inner bag using a gas-permeable packing material on one side, which has an oxygen diffusion amount of 5500 ± 1100 Nl / m ² 24h when measured by flowing the surface of the packing material so as to scavenge it. The exothermic composition that generates heat upon contact is stored,
Further, the heat generating bag for shoes is characterized by being sealed in a non-breathable outer bag.

As the oxygen-free carrier gas of the present invention, nitrogen is preferable. In addition, argon, helium,
Carbon dioxide or the like can also be used, and is not particularly limited to a gas type. In the present invention, “does not include oxygen” does not exclude the inclusion of oxygen to such an extent that the measurement of the ventilation rate is not affected.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is applied to the measurement of the air permeability of a breathable packaging material used for a heating bag, an oxygen scavenger and the like. Further, the present invention is applied to a heat generating bag for a body, a heat generating bag for a pocket, and a heat generating bag for shoes in which a ventilation amount is defined by an oxygen diffusion amount.

In the oxygen diffusion amount measuring method and oxygen diffusion amount measuring apparatus of the present invention, it is possible to quickly measure the air permeability of a packaging material having extremely low air permeability from a packaging material having high air permeability.

In the method and apparatus for measuring the amount of oxygen diffusion according to the present invention, the front and back surfaces of the gas permeable packing material are maintained at substantially equal total pressure conditions, and the oxygen partial pressure difference in the gas in contact with these surfaces is reduced by the oxygen partial pressure difference. It measures a quantity, and is configured to be able to be measured under such a condition that the pressure difference of the total pressure between both surfaces is almost zero.

The surface of the air-permeable packaging material that is in contact with air is always kept in contact with fresh air, that is, the surface that is in contact with air is kept open to the atmosphere. On the other hand, the surface of the gas-permeable packaging material that is in contact with nitrogen needs to be configured so that fresh nitrogen is always supplied so that the partial pressure difference of oxygen can be kept constant even when oxygen diffuses and permeates. Yes, specifically, a method of continuously supplying and exhausting nitrogen is used.

Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows an example of a sectional view of a diffuser of the oxygen diffusion amount measuring device of the present invention. FIG. 2 shows an example of an oxygen diffusion amount measuring apparatus in which two series of diffusers are provided in parallel.

In FIG. 1, the diffuser 1 comprises a chamber 2 and a lid 3. The chamber 2 has a cylindrical shape, and a nitrogen gas supply pipe 5 is provided at a central portion thereof. An exhaust pipe 6 is provided in a portion near the outer periphery of the chamber. A cylindrical partition barrier 7 is provided in the chamber to prevent a short path of nitrogen gas.

The lid portion 3 is made up of metal frames 8 and 9 and sheet packings 10 and 11, and the space between the cover and the chamber is airtightly held via a ring-shaped sheet packing 13. Both the frames 8 and 9 and the sheet packings 10 and 11 have a portion corresponding to the surface 12 to be measured of the breathable packaging material 4 cut out. The gas permeable packing material 4 is sandwiched between the sheet packings 10 and 11, and is entirely fixed between the bottom frame 14 and the lid portion 3 with a stat bolt 15 and a nut 16. In such a state, nitrogen gas is passed through the nitrogen gas supply pipe 5 at a constant flow rate, and the oxygen concentration in the gas flowing out of the exhaust pipe 6 is measured, thereby measuring the oxygen diffusion amount of the gas-permeable packing material. Can be.

FIG. 2 shows the configuration of an oxygen diffusion amount measuring apparatus having two diffusers. Nitrogen gas pressure reducing valve 17
Is supplied to the diffuser 1 through the nitrogen gas flow rate setting device 18. The outlet gas of the diffuser 1 is exhausted through the oxygen concentration detector 19 and the purge line 21. FIG. 2 also shows the case where the oxygen concentration is measured using one gas chromatograph 23. The gas flow path from the diffuser 1 is a branch 2
0, which is connected to a gas chromatograph 23 via a switching valve 22. A gas suction unit 25 is connected to the gas chromatograph 23 behind the gas sampling unit 24.
Thereby, even if there is a flow path resistance from the branching section 20 to the gas sampling section 24, it is set so that a constant flow rate is always obtained.

In the present invention, in addition to the structure and shape of the diffuser shown in FIG. 1, the shape of the chamber may be a rectangular box, an elliptic cylinder, or the like. In addition to the scavenging of nitrogen gas flowing from the center of the chamber to the periphery, it is also possible to scavenge from the periphery to the center, or in the case of a box-shaped chamber, from one end to the opposite side in parallel with the surface to be measured. The size of the chamber is set to a size corresponding to the size of the surface to be measured of the gas-permeable packaging material to be measured, and nitrogen gas can be almost uniformly scavenged on the surface to be measured of the gas-permeable packaging material. There is no particular limitation as long as the gas inside the chamber is replaced in a short time.

The shape and form of the frame are not particularly limited.
It can also be square, rectangular, circular or the like. The shape and size of the frame are not particularly limited as long as a measured surface having an area sufficient to represent the air permeability of the air-permeable packaging material can be obtained. If the area of the surface to be measured is too small, the measurement accuracy is reduced. If the area is too large, it becomes difficult to hold the surface to be measured in a plane.
~300cm ^2, preferably 10 to 100 cm ² approximately. As the sheet packing, a rubber packing having rubber elasticity or a packing made of a synthetic resin is used so as to prevent gas leakage even in the case of a gas permeable packing material having fine irregularities.

FIG. 1 shows an example of a structure in which the chamber and the lid can be divided. However, the chamber and the lid can be integrated. In addition, the breathable packaging material can be tightened and fixed to the chamber by one operation using a rotating handle, a lever, a pneumatic cylinder, or the like. In addition, when attaching a breathable packaging material to a chamber, it is preferable to attach according to the state used for a heating bag. That is, it is preferable to set the inner bag so that the outer surface of the inner bag comes into contact with the atmosphere and the inner surface of the inner bag becomes a nitrogen scavenging surface.

The oxygen concentration can be measured by an oxygen concentration meter using an oxygen gas sensor, a gas chromatograph, or the like. Regardless of the type of equipment used, it is necessary to provide a flow path having a low flow resistance so as not to generate a pressure difference between the inside of the diffuser chamber and the atmosphere. For this reason, when measuring using an oxygen gas sensor, there are a method in which the gas is provided close to the exhaust pipe in the chamber, a method in which the gas is provided immediately after the exhaust pipe, and the like.
In the case of measurement using a gas chromatograph, it is preferable to use a condition that does not cause a pressure difference between the chamber and the atmosphere, for example, a method of sucking a certain amount of gas to a sampling portion of the gas chromatograph.

By further arranging two series of diffusers as shown in FIG. 2 for more efficient measurement,
While the measurement is performed in one series, the other series can exchange and mount the measurement sample. In addition, depending on the distribution state of the ventilation holes of the breathable packaging material, for example, when the ventilation holes are continuously provided in a dotted line, when the holes are provided intensively in the center portion, and the like, the area to be measured is measured. Can be set relatively large so that the measured value can be converted as a representative value of the air-permeable packaging material.

As the nitrogen gas supplied to the diffuser, it is preferable to use a high-purity nitrogen gas so that the gas can be measured with high accuracy even when measuring a gas-permeable packaging material having a small oxygen diffusion amount. If the supply amount of nitrogen gas is too large, vibration or deformation may occur on the surface of the sample to be measured. If the supply amount is too small, the oxygen concentration in the nitrogen gas increases due to oxygen diffusion and penetration, and the gas-permeable packaging material The difference is usually 50 to 2000 ml / cm ² h, preferably 100 to 500 ml / cm ² h, per unit area to be measured of the gas-permeable packaging material, because there is a disadvantage that the oxygen partial pressure difference between the front and back is reduced. In addition to controlling the flow rate of the supplied nitrogen using a flow meter and a needle valve, the use of a mass flow controller is convenient because it can be controlled with high accuracy.

In the diffuser, if there is a pressure difference between the pressure on the atmosphere side and the pressure in the chamber, a viscous flow based on the pressure difference is generated in a gas permeable packing material having a large pore size, and as a result, the diffusion and permeation are caused. This may cause oxygen to flow into the chamber from the atmosphere side or nitrogen to flow from the chamber to the atmosphere side. Therefore,
Although it depends on the hole diameter, the pressure difference between the two is usually 3 m
For example, the diameter of the exhaust pipe of the chamber may be increased so as to be equal to or less than mH ₂ O, preferably 1 mmH ₂ O or a method of suctioning the exhaust pipe. The oxygen concentration can be measured by a gas chromatograph equipped with a thermal conductivity detector, but a zirconia electrode type oxygen meter can also be used easily. When the oxygen concentration is measured by a gas chromatograph with the configuration shown in FIG. 2, the suction flow rate of the sampling gas and the purge line
A consideration such as the length of one is made. In any case, it is necessary to operate so as not to generate a large pressure difference between the pressure in the diffuser chamber and the outside air pressure.

The air-permeable packaging material to be measured in the present invention is:
Regardless of the amount of ventilation, it includes all packaging materials through which gas can diffuse and vent through the holes, and has a hole with an equivalent diameter of usually 1 mm or less. Also,
Any packaging material, which is generally called a film, a sheet, a membrane, or the like, as long as it has a hole with an equivalent diameter of 1 mm or less and has air permeability, is included in the measurement object of the present invention. Therefore, the present invention is not limited to the material and thickness of the breathable packaging material, the shape of the ventilation holes, and the like. Here, the equivalent diameter refers to a diameter obtained by converting the area of the hole into a circle even if the shape of the air hole is elliptical, square, slit, triangular, or the like. The present invention can also be included in a measurement object, even a gas-permeable packaging material having a hole having an equivalent diameter of 1 mm or more. In this case, the inflow of oxygen without diffusion from the atmosphere side of the surface to be measured into the chamber, or Due to the outflow of nitrogen from the inside of the chamber to the atmosphere side due to non-diffusion, the measured value of the oxygen diffusion amount may become inaccurate as the pore diameter increases.

According to the method and apparatus for measuring an oxygen diffusion amount of the present invention, it is possible to accurately measure an air diffusion amount as an oxygen diffusion amount irrespective of the shape and size of a ventilation hole. That is, as a means for imparting air permeability to the air-permeable packaging material, a gas-permeable packaging material having mechanically perforated holes using a needle-shaped projection or the like on a non-air-permeable film, It has relatively large pores with an equivalent diameter of 0.03 to 0.5 mm, such as a material, a heated needle-like projection, or a gas-permeable packaging material in which a part of a film or film is melted by electric discharge machining to form a hole. Can be measured with high accuracy. In addition, calcium carbonate, barium sulfate, etc. are dispersed and mixed in a polyolefin-based synthetic resin such as polyethylene or polypropylene, and then extruded into a film, and further monoaxially or biaxially stretched, so that a number of fine particles having an equivalent diameter of 10 μm or less are formed. The air-permeable packaging material having the air holes can be measured accurately in a short time.

In addition, a non-woven fabric made of a heat-fusible synthetic fiber such as polyethylene or polypropylene is heat-pressed and the air permeability of the non-woven fabric can be similarly measured in a short time and accurately. These air-permeable packaging materials are used as they are or bonded to a non-woven fabric or the like to form a gas-permeable packaging material for a heat generating bag. In any case, the air permeability can be measured by the present invention. The oxygen diffusion amount measuring method and measuring device of the present invention, in addition to the air-permeable packaging material for the heat generating bag, a gas-permeable packaging material or a gas-permeable wallpaper for a deoxidizer, and even a non-permeable and air-permeable. The breathability of clothing or the like having the same can be measured as the oxygen diffusion amount. Further, a film or tube made of a polyfluoroethylene resin or the like can be stretched to have a fine fibril structure, and the air permeability can be measured.

However, in particular, when measuring the ventilation rate of the gas permeable packaging material for a heat generating bag, it is an extremely useful measurement method since the measurement is performed under the condition close to the condition where the heat generating bag is actually used. That is, when measuring the oxygen diffusion amount, one side of the air-permeable packaging material is exposed to the atmosphere, which corresponds to a state in which the heating bag is in contact with the outside air, while nitrogen is scavenged on one side. However, this corresponds to a state in which the oxygen concentration is always close to zero in the heating bag. Therefore, the method for measuring air permeability for a heat generating bag has applicability not seen in the conventional air permeability measuring method.

In general, the heat generating bag is formed by filling a heat generating composition in a flat inner bag having air permeability. Further, although it depends on the type of the heat generating bag, the purpose of use, and the like, there are many cases where the inner bag is formed of a gas permeable packing material on one side and a non-air permeable packing material on one side. FIGS. 3 to 6 show examples of inner bags of heat-producing bags which are manufactured using these air-permeable packing materials and are commercially available. FIG. 3B is a cross-sectional view taken along line AA ′ of FIG.
These inner bags are generally made of a gas permeable packing material on one side and a non-air permeable packing material on one side, and are heat-sealed around to form a flat inner bag.

According to the present invention, the oxygen diffusion amount of the gas-permeable packaging material can be obtained by the following equation (1). In other words, assuming that the amount of oxygen diffusing into the chamber from the atmosphere side through the gas permeable packing material is equal to the amount of nitrogen diffusing and diffusing into the chamber through the gas permeable packing material through the gas permeable packing material. The oxygen diffusion amount of the packaging material can be obtained from the equation 1 from the nitrogen supply amount and the oxygen concentration in the nitrogen after scavenging.

[0042]

## EQU1 ## Oxygen diffusion amount (Nl / m ² 24h) = oxygen concentration ((%) / 100) × nitrogen supply amount (Nl / h) × 24 ×
1 / measurement area (m ² ) In the case where the ventilation holes of the measurement sample are distributed in a part of the surface to be measured, determine the average oxygen diffusion amount of the gas-permeable packaging material by appropriately correcting the area. Can also.
Further, as described above, in the oxygen diffusion amount measuring method and measuring apparatus of the present invention, since the gas permeability is measured from the nitrogen supply amount to the diffuser and the oxygen concentration in the nitrogen after scavenging, regardless of the magnitude of the gas permeability. The amount of ventilation can be accurately measured in a short time.

When a heat generating bag is designed using the air-permeable packaging material defined by the oxygen diffusion amount measured in this way, there is a high correlation between the air flow rate and the heat generation characteristics of the heat generating bag. For this reason, not only is it easy to design a heat generating bag having desired heat generating characteristics, but also it is possible to manufacture a heat generating bag always having stable heat generating characteristics. For example, when a heating bag is manufactured by changing the oxygen diffusion amount of the air-permeable packaging material, a linear relationship exists between the oxygen diffusion amount and the rise time, maximum temperature, and duration in the heat generation test defined in JIS S4100. The square (R ² : contribution ratio) of the correlation coefficient at the time of approximation is 0.85 or more in each case.
It can be 90 or more, or even 0.95 or more.

In the method for measuring the amount of diffusion of oxygen of the present invention, another carrier gas containing no oxygen (scavenging gas) may be used in place of nitrogen for scavenging one side of the gas permeable packing material. For example, argon, helium, carbon dioxide, or the like can be used. However, when these gases are used, the partial pressure difference between these gases and the atmosphere side is significantly larger than that of nitrogen, and some gases have large diffusion constants themselves. As a result, a large amount of the gas escapes to the atmosphere. Therefore, the amount of exhaust gas from the measurement chamber may be smaller than the amount of supply gas. Therefore, in that case, Equation 1 cannot be applied as it is. For example, when helium is used in place of nitrogen, the amount of exhaust gas must be accurately obtained, substituted for the amount of nitrogen supply in Equation 1 and calculated.
Since the amount of exhaust gas must be accurately obtained while maintaining the pressure difference from the atmosphere side at 1 mmH ₂ O or less, the configuration of the oxygen diffusion amount measuring device becomes slightly more complicated than in the case of using nitrogen.

The size and the heat generation characteristics of the heat generating bag are preferably set according to the use, the part to be used, the state of use, and the like. For example, there are two types of heat generating bags for the body that are worn over the underwear such as the waist and shoulders to keep the body warm, so-called regular heating bags having a relatively large area, and so-called mini heating bags having a small area. . These heat generating bags for body having different sizes are basically designed as heat generating bags having a relatively small heat generation amount per unit time, although there is a slight difference in preferable heat generation performance. In addition, since a pocket heat generating bag used in a pocket or glove is used under conditions of poor heat retention, it is designed as a heat generating bag that generates a relatively large amount of heat per unit time.
On the other hand, in the case of a shoe heat generating bag, since the shoe has poor heat retention and is used under conditions of large heat dissipation such as contact with water, snow, etc., the heat generation amount per unit time is reduced. It is a very large fever bag.

The air-permeable wrapping material for the body heating bag of the present invention is
Under a condition of 0 ° C. and a relative humidity of 65%, one side of the breathable packaging material is exposed to the atmosphere, and nitrogen gas is applied to one side at 0.193 Nl / c.
The flow rate of m ² h was set so that the air-permeable packing material surface was scavenged, and the oxygen diffusion amount when the pressure difference between the atmosphere side and the nitrogen gas side was measured at 1 mmH ₂ O or less was usually 1100 ± 220.
Nl / m ² 24 h, preferably 1100 ± 150 Nl /
m ² 24 h, more preferably 1100 ± 100 Nl /
A breathable packaging material corresponding to m ² 24h is used. In the conventional method for measuring the amount of ventilation, the fluctuation range of the heat generation characteristic is too large to obtain the desired heat generation performance, and the quality of the heat generation bag cannot be controlled. However, by defining the amount of ventilation as described above by the method for measuring the amount of diffusion of oxygen of the present invention, a heating bag having desired heating characteristics can be obtained with high accuracy that cannot be achieved by the conventional technology.

Here, the air permeability is based on the case where the air-permeable packaging material is used on one side of the inner bag, and the air-permeable packaging material is used on both sides of the inner bag, and both sides are almost equal. In the case where the air permeability can be maintained, it can be set to about 1/2 of the above value. When partially used, a packaging material having a ventilation rate corrected according to the area ratio can be used.

As described above, the body heating bag has a so-called regular type inner bag having a size of (90 to 1).
10 mm) x (125 to 145 mm) and the size of the inner bag called mini type is (55 to 75 m
m) × (85-105 mm). Further, there are also those having a size of about 1.5 times, 2 times, or 3 times the regular size. However, in the present invention, all of these are included in the body heating bag.

In the heat generating bag for a pocket according to the present invention, one side of the permeable packaging material is exposed to the atmosphere under the conditions of 20 ° C. and 65% relative humidity, and nitrogen gas is applied to one side. At a flow rate of 0.193 Nl / cm ² h so as to scavenge the air-permeable packaging material surface, and the oxygen diffusion amount when the pressure difference between the atmosphere side and the nitrogen gas side is measured at 1 mmH ₂ O or less is usually 1600 ± 350 Nl / m ² 24 h, preferably 16
00 ± 220 Nl / m ² 24 h, more preferably 160
A breathable packaging material equivalent to 0 ± 150 Nl / m ² 24 h is used. Within this range, the heat generating bag exhibits extremely good heat generating characteristics. Also in this case, the ventilation rate is based on the case where the air-permeable packaging material is used on one side of the inner bag, and the air-permeable packaging material is used on both sides of the inner bag, or is partially used, and has substantially the same ventilation. In the case where the property can be maintained, the ventilation rate can be set in the same manner as in the case of the body.

In the heat generating bag for a pocket of the present invention, the size of the inner bag is usually (55 to 75 mm) × (85 to 105 mm).
mm). However, the size is not particularly limited as long as it is used for pockets and gloves.

The air permeability of the gas permeable packaging material of the shoe heat generating bag of the present invention is such that one side of the gas permeable packaging material is exposed to the atmosphere at 20 ° C. and a relative humidity of 65%, and nitrogen gas is applied to one side surface at 0%. .193N
1 / cm ² h at a flow rate such that the air-permeable packaging material surface is scavenged, and the pressure difference between the atmosphere side and the nitrogen gas side is 1 mmH ₂ O.
The oxygen diffusion amount as measured below is usually 5500 ± 11
00Nl / m ² 24h, preferably 5500 ± 800N
1 / m ² 24h, more preferably 5500 ± 500Nl
/ M ² 24 h. By regulating the amount of ventilation in this manner, a shoe heat generating bag, which has conventionally been difficult to design a desired heat generating characteristic, can be obtained. In general, heat dissipation is large, and a comfortable feeling of warmth can be obtained even when used by inserting into a device having poor air permeability.

The inner bag of the shoe heating bag of the present invention includes:
In addition to the so-called horseshoe shape shaped to match the toe of the shoe,
Trapezoidal and rectangular shapes are also included.

[0053]

EXAMPLES Preferred embodiments of the present invention will be described more specifically based on the following examples, but the present invention is not limited thereto. Examples 1 to 9 Examples 1 to 9 are examples relating to the oxygen diffusion amount measuring method and the oxygen diffusion amount measuring apparatus of the present invention. Of these, Examples 3 to 7 are also examples relating to the heat generating bag for a pocket of the present invention.

An oxygen diffusion amount measuring apparatus similar to that shown in FIGS. 1 and 2 was manufactured. Figure 1 shows the configuration of each device.
It was configured as follows according to FIG. The chamber 2 of the diffuser 1 is a stainless steel cylinder having an inner diameter of 102 mm and a depth of 37.5 mm, and has a cylindrical partition barrier 7 having a height of 25 mm for preventing a short path of nitrogen gas and an outer diameter of 60 mm inside. The space volume is 285 ml. In addition, the central portion of the chamber 2 has an outer diameter of 6.35 mm and an inner diameter of 4.57.
The nitrogen gas supply pipe 5 mm is provided so as to protrude 15 mm from the bottom surface. Further, an exhaust pipe 6 is provided at a peripheral portion in the chamber. The frame 8 has a measured surface 12 of 72 mm × 72 mm. The nitrogen gas flow controller 18 is a mass flow controller (SEK Co., Ltd., SEK-400MK3).

The oxygen concentration detector 19 is a zirconia electrode type oxygen meter (manufactured by Toray Engineering Co., Ltd., LC-750).
L), so that the gas chromatograph 23 can be used together. In addition, a suction pump that does not generate pulsation was used as the suction pump 25.

As the air-permeable packaging material 4, a rotating blade having needle-like projections was used as a non-air-permeable packaging material obtained by laminating a nonwoven fabric made of nylon (N5051 manufactured by Asahi Kasei Corporation) with a polyethylene film having a thickness of 50 microns. Using a punch, 31 rows of slit-shaped holes were continuously formed at intervals of 4 mm within a width of 32 mm. In addition, nine kinds of air-permeable packing materials having different air-permeation amounts were manufactured by changing the size of the air hole by changing the depth of the needle perforation stepwise. The size of each of these vents was such that the equivalent diameter was in the range of 0.03 to 0.7 mm. The oxygen diffusion amounts of the nine kinds of air-permeable packaging materials were measured using the above-mentioned oxygen diffusion amount measuring device. The measurement was performed at room temperature 20 ° C.
Supply rate of nitrogen gas 10Nl / h under conditions of 65% relative humidity
(The nitrogen supply rate per unit area of the air-permeable packaging material to be measured was 0.193 Nl / cm ² h), and the suction rate of the sample gas by the suction pump was 1.2 Nl / h. The pressure difference between the atmosphere and the inside of the chamber was 1 mmH ₂ O or less. The time required for the oxygen concentration in the chamber to reach equilibrium was about 12 minutes. The results are shown in Table 1.

Next, using these nine types of breathable packaging materials,
The back seal is provided so that the ventilation holes are distributed on one side.
A 7 mm × 70 mm bag was prepared. In this bag, iron powder 55
Exothermic composition 20 made by mixing ratio of 6 parts by weight of activated carbon, 12 parts by weight of wood flour, 3 parts by weight of salt and 24 parts by weight of water
g, and heat-sealed to produce nine types of flat inner bags as shown in FIG. Further, this inner bag was sealed in a non-breathable outer bag to form a heating bag.

The nine types of exothermic bags were left in an environment of room temperature of 20 ° C. and a relative humidity of 65% for 12 hours to acclimate to the environment, then the inner bag was taken out, and the exothermic bag was produced by the test method specified in JIS S 4100. The properties were measured. The results are shown in Table 1. FIG. 7 shows the relationship between the amount of oxygen diffusion and the maximum temperature (the maximum temperature reached by the heating bag), and FIG. 8 shows the relationship between the amount of oxygen diffusion and the rise time (the time required to raise the temperature to 40 ° C. immediately after the start of the heat generation). In addition, the amount and duration of oxygen diffusion (4
FIG. 9 shows the relationship between the time when the temperature reaches 0 ° C. and the time when the temperature reaches the maximum temperature and reaches 40 ° C.). The square (R ² : contribution ratio) of the correlation coefficient when the relationship between the oxygen diffusion amount and the maximum temperature, the rise time, and the duration is linearly approximated is 0.915 for the maximum temperature and 0 for the rise time, respectively. .92
2. The duration was 0.975. Thus, in each case, a good correlation was recognized with the oxygen diffusion amount.

[0059]

Table 1 Example 1 Oxygen diffusion amount Maximum temperature Rise time Duration (Nl / m ² 24h) (° C) (min) (h) 1 1125 52.5 11.5 14.2 2 1247 55.8 9 8.8 12.6 3 1710 62.2 7.9 8.0 4 1754 63.5 6.3 7.5 5 1766 61.3 7.5 7.6 6 1863 65.1 6.2 6.8 7. 1882 65.6 6.1 6.4 8 1987 65.8 5.5 5.9 9 2032 63.7 6.3 6.3

Examples 10 to 13 Here, Examples 10 to 13 are examples relating to the oxygen diffusion amount measuring method and the oxygen diffusion amount measuring apparatus of the present invention. Of these, Examples 11 and 12 are also examples relating to the body heating bag of the present invention. Four types of air-permeable packaging materials (Nitto Denko Co., Ltd.) composed of a polyethylene microporous membrane having a large number of micropores having an equivalent diameter of 10 μm or less and a nylon non-woven fabric and having different air permeability are bonded as the air-permeable packaging material. Made,
(Brethlon), the oxygen diffusion amount was measured in the same manner as in Examples 1 to 9. Next, each of the air-permeable packaging materials is used on one side, and a non-air-permeable packaging material formed by laminating polyethylene / nylon nonwoven fabric / polyethylene / adhesive / release paper in this order is used on one side, and the polyethylene surfaces are mutually bonded. Four types of bags of 135 mm × 100 mm were manufactured by heat-sealing the three sides so as to be in contact with each other. Each of these four types of inner bags, 53 parts by weight of iron powder,
Activated carbon 8 parts by weight, wood flour 7 parts by weight, salt 4 parts by weight and water 2
40 g of the exothermic composition prepared at a blending ratio of 8 parts by weight was filled to obtain an inner bag as shown in FIG. This was further sealed in a non-breathable outer bag to form a heating bag.

The temperature characteristics test of this heating bag was conducted in Examples 1 to 9.
Was performed in the same manner as described above. The results are shown in Table 2 as Examples 10 to 13. Fig. 1 shows the relationship between the oxygen diffusion amount and the maximum temperature.
FIG. 11 shows the relationship between the oxygen diffusion amount and the rise time.
FIG. 12 shows the relationship between the oxygen diffusion amount and the duration. Also,
The square (R ² : contribution ratio) of the correlation coefficient when the relationship between the oxygen diffusion amount and the maximum temperature, rise time, and duration is linearly approximated is 0.940 for the maximum temperature and 0.974 for the rise time, respectively. , Duration was 0.985. Thus, in each case, a good correlation was recognized with the oxygen diffusion amount.

[0062]

Table 2 Example 2 Oxygen diffusion amount Maximum temperature Rise time Duration (Nl / m ² 24h) (° C) (min) (h) 10 1567 68.6 6.4 8.7 11 1310 62.18 .5 12.3 12 988 51.6 15.0 18.8 13 677 49.7 18.0 22.0

Examples 14 to 21 Examples 14 to 21 are examples relating to the oxygen diffusion amount measuring method and the oxygen diffusion amount measuring apparatus of the present invention. Examples 14 to 21 are also examples relating to the heat generation bag for the body of the present invention. The equivalent diameter is 10 μm as a breathable packaging material
About eight kinds of air-permeable packaging materials (Nitto Denko Co., Ltd., Breslon), which are formed by laminating a polyethylene microporous membrane having a number of micropores and a nylon nonwoven fabric and having different air permeability, Examples 1 to In the same manner as in 9, the oxygen diffusion amount was measured. Using each of the air-permeable packaging materials on one side, polyethylene / nylon nonwoven fabric / polyethylene / adhesive /
A non-breathable sheet formed by laminating release paper in order is used on one side, and the three sides are heat-sealed on the three sides so that the polyethylene surfaces are in contact with each other.
Eight types of bags of 0 mm were produced.

Each of these eight types of bags was filled with 34 g of a heat-generating composition prepared by mixing 53 parts by weight of iron powder, 8 parts by weight of activated carbon, 7 parts by weight of wood flour, 4 parts by weight of salt and 28 parts by weight of water. An inner bag as shown in FIG. 3 was manufactured. This was further sealed in a non-breathable outer bag to form a heating bag. The exothermic characteristics of this exothermic bag were examined in the same manner as in Examples 1 to 9. The results are shown in Table 3. Fig. 1 shows the relationship between oxygen diffusion and maximum temperature
FIG. 14 shows the relationship between the oxygen diffusion amount and the rise time in FIG.
FIG. 15 shows the relationship between the oxygen diffusion amount and the duration. Also,
The square (R ² : contribution ratio) of the correlation coefficient when the relationship between the oxygen diffusion amount and the maximum temperature, the rise time, and the duration was linearly approximated was 0.968 for the maximum temperature and 0.887 for the rise time, respectively. , Duration was 0.961. Thus, in each case, a good correlation was recognized with the oxygen diffusion amount.

[0065]

Table 3 Example 3 Oxygen diffusion amount Maximum temperature Rise time Duration (Nl / m ² 24h) (° C) (min) (h) 14 1042 54.7 10.3 15.2 15 1148 58.4 9 0.0 12.5 16 1005 53.2 10.5 15.2 17 1185 58.9 8.9 12.2 18 1222 61.9 8.0 9.9 19 1319 63.0 7.9 8.6 20 1273 63.4 7.0 8.9 21 1315 63.7 7.7 9.0

Examples 22 to 28 Examples 22 to 28 are examples relating to the heat generating bag for shoes according to the present invention. Basis weight 50 g / m and ² nylon non-woven fabric and sheet obtained by bonding a polyethylene film having a thickness of 50 [mu] m, a basis weight of 50 g / m ² nylon nonwoven fabric and a thickness of 10
Oxygen diffusion amount bonded to a polyethylene porous film having a maximum pore diameter of about 1.1 μm and a pore diameter of about 4800 to 63 μm.
00Nl / m ² 24h 7 types of breathable wrapping materials are overlapped so that the polyethylene surfaces are in contact with each other, and cut into a horseshoe shape of 8.8cm in length and 6.6cm in width,
The periphery was heat sealed to form a bag.

In this bag, 66.4 parts by weight of iron powder and 6.
4 parts by weight, 1.5 parts by weight of sodium chloride, 22.2 parts by weight of water, 3.1 parts by weight of perlite powder and 0.1 part of superabsorbent resin.
An inner bag was manufactured by filling 14 g of the exothermic composition consisting of 4 parts by weight. The inner bag was further sealed in a non-breathable outer bag to form a heating bag for shoes, and left at 25 ° C. for one week. The inner bag was taken out from the outer bag, and an aluminum plate and a rubber plate having a thickness of 4 mm were set in this order on a polystyrene foam at 20 ° C., and a heating bag for shoes sandwiched between two upper and lower gauze sheets was placed. It was placed on it, and three rubber plates were further stacked, and covered with two flannels from above, and the heat generation characteristics were measured. Table 4 shows the results.
The square (R ² : contribution ratio) of the correlation coefficient when the relationship between the oxygen diffusion amount and the maximum temperature, the rise time, and the duration is linearly approximated is 0.930 for the maximum temperature and 0 for the rise time. .966, duration 0.982. Thus, in each case, a good correlation was recognized with the oxygen diffusion amount. In addition, Example 23 and Example 24
The inner bag of the heat generating bag for shoes was inserted into the work shoes with the air-permeable side facing up, and an adult man performed light work in an environment at an outside air temperature of 5 ° C. As a result, all maintained a comfortable temperature.

[0068]

Table 4 Example 4 Oxygen diffusion amount Maximum temperature Rise time Duration (Nl / m ² / 24h) (° C) (min) (h) 22 4800 40.5 14.0 7.5 23 5600 41.5 10.5 6.2 24 6000 42.5 8.6 5.4 25 5800 42.0 9.6 6.0 26 5950 42.5 9.0 5.6 275830 42.0 9.0 6.0 28 6300 43.5 6.0 5.0

Comparative Examples 1 to 8 The same eight kinds of air-permeable packaging materials used in Examples 14 to 21 were measured for moisture permeability by the method specified in JIS Z0208. Table 5 shows the results. Since this air-permeable packaging material is the same as the packaging materials of Examples 14 to 21, the moisture permeability and the heat generation test results of Examples 14 to 21 can be made to correspond to each other. As shown in FIG. From FIG. 16, it was recognized that the maximum temperature was abnormally greatly changed in the portion where the moisture permeability was low, even though the difference in moisture permeability was small. The square of the correlation coefficient (R ² : contribution ratio) when the relationship between the moisture permeability and the maximum temperature, the rise time, and the duration was linearly approximated was 0.641 for the maximum temperature and 0.5 for the rise time, respectively.
617, duration 0.684. Thus, the correlation between the moisture permeability and the heat generation characteristics was very low.

[0070]

[Table 5]

Comparative Example 9 A nonwoven fabric made of nylon (Asahi Kasei Corporation) was used as a breathable packaging material.
N5051) and a 50-micron-thick polyethylene film attached to a non-breathable packing material using a punching device using a rotary blade having needle-like projections, and a hole interval of 4 mm.
, 31 rows of slit-shaped holes were continuously formed within a width of 32 mm. Here, the size of the perforated hole was such that the equivalent diameter was in the range of 0.1 to 0.15 mm. When the air permeability of this air permeable packing material was measured with a Gurley air permeability tester specified in JIS P 8117, it was 7 sec / 100 m.
l.

This air-permeable packaging material is used on one side, and a non-air-permeable packaging material formed by laminating polyethylene / adhesive / release paper in this order is used on one side, so that the polyethylene surfaces are in contact with each other. Heat seal the three sides together, 9
A 6 mm × 70 mm bag was manufactured. This bag is filled with 13 g of an exothermic composition made up of 53 parts by weight of iron powder, 8 parts by weight of activated carbon, 7 parts by weight of wood flour, 4 parts by weight of salt and 28 parts by weight of water, and heat-sealed to obtain a flat shape. I made an inner bag. This was further sealed and stored in a non-breathable outer bag. The exothermic characteristics of this exothermic bag were measured in the same manner as in Examples 1 to 9. The results are shown in Table 6.

Comparative Example 10 The same breathable packaging material as used in Example 11 was used according to JIS P8.
When the air permeability was measured with a Gurley air permeability meter specified in 117, it was 12000 sec / 100 ml. This air-permeable packaging material is used on one side, and a non-air-permeable packaging material composed by laminating polyethylene / adhesive / release paper in this order is used on one side, and the polyethylene surfaces are overlapped so as to be in contact with each other. Heat sealed on three sides, 96mm x 70m
m bags were manufactured. 53 parts by weight of iron powder and 8 pieces of activated carbon
A flat inner bag was manufactured by filling 13 g of the heat-generating composition prepared in a mixing ratio of 7 parts by weight of wood flour, 7 parts by weight of wood flour, 4 parts by weight of salt and 28 parts by weight of water, and heat-sealed. This was further sealed and stored in a non-breathable outer bag. The exothermic characteristics of this exothermic bag were measured in the same manner as in Examples 1 to 9. The results are shown in Table 6, and although the Gurley air permeability was significantly different from that of Comparative Example 9, the heat generation performance was similar.

[0074]

Table 6 Comparative Example Gurley air permeability Maximum temperature Rise time Duration (sec / 100 ml) (° C) (min) (h) 9759.1 6.6 10.5 10 12000 58.2 6.6 11.5

[0075]

According to the oxygen diffusion amount measuring method and oxygen diffusion amount measuring apparatus of the present invention, the air permeability of the air permeable packaging material can be measured quickly and accurately, and the obtained oxygen diffusion amount can be measured. A high correlation is obtained between the measured value and the heat generation characteristics.
That is, (1) The amount of oxygen diffusion can be obtained in a short time regardless of the size of the vent hole. (2) Even when the type of the breathable packaging material is different, there is a correlation between the measured value of the oxygen diffusion amount and the heat generation characteristics, and the comparison can be made as it is. (3) This facilitates the design and quality control of the heating bag. (4) The desired heat generation characteristics can be set with high accuracy by specifying the air diffusion material of the heat generation bag for the body, the heat generation bag for the pocket, and the heat generation bag for the shoes by the oxygen diffusion amount. Further, the heating bag of the present invention, (5) body heating bag, pocket heating bag, shoes heating bag,
Each is a heat generating bag having heat generating characteristics most suitable for each application. (6) Even when the type of air-permeable packaging material, the hole diameter, and the like are different, it has heat generation characteristics according to the purpose of the heat generation bag for the body, the heat generation bag for the pocket, and the heat generation bag for the shoes. (7) An excellent exothermic bag for shoes with temperature characteristics that could not be developed conventionally.

[Brief description of the drawings]

FIG. 1 is an example of a cross-sectional view of a diffuser.

FIG. 2 is a block diagram showing the principle of the oxygen diffusion amount measuring device of the present invention.

FIG. 3 is an example of an inner bag using a breathable packaging material having microporosity. (A) Plan view (b) AA 'line sectional view

FIG. 4 is an example of an inner bag using a gas-permeable packaging material partially having microporosity.

FIG. 5 is an example of an inner bag using a breathable packaging material in which needle holes are concentrated in the center.

FIG. 6 is an example of an inner bag with a back seal using a breathable packaging material in which a needle hole is connected to a central portion. (A) Plan view (b) BB 'line sectional view

FIG. 7 shows the relationship between the oxygen diffusion amount and the maximum temperature in Examples 1 to 9.

FIG. 8 shows the relationship between the oxygen diffusion amount and the rise time in Examples 1 to 9.

FIG. 9 shows the relationship between the oxygen diffusion amount and the duration in Examples 1 to 9.

FIG. 10 shows the relationship between the oxygen diffusion amount and the maximum temperature in Examples 10 to 13.

FIG. 11 shows the relationship between the oxygen diffusion amount and the rise time in Examples 10 to 13.

FIG. 12 shows the relationship between the oxygen diffusion amount and the duration in Examples 10 to 13.

FIG. 13 shows the relationship between the oxygen diffusion amount and the maximum temperature in Examples 14 to 21.

FIG. 14 shows the relationship between the oxygen diffusion amount and the rise time in Examples 14 to 21.

FIG. 15 shows the relationship between the oxygen diffusion amount and the duration in Examples 14 to 21.

FIG. 16 shows the relationship between the moisture permeability and the maximum temperature in Comparative Examples 1 to 8.

[Explanation of Signs] 1 Diffuser 2 Chamber 3 Lid 4 Air-permeable packaging material 5 Nitrogen gas supply pipe 6 Exhaust pipe 7 Partition barrier 8, 9 Frame 10, 11 Sheet packing 12 Measurement surface of air-permeable packaging material 13 Ring shape Seat packing 14 Bottom frame 15 Stud bolt 16 Nut 17 Pressure reducing valve 18 Nitrogen gas flow setting device 19 Oxygen concentration detector 20 Branch unit 21 Purge line 22 Switching valve 23 Gas chromatograph 24 Gas sampling unit 25 Gas suction unit 26 Inner bag 27 Heat generation composition Object 28 Sealing part 29 Non-breathable packaging material 30 Vent part (central concentrated needle hole) 31 Vent part (entire microporous surface) 32 Vent part (partially microporous) 33 Vent part (central concentrated continuous needle hole) 34 Back seal part

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayuki Fujisawa 5181 Tamura, Hiratsuka-shi, Kanagawa Japan Inside the Hiratsuka Research Laboratories, Inc. In-house (72) Inventor Satoshi Ochi 5181 Tamura, Hiratsuka-shi, Kanagawa Prefecture Japan Hiratsuka Research Laboratories

Claims (12)

[Claims] 1. Exposing one side of a gas-permeable packaging material to the atmosphere, scavenging a carrier gas containing no oxygen on the opposite surface, and measuring the oxygen gas concentration in the carrier gas after the gas scavenging. A method for measuring the amount of oxygen diffusion of a gas-permeable packaging material, comprising measuring gas permeability. 2. The method according to claim 1, wherein the carrier gas is nitrogen. 3. The method for measuring the amount of oxygen diffusion according to claim 1, wherein a pressure difference between the pressure of the air in contact with the air-permeable packaging material and the pressure of the carrier gas is 3 mmH ₂ O or less. 4. Exposing one side of the gas-permeable packaging material to the atmosphere and bringing the opposite surface into contact with a carrier gas containing no oxygen, oxygen gas in the atmosphere diffuses and transmits the gas-permeable packaging material to the carrier gas side. An apparatus for measuring the amount of oxygen diffusion of a gas-permeable packaging material, comprising: 5. The oxygen diffusion amount measuring device according to claim 4, wherein the carrier gas is nitrogen. 6. The oxygen diffusion amount measuring device according to claim 4, wherein the diffuser has at least one carrier gas supply pipe and at least one exhaust pipe. 7. An oxygen concentration detector in a diffuser chamber and / or via a diffuser exhaust pipe.
The oxygen diffusion amount measuring device according to 1. 8. The oxygen diffusion amount measuring device according to claim 4, wherein an exhaust pump is connected to the exhaust pipe. 9. Under a condition of 20 ° C. and a relative humidity of 65%, one side of the gas-permeable packaging material is exposed to the atmosphere, and a carrier gas containing no oxygen is applied to the other surface at 0% per unit area of the gas-permeable packaging material. The oxygen diffusion amount was 11 when measured by flowing the surface of the gas permeable packing material so as to scavenge it at a flow rate of 193 Nl / cm ² h.
A heat-generating composition that generates heat in contact with oxygen in the air is stored in a gas-permeable inner bag using a gas-permeable packaging material equivalent to 00 ± 220 Nl / m ² 24 h on one side, and a non-gas-permeable outer bag. A heat-producing bag for a body, characterized by being sealed in a bag. 10. Under a condition of 20 ° C. and a relative humidity of 65%, one side of the gas-permeable packaging material is exposed to the atmosphere, and a carrier gas containing no oxygen is applied to the other surface at a rate of 0% per unit area of the gas-permeable packaging material. The oxygen diffusion amount was 1 when measured by flowing the surface of the air-permeable packaging material so as to scavenge it at a flow rate of 193 Nl / cm ² h.
A heat-generating composition that generates heat in contact with oxygen in the air is contained in a gas-permeable inner bag using a gas-permeable packaging material equivalent to 600 ± 350 Nl / m ² 24 h on one side, and a non-gas-permeable outer bag. A heat generating bag for a pocket, characterized in that the heat generating bag is sealed in a pocket. 11. Under a condition of 20 ° C. and a relative humidity of 65%, one side of the gas-permeable packaging material is exposed to the atmosphere, and a carrier gas containing no oxygen is added to the other surface at a rate of 0% per unit area of the gas-permeable packaging material. The oxygen diffusion amount was 5 when measured by flowing the surface of the air-permeable packaging material so as to scavenge it at a flow rate of 193 Nl / cm ² h.
A heat-generating composition that generates heat in contact with oxygen in the air is stored in a gas-permeable inner bag using a gas-permeable packaging material corresponding to 500 ± 1100 Nl / m ² 24 h on one side, and a non-gas-permeable outer bag. A heating bag for shoes, characterized by being sealed in a bag. 12. The heating bag according to claim 9, wherein the carrier gas is nitrogen.