JPWO2018131719A1 - Total heat exchange element sheet and method for producing total heat exchange element sheet - Google Patents

Abstract

Provided are a total heat exchange element sheet and a method for producing a total heat exchange element sheet, which have high moisture permeability as well as the ability to block ventilation and can suppress odor migration of a water-soluble odor substance. [MEANS FOR SOLVING PROBLEMS] Gelatin 3 that suppresses the odor transfer of a water-soluble odor substance and a bisvinylsulfone compound that is added to gelatin 3 and stabilizes its polymer structure are formed into a film-like substrate 2 having moisture permeability. In addition to lithium chloride, lithium chloride that improves hygroscopicity is supported.

Description

  The present invention relates to a sheet for a total heat exchange element and a method for producing a sheet for a total heat exchange element, which have moisture permeability as well as the ability to block ventilation.

  Under the Building Standards Act (Amendment of the 2003 Law), it was obliged to install machines that provide 24-hour ventilation in all buildings with living rooms. However, in seasons where the temperature difference between indoor and outdoor is large, such as in summer and winter, indoor heat is released to the outside with ventilation, and there is a problem that loss of heat energy is large. In view of this, heat exchangers have been commercialized in which heat exchange is performed between the exhaust discharged to the outdoors by ventilation and the intake air taken in indoors to suppress heat energy loss.

  By the way, the water vapor present in the air contains thermal energy called latent heat. For this reason, at the time of heat exchange, highly efficient heat exchange can be performed by performing what is called total heat exchange which performs latent heat exchange which moves water vapor with sensible heat exchange by heat transfer by the temperature difference of air. It is also desirable to perform latent heat exchange with water vapor from the viewpoint of preventing indoor overdrying.

  In general, the total heat exchange element of the total heat exchanger has a ventilation layer for ventilation and an air supply layer for supplying air alternately arranged as shown in FIG. 4, and a partition for constituting each layer. A sheet for a total heat exchange element is used as the plate. Since this total heat exchange element sheet performs total heat exchange as described above, it is necessary to satisfy both the performance of blocking ventilation and supply of air and moisture permeability for latent heat exchange. Thus, various inventions related to the total heat exchange element sheet have been proposed so far.

For example, International Publication No. WO02 / 099193 proposes a total heat exchange element paper composed of paper containing natural pulp that has been loosened by hitting fibers so that the freeness is 150 ml or less ( Patent Document 1). In addition, International Publication No. 2014/014099 discloses a multilayer structure including at least one non-woven fabric layer made of fine cellulose fibers and having a density of 0.10 g / cm ³ or more and 0.90 g / cm ³ or less. A heat exchanger sheet has been proposed (Patent Document 2). The inventions described in Patent Document 1 and Patent Document 2 have a function of blocking ventilation by making the gaps and holes dense while ensuring moisture permeability by the gaps and holes formed between the fibers. It is a thing.

  JP 2008-14623 A discloses a hydrophilic polymer in which a porous sheet containing hydrophilic fibers is coated with an aqueous solution containing a hydrophilic polymer to close the pores of the porous sheet. A total heat exchanger sheet made of a processed sheet has been proposed (Patent Document 3). In Japanese Patent Laid-Open No. 53-16950, a fibrous material mainly composed of rock wool or glass fiber and a slurry-like aqueous solution in which a binder is dispersed in a large amount of water are used to make a paper using a papermaking machine. A total heat exchanger as a leaf-like material has been proposed (Patent Document 4). Furthermore, Japanese Patent No. 4736718 proposes a base paper for a total heat exchanger element in which calcium chloride is added to a base paper and a polymer resin is applied or impregnated (Patent Document 5). Japanese Patent No. 3791726 discloses a total heat exchanger sheet comprising papermaking fibers, microfibrillated cellulose and moisture-releasing powder as a main component, and a moisture-absorbing / releasing coating layer such as silica gel or activated clay. Has been proposed (Patent Document 6). Further, JP-A-2015-59286 proposes a total heat exchange element paper having a base sheet made of natural pulp and a coating layer in which the gap of the base sheet is filled with calcium carbonate or the like. (Patent Document 7).

  The inventions described in Patent Document 3 to Patent Document 7 described above are moisture permeable by containing hydrophilic or moisture permeable fibers as a main component, or containing calcium chloride or the like having high hygroscopicity with respect to the base paper. It is provided with a function of blocking air flow by closing gaps or holes between the fibers with a polymer material or the like while securing the above.

  Furthermore, in Japanese Patent Application Laid-Open No. 2007-64508, the cellophane was found to have a high moisture permeability and a performance capable of blocking the ventilation, and was used as a sheet for a total heat exchange element. A heat exchanger sheet has been proposed (Patent Document 8).

International Publication No. 02/099193 International Publication No. 2014/014099 JP 2008-14623 A JP-A-53-16950 Japanese Patent No. 4736718 Japanese Patent No. 3791726 Japanese Patent Laying-Open No. 2015-59286 JP 2007-64508 A

  However, as in the inventions described in Patent Document 1 and Patent Document 2, those having gaps or holes between fibers have gaps or holes as in the inventions described in Patent Documents 3 to 8. There is a problem that the performance of blocking the ventilation is lower than that filled with a hygroscopic substance.

  In addition, the conventional sheet for total heat exchange element described in Patent Document 1 to Patent Document 8 exchanges water-soluble odorous substances such as ammonia together with water vapor as described in Example 1 described later. Therefore, there is a problem that malodorous gas and toxic gas containing a water-soluble odorous substance as a component cannot be discharged outside the room by ventilation.

  Furthermore, as in the inventions described in Patent Documents 3 to 7, when forming a hygroscopic substance coating layer on a base paper, ventilation is required unless the thickness of the hygroscopic substance is uniform. There is a problem that unevenness is generated in the performance to block or moisture permeability.

  The present invention has been made in order to solve these problems, has a high moisture permeability as well as the ability to block ventilation, and can suppress the odor transfer of a water-soluble odor substance. It aims at providing the sheet | seat for exchange elements, and the sheet | seat manufacturing method for total heat exchange elements.

  As a result of intensive research to solve the above-mentioned problems, the present inventor has excellent performance for inhibiting the odor transfer of water-soluble odorous substances while gelatin has a high moisture permeability performance while blocking ventilation. I found out. In addition, it has been found that moisture permeability is improved by supporting lithium chloride that improves hygroscopicity, but on the other hand, there is a problem that the ventilation performance and the performance of water-soluble odorous substances such as ammonia are reduced. . Based on these findings, the following inventions useful for practical use have been completed.

  That is, the sheet for a total heat exchange element according to the present invention has a water-soluble odor in order to achieve both the performance of blocking ventilation and the moisture permeability, and to solve the problem of suppressing the odor transfer of the water-soluble odor substance. Gelatin that suppresses the odor transfer of substances and a bisvinylsulfone compound that is added to this gelatin and stabilizes its polymer structure are contained in a film-like substrate having moisture permeability, and has a hygroscopic property. Improved lithium chloride is supported.

In one embodiment of the present invention, in order to solve the problem of specifying a suitable content of the bisvinylsulfone compound and a suitable loading amount of the lithium chloride, the bisvinylsulfone compound is a dry weight of the gelatin. The lithium chloride may be supported at 5 to 10 g / m ² while being contained at 0.5 to 5% by weight.

  Furthermore, as one aspect of the present invention, in order to solve the problem of coating gelatin with a uniform thickness on a base material, methylcellulose as a thickener is 0.1 to 0. It is preferably contained in a weight ratio of 3 times.

  The sheet manufacturing method for a total heat exchange element according to the present invention adds a thickener for increasing the viscosity of the aqueous solution to the aqueous gelatin solution in order to solve the problem of uniformly applying the aqueous gelatin solution to the substrate. And a step of allowing the aqueous solution to be contained in a moisture-permeable film-like substrate and drying.

  Further, as one aspect of the present invention, in order to solve the problems that the air blocking performance and the blocking performance of water-soluble odorous substances such as ammonia are lowered by supporting lithium chloride, Add a thickener to increase viscosity and a cross-linking agent to stabilize the polymer structure of gelatin, add the aqueous solution to the substrate and dry it, then dipping the aqueous solution of the hygroscopic material to improve the hygroscopicity Or it is preferable to dry after spraying and to carry the hygroscopic material.

Furthermore, as one aspect of the present invention, in order to solve the problem of more suitably exhibiting the performance of each material of the thickener, the cross-linking material, and the hygroscopic material added to the gelatin content, To an aqueous solution containing 3 to 5% by weight, 0.5 to 1% by weight of methylcellulose and 0.5 to 5% by weight of a bisvinylsulfone compound based on the dry weight of the gelatin are added. It is preferable that the lithium chloride aqueous solution is dipped or sprayed and then dried to carry 5 to 10 g / m ² of lithium chloride after being contained in the substrate and dried.

  ADVANTAGE OF THE INVENTION According to this invention, it has high moisture permeability with the performance which interrupts | blocks ventilation | gas_flowing, and can suppress the odor transfer of a water-soluble odor substance.

It is sectional drawing which shows one Embodiment of the sheet | seat for total heat exchange elements which concerns on this invention. It is a flowchart figure which shows one Embodiment of the sheet | seat manufacturing method for total heat exchange elements which concerns on this invention. It is a schematic diagram showing a moisture permeation mechanism of (a) molecular diffusion mechanism and (b) a moisture permeation mechanism of dissolution and diffusion mechanism. It is a schematic diagram which shows the total heat exchange element in this embodiment. It is a schematic diagram which shows the structure of each layer in the total heat exchange element in other embodiment, and the direction of the airflow in each layer. It is a schematic diagram which shows the moisture permeable cup used for the moisture permeability experiment in the present Example 1. FIG. It is a schematic diagram which shows the experimental apparatus used for the odor transfer rate measurement experiment in the present Example 1. FIG. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of the polyolefin-type film in the odor transfer experiment of the present Example 1. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of the polypropylene nonwoven fabric in the odor transfer experiment of the present Example 1. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of the moisture-permeable waterproof sheet for construction in the odor transfer experiment of the first embodiment. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of Kent paper in the odor transfer experiment of the present Example 1. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of a cellulose membrane in the odor transfer experiment of the present Example 1. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of tracing paper in the odor transfer experiment of the present Example 1. It is a graph which shows the relationship between the water vapor pressure regarding a polyolefin-type film and a cellulose membrane, and an odor transfer rate in the odor transfer experiment of the present Example 1. 4 is a graph showing moisture permeability of a half paper, a cellulose film, a gelatin film, an agar film, a salt-carrying gelatin film, and a salt-carrying agar film in a moisture permeability experiment of Example 2. It is a graph which shows the relationship between the water vapor pressure and an odor transfer rate regarding a gelatin film, a salt carrying gelatin film, an agar film, and a cellulose film in the odor transfer experiment of the present Example 2. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of a cellulose membrane in the odor transfer experiment of the present Example 2. It is a graph which shows the voltage value of the ammonia sensor with respect to the time passage of a gelatin film | membrane in the odor transfer experiment of the present Example 2. It is a graph which shows the water vapor transmission rate of the half paper, the cellulose film | membrane, the gelatin film | membrane, and the agar film | membrane measured in the present Example 2. In this example 3 is a schematic diagram showing an experimental apparatus used in CO ₂ transfer rate measurement experiment. It is a schematic diagram which shows the experimental apparatus used for the odor transfer rate measurement experiment in the present Example 4. It is a figure which shows the time change of the ammonia concentration measured by the ammonia sensor at the time of using the viscose coated paper which is a conventional product for the moisture-permeable film of the experimental apparatus of FIG. It is a figure which shows the time change of the ammonia concentration measured by the ammonia sensor at the time of using the sheet | seat for total heat exchange elements which concerns on this invention in the moisture-permeable film of the experimental apparatus of FIG.

  Hereinafter, an embodiment of a total heat exchange element sheet and a total heat exchange element sheet manufacturing method according to the present invention will be described with reference to the drawings.

  As shown in FIG. 1, the total heat exchange element sheet 1 of the present embodiment mainly includes a film-like base material 2 having moisture permeability, and odor transfer of a water-soluble odor substance contained in the base material 2. Gelatin 3 or agar 4 that suppresses moisture, and various additives 5, 6, 7, etc. that improve moisture permeability and the like. Each configuration will be described below.

  The base material 2 is a thin film-like material provided with fine gaps between fibers, and has a so-called moisture permeability that allows moisture such as water vapor to pass through the gaps. This base material 2 is comprised with paper, a nonwoven fabric, a porous sheet, etc., and the paper of thickness about 62 micrometers is used in this embodiment.

  The gelatin 3 or the agar 4 is for blocking the aeration by closing the gap existing in the base material 2 and for suppressing the odor transfer of the water-soluble odor substance while improving the moisture permeability as compared with the base material 2. .

  Here, the thin film permeation mechanism of water vapor includes a molecular diffusion mechanism and a dissolution diffusion mechanism. As shown in FIG. 3A, the molecular diffusion mechanism is a phenomenon in which water vapor diffuses with a concentration gradient in voids of a thin film made of a fiber material, a porous material, or the like. On the other hand, as shown in FIG. 3 (b), the dissolution / diffusion mechanism is such that water vapor molecules that have reached the material surface are dissolved inside the material, and the concentration gradient becomes a driving force to diffuse inside the material, and from the opposite surface. It is a phenomenon to be released.

  In the present invention, moisture permeability is secured by utilizing the dissolution and diffusion mechanism of gelatin 3 or agar 4.

  Here, gelatin 3 is mainly composed of proteins extracted from animal skin, bones, tendons, etc., and is dissolved in water in high-temperature water and solidified as a gel by cooling. have.

  The agar 4 is a dietary fiber obtained by freezing and drying mucus of red algae such as agus. In high-temperature water, it has the property of dissolving in water and solidifying by cooling.

  In this embodiment, as shown in FIG. 2, the base material 2 is impregnated with an aqueous solution obtained by dissolving gelatin 3 or agar 4 in water (S1 to S3), and finally dried (S4 and S6). The gelatin 3 or the agar 4 is contained in the minute gaps of the base material 2.

At this time, as described in Example 3 to be described later, in order to effectively exhibit the performance of blocking the ventilation and the high moisture permeability and suppressing the odor transfer of the water-soluble odor substance, It is preferable to contain about 2 to 6 g / m ² when the substrate 2 is impregnated with a gelatin aqueous solution of about 3 to 5% by weight and dried, and then completely dried.

  Next, as an additive in this embodiment, a thickener 5 that increases the viscosity of an aqueous gelatin solution or an agar solution, a cross-linking material 6 that stabilizes the polymer structure of gelatin 3 or an agar 4, and a hygroscopic property. And a hygroscopic material 7 to be improved.

  The thickening material 5 is for adjusting the viscosity of the gelatin aqueous solution or the agar aqueous solution impregnated in the base material 2, and particularly for preventing dripping or the like when the base material 2 is impregnated with each of the aqueous solutions. It is. One of the preferred thickeners 5 in the present embodiment is methylcellulose, and an appropriate amount is added to the gelatin aqueous solution or the agar aqueous solution as shown in FIG. 2 (S2).

  As will be described later in Example 3, the methylcellulose is added in an amount of about 0.5 to 1% by weight based on the gelatin aqueous solution when the gelatin concentration is about 3 to 5% by weight. Is preferred.

  Then, the aqueous solution to which methylcellulose is added is coated on one or both sides of the substrate 2 using a roll coater or spray used in a papermaking process or the like (S3). At this time, since the viscosity of the gelatin aqueous solution or the agar aqueous solution is increased by the addition of methylcellulose, the dripping before the drying is prevented, and the gelatin aqueous solution or the agar aqueous solution is applied to the substrate 2 with an equal thickness. It is possible to work. Methyl cellulose is preferably contained in a weight ratio of about 0.1 to 0.3 times the weight of gelatin 3 in the completed sheet 1 for total heat exchange elements.

  In addition, the thickener 5 is not limited to methylcellulose, for example, carboxymethylcellulose such as methylcellulose, cellulose derivatives such as hydroxyethylcellulose, pectin, carrageenan, guar gum, locust bean gum, tamarind gum, xanthan gum, curdlan, etc. Can be used.

Next, the cross-linking material 6 will be described. The cross-linking material 6 stabilizes the polymer structure of the gelatin 3 or the agar 4, thereby suppressing the destruction of a part of the polymer network structure in the gelatin 3 or the agar 4 by the moisture absorbent 7 described later. It fulfills the function of blocking the ventilation by gelatin 3 or agar 4 and maintaining the performance of blocking water-soluble odorous substances such as ammonia. For example, as shown in the following chemical formula 1, when a vinyl sulfone group (CH2 = CH-SO2-) is added as the cross-linking material 6, the vinyl sulfone group is a hydroxyl group (-OH) or an amine group (-NH2) of gelatin 3. ) To form a crosslinked structure of gelatin 3 and stabilize the polymer structure. Moreover, in this reaction, since gas etc. do not generate | occur | produce, it is easy to use as the crosslinking material 6. Therefore, the cross-linking material 6 is preferably one that reacts with amine groups or hydroxyl groups in gelatin 3 or agar 4, and is preferably a vinyl sulfone group or vinyl carboxylic acid.
[Chemical Formula 1]

［構造式２］

［構造式３］

An example of the cross-linking material 6 in the present embodiment is a bisvinylsulfone compound, which is added to a gelatin aqueous solution or an agar aqueous solution together with methylcellulose as shown in FIG. 2 (S2). Examples of the bisvinylsulfone compound include N, N′-bis (vinylsulfonylacetyl) trimethylenediamine represented by the following structural formula 1, and N, N′-bis (vinylsulfonylacetyl) ethylenediamine represented by the following structural formula2. 1,3-bis (vinylsulfonyl) -2-propanol shown in the following structural formula 3 can be used.
[Structural Formula 1]

[Structural Formula 2]

[Structural Formula 3]

As will be described in Example 3 described later, the bisvinylsulfone compound is about 0.5 to 5% by weight based on the dry weight of the gelatin when the lithium chloride is supported at 5 to 10 g / m ^2. It is preferable to add them.

  In addition, the crosslinking material 6 is not limited to a bisvinyl sulfone compound, For example, what has carbonyl groups, such as formaldehyde and glutaraldehyde which bridge | crosslink with an amine group, can be utilized. Furthermore, amine-reactive cross-linking materials such as isothiocyanate, isocyanate, acyl azide, NHS ester, sulfonyl chloride, glyoxal, epoxide, oxirane, carbonate, aryl halide, imide ester, carbodiimide can also be used.

  Next, the hygroscopic material 7 will be described. The hygroscopic material 7 is for improving the moisture absorption performance of the base material 2 containing gelatin 3 or agar 4 and improving moisture permeability. An example of the hygroscopic material 7 in the present embodiment is lithium chloride. As shown in FIG. 2, the base material 2 is impregnated with an aqueous gelatin solution or an agar aqueous solution to which methylcellulose and a bisvinylsulfone compound are added and dried. After that, it is supported by dipping in an aqueous solution of lithium chloride or spraying an aqueous solution of lithium chloride on its surface (S5).

As described in Example 3 below, lithium chloride is added to a gelatin aqueous solution having a gelatin concentration of about 3 to 5% by weight at about 0.5 to 5% by weight based on the dry weight of gelatin. In the case where the substrate 2 is impregnated and dried, it is dipped in a lithium chloride aqueous solution or dried after spraying a lithium chloride aqueous solution on the surface thereof, and supported at about 5 to 10 g / m ² . It is preferable to make it. As a result, lithium chloride is supported at a weight ratio of about 0.8 to 5 times the gelatin 3 in the finished sheet 1 for the total heat exchange element.

  The hygroscopic material 7 is not limited to lithium chloride, and can be appropriately selected from, for example, chlorides such as calcium chloride, sodium chloride, magnesium chloride, potassium chloride, and lithium bromide.

  Finally, as shown in FIG. 2, the sheet for total heat exchange element 1 is completed by dipping into an aqueous solution of lithium chloride or spraying an aqueous solution of lithium chloride on the surface and then drying (S6).

  The total heat exchange element sheet 1 is used for the total heat exchange element 8. Therefore, the configuration of the total heat exchange element 8 will be briefly described below.

  For example, as shown in FIG. 4, the total heat exchange element 8 includes a partition plate 81 that partitions two types of airflows having different temperatures and / or humidity, and a spacing plate 82 provided between the partition plates 81. These plate members form a ventilation layer 83 for ventilation and an air supply layer 84 for supplying air.

  The partition plate 81 is configured by the total heat exchange element sheet 1 according to the present invention. The partition plate 81 partitions the ventilation layer 83 and the air supply layer 84 to block ventilation between the layers, and exchange sensible heat and latent heat. Is possible.

  The spacing plate 82 is configured by the total heat exchange element sheet 1 similarly to the partition plate 81, and supports the partition plates 81 at intervals that allow ventilation. The spacing plate 82 is formed in a wave shape having the same wave height as the spacing of the partition plate 81, and the top portion and the valley portion are bonded and fixed to the partition plate 81.

  The spacing plate 82 is also for determining the direction of the airflow. That is, the space | interval board 82 can be made to flow the airflow of each layer in the direction along the wave-like top part or trough part. Therefore, the interval plate 82 is arranged so as to be alternately rotated by 90 degrees, and is configured such that the direction of the airflow is perpendicular to the ventilation layer 83 and the air supply layer 84.

  The shape of the spacing plate 82 is not limited to the wave shape as long as the function can be achieved, and other shapes may be appropriately selected. Moreover, the direction of the airflow in the ventilation layer 83 and the air supply layer 84 is not limited to the orthogonal direction, and may be appropriately selected from arrangements having various facing relationships as shown in FIG.

  Next, the operation of each component in the total heat exchange element sheet 1 of the present embodiment will be described together with the operation of the total heat exchange element 8 using the total heat exchange element sheet 1.

  In the total heat exchange element 8, when the temperature of the air flowing through the ventilation layer 83 and the supply layer 84 is different, the heat exchange of the sensible heat in each layer 83, 84 via the total heat exchange element sheet 1 that is the partition plate 81. Is done. Since the total heat exchange element sheet 1 is formed in a thin film shape, sensible heat is easily transmitted between the layers 83 and 84.

  Therefore, when the temperature of the indoor air is warmed higher than the temperature of the outdoor air by heating in winter, etc., the air that is exhausted from the indoor to the outdoor to the air supplied from the outdoor to the indoor The sensible heat is transmitted. Therefore, air that is warmer than outdoor air is supplied indoors, and loss of thermal energy required for heating is suppressed.

  When the temperature of the indoor air is cooled to a low temperature compared to the temperature of the outdoor air by cooling in summer, etc., it appears in the air exhausted from the indoor to the outdoor from the air supplied from the outdoor to the indoor. Heat is taken away. Therefore, air cooled from outdoor air is supplied indoors, and loss of heat energy required for cooling is suppressed.

  Next, when the humidity of the air flowing through the ventilation layer 83 and the air supply layer 84 is different, heat exchange of latent heat is performed by the dissolution / diffusion mechanism via the partition plate 81 made of the total heat exchange element sheet 1.

  That is, gelatin 3 or agar 4 dissolves water vapor from the air-side surface with high humidity and releases water vapor from the air-side surface with low humidity. The moisture permeability of the total heat exchange element sheet 1 at this time is higher than the moisture permeability of the substrate 2 itself. Therefore, in the total heat exchange element sheet 1 of the present embodiment, heat exchange of latent heat is performed efficiently.

The hygroscopic material 7 further improves the moisture permeability of the gelatin 3 or the agar 4. For example, when lithium chloride is used, as will be described later in Example 3, about 100 to about 110 g / (m ² · m ² ) which is equal to or higher than that of a conventional cellulose film (viscose coated paper). h) moisture permeability.

  Moreover, the gelatin 3 or the agar 4 can suppress the odor transfer of a water-soluble odor substance such as ammonia dissolved in water vapor. For example, in the case of the total heat exchange element sheet 1 containing gelatin 3, the odor transfer rate η of ammonia is set to 0. 0 at a temperature of 20 ° C and a humidity of 20% RH as described in Example 2 described later. The odor transfer rate η of ammonia can be suppressed to 0.49 under conditions of a temperature of 40 ° C. and a humidity of 90% RH, which are high temperature and high humidity conditions.

  Similarly, in the case of the total heat exchange element sheet 1 having the agar 4, the odor transfer rate η of ammonia can be suppressed to 0.1 under the conditions of a temperature of 20 ° C. and a humidity of 20% RH. Further, the odor transfer rate η of ammonia can be suppressed to 0.67 even under high temperature and high humidity conditions of a temperature of 40 ° C. and a humidity of 90% RH.

The cross-linking material 6 stabilizes the polymer structure of gelatin 3 or agar 4. Thereby, the crosslinking material 6 suppresses the destruction of the polymer structure of the gelatin 3 or the agar 4 by the hygroscopic material 7, and blocks the aeration by the gelatin 3 or the agar 4 and the performance of blocking water-soluble odor substances such as ammonia. Can be maintained. When a bisvinylsulfone compound is used, as shown in Example 3 described later, it has a CO ₂ migration rate of about 9%, which is the same as or higher than that of a conventional cellulose membrane (viscose coated paper). And the odor transfer of ammonia can be blocked almost completely.

According to the total heat exchange element sheet 1 and the total heat exchange element sheet manufacturing method of the present embodiment as described above, the following effects can be obtained.
1. By containing gelatin 3 or agar 4 in the gap between the base materials 2, it is possible to suppress the odor transfer of the water-soluble odor substance while having moisture permeability by the dissolution and diffusion mechanism by the gelatin 3 or the agar 4.
2. Addition of a bisvinylsulfone compound as the cross-linking material 6 improves moisture permeation performance by supporting the hygroscopic material 7, performance of blocking air flow by gelatin 3 or agar 4, and blocking water-soluble odorous substances such as ammonia. The maintenance of the performance to be achieved can be achieved.
3. By adding the thickener 5, the thickness of the gelatin 3 or the agar 4 with respect to the substrate 2 can be made uniform.
4). The gelatin 3 or the agar 4 can suppress the odor transfer of the water-soluble odor substance under high temperature and high humidity conditions.
5). As a production method, a method used in an existing paper making process for producing paper such as a roll coater can be used, so that the introduction cost of the production line is low and continuous production can be performed.

"Performance evaluation of conventional products"
In Example 1, experiments were conducted on moisture permeability and odor transferability of water-soluble odorous substances with respect to a plurality of moisture permeable membranes having a molecular diffusion mechanism and a plurality of moisture permeable membranes having a dissolution and diffusion mechanism, respectively. .

  As shown in Table 1 below, the moisture permeable membrane having a molecular diffusion mechanism is a polyethylene nonwoven fabric having a film thickness of about 0.1 mm used for a moisture permeable waterproof sheet for construction, a membrane used as a sheet for a total heat exchange element. About 0.06 mm thick polyolefin film, about 0.2 mm thick polypropylene non-woven fabric used for paper diapers and masks, and about 0.3 mm thick Kent paper used for drawing paper were used.

On the other hand, a moisture permeable membrane having a dissolution / diffusion mechanism is a cellulose membrane (viscose processed paper) having a film thickness of about 0.06 mm used for a sheet for a total heat exchange element as a conventional product, and a film thickness used for a translucent paper. About 0.045 mm of tracing paper was used. The tracing paper is a tracing paper (model number: T-50N) having a grammage of 40 g / m ² sold by the National University Co-op Association.
[Table 1]

(1) About moisture permeability The moisture permeability of each said moisture-permeable film was measured, and each moisture permeability was examined. In this Example 1, the measurement of moisture permeability is based on JIS L 1099 A-1, and, as shown in FIG. 6, a moisture permeable cup containing calcium chloride and using each moisture permeable membrane as a lid, It was calculated by placing in a constant temperature and humidity chamber at a temperature of 40 ° C. and a humidity of 90% RH for 1 hour, measuring the amount of change in the mass of the calcium chloride before and after charging, and substituting the value into the following equation 1.
[Formula 1]
P = (m ₂ −m ₁ ) / A
Here, P is moisture permeability (g / (m ² · h)), (m ₂ -m ₁ ) is the amount of change in calcium chloride mass (g / h), and A is the moisture permeable area (m ² ). .

The results of calculating the moisture permeability P of each moisture permeable membrane are summarized in Table 2 below. In the moisture permeable membrane having a molecular diffusion mechanism, a polypropylene nonwoven fabric used for a polyolefin film or a mask used as a sheet for a total heat exchange element, and in the moisture permeable film having a dissolution diffusion mechanism, the sheet for a total heat exchange element. The moisture permeability of the cellulose membrane used was high.
[Table 2]

  From the above, the moisture-permeable performance was high in the moisture-permeable membrane polyolefin film and polypropylene nonwoven fabric having a molecular diffusion mechanism and the moisture-permeable cellulose membrane having a dissolution and diffusion mechanism.

(2) Odor transferability of ammonia (water-soluble odor substance) The odor transfer rate of each moisture permeable membrane was measured, and the performance of blocking ammonia (water-soluble odor substance) was examined. As shown in FIG. 7, the experiment used an experimental apparatus in which a moisture permeable cup used for measuring moisture permeability was installed in a small chamber, and ammonia sensors were arranged inside and outside the moisture permeable cup.

Further, as experimental conditions, about 50 ppm of ammonia (NH ₃ ) was injected into the chamber at a temperature of 20 ° C. and a humidity of 20% RH, and the ammonia inside the moisture permeable cup and outside the moisture permeable cup for 10 minutes after the injection. The concentration was measured and calculated by substituting the measured value into Equation 2 below.
[Formula 2]
η≡C ₂ / C ₁
Here, η is the odor transfer rate (−), C ₁ is the average concentration (ppm) in the chamber 10 minutes after gas injection, and C ₂ is the concentration (ppm) in the moisture permeable cup 10 minutes after gas injection. .

  8 to 13 show the results measured by each ammonia sensor after ammonia injection. In each figure, the horizontal axis shows the elapsed time after ammonia injection, and the vertical axis shows the value of the ammonia sensor. It shows that ammonia concentration is so deep that the value of a vertical axis | shaft is large.

  First, as shown in FIG. 8, the ammonia concentration outside the moisture permeable cup increased rapidly after the ammonia injection, and became a substantially constant value within one minute. This indicates that the ammonia injected into the chamber diffused in the chamber and became an even concentration within 1 minute. This tendency is the same in other experiments as shown in FIGS.

  On the other hand, the ammonia concentration in the moisture permeable cup varied in concentration depending on the type of material used for the lid of the moisture permeable cup. Hereinafter, it demonstrates, referring each drawing.

  First, in the case where a polyolefin film or a polypropylene non-woven fabric, which is a moisture permeable membrane having a molecular diffusion mechanism, is used for the lid of the moisture permeable cup, the ammonia in the moisture permeable cup is injected after ammonia injection, as shown in FIGS. The concentration rose rapidly and became almost constant within 1 minute. Moreover, the ammonia concentration in the moisture permeable cup became a value close to the ammonia concentration outside the moisture permeable cup. From these facts, it was found that in the polyolefin film and the polypropylene nonwoven fabric, ammonia is easily transferred and there is almost no ability to block the odor transfer of ammonia.

  Next, in the case where a polyethylene nonwoven fabric or Kent paper, which is a moisture permeable membrane having a molecular diffusion mechanism, is used for the lid of the moisture permeable cup, as shown in FIGS. 10 and 11, the ammonia concentration in the moisture permeable cup after ammonia injection is shown. The ascending speed is moderate as compared with the polyolefin-based film shown in FIGS. However, since it gradually approaches the ammonia concentration outside the moisture permeable cup with the passage of time, it was found that the polyethylene nonwoven fabric and the Kent paper have a very low ability to block the odor transfer of ammonia, like the polyolefin-based film.

  Next, when a cellulose membrane or a tracing paper, which is a moisture permeable membrane having a dissolution / diffusion mechanism, is used for the lid of the moisture permeable cup, as shown in FIGS. 12 and 13, the change in the ammonia concentration in the moisture permeable cup is changed. Was very gradual or not changed at all. In other words, it was found that the cellulose membrane and tracing paper have very high performance for blocking the odor transfer of ammonia.

Here, the results of calculating the odor transfer rate η of each material are summarized in Table 3 below. As shown in Table 3, polyethylene nonwoven fabric, polyolefin film, polypropylene nonwoven fabric and Kent paper, which are moisture permeable membranes having a molecular diffusion mechanism, had a relatively high odor transfer rate of 0.37 or more. On the other hand, it was 0.05 for the cellulose membrane, which is a moisture permeable membrane having a dissolution and diffusion mechanism, less than the detection limit for the tracing paper, and a value lower by one digit or more than each moisture permeable membrane having the molecular diffusion mechanism.
[Table 3]

  From the above, it was shown that the moisture-permeable membrane having a dissolution / diffusion mechanism is high in the performance of suppressing the odor transfer of ammonia under the experimental conditions of a temperature of 20 ° C. and a humidity of 20% RH.

(3) Odor transferability with respect to water vapor pressure and odor transfer with respect to the type of gas By changing the water vapor pressure in the chamber, a polyolefin film that is a moisture permeable membrane having a molecular diffusion mechanism and a moisture permeable membrane having a dissolution diffusion mechanism The odor transfer rate η of a certain cellulose membrane was measured, and the odor transfer property with respect to the water vapor pressure was examined. In addition, ammonia, which is a water-soluble odor substance, and toluene, which is sparingly soluble in water, were injected as gases, and the odor transferability with respect to the type of gas was examined.

  As in (2) of the first embodiment, the experiment for ammonia was performed using an experimental apparatus including a moisture permeable cup and an ammonia sensor provided inside and outside the moisture permeable cup as shown in FIG. It was. In the experiment for toluene, the same moisture permeable cup and the same chamber were used, and an experimental apparatus provided with a volatile organic compound (VOC) sensor inside and outside the moisture permeable cup instead of the ammonia sensor was used.

  The experimental conditions were that the water vapor pressure in the chamber was about 1000 Pa, about 4400 Pa, and about 6500 Pa, and the odor transfer rate η in each state was measured.

  The measurement results are shown in FIG. In the case of a polyolefin film that is a moisture permeable membrane having a molecular diffusion mechanism, the odor transfer rate η showed a value close to 1 regardless of the water vapor pressure or the type of gas. Therefore, it was found that the polyolefin film or the like has a very low ability to block odor transfer in both ammonia, which is a water-soluble odor substance, and toluene which is hardly soluble in water.

  On the other hand, in the case of a cellulose membrane that is a moisture permeable membrane having a dissolution and diffusion mechanism, toluene, which is hardly soluble in water, has a high performance of blocking odor transfer because the odor transfer rate η is 0.1 or less regardless of the water vapor pressure. It was. However, in the case of water-soluble ammonia, as the water vapor pressure increased, the value of the odor transfer rate η suddenly increased, and the performance of blocking the odor transfer significantly decreased.

(4) Summary of conventional products As described above, among the conventional products, the cellulose membrane, which is a moisture permeable membrane having a dissolution and diffusion mechanism, showed high performance in both the moisture permeable and water-soluble odor substances. . However, even with this cellulose membrane, it was found that the ability to block odor transfer of a water-soluble odor substance made of ammonia or the like under high temperature and high humidity conditions is low.

"Examination of sheet for total heat exchange element using gelatin and agar"
In this Example 2, based on the knowledge that the moisture permeable membrane having the dissolution / diffusion mechanism in Example 1 has a high barrier property against moisture permeability and water-soluble odorous substances, a new dissolution in which the base material contains gelatin and agar A moisture permeable membrane with a diffusion mechanism was developed. In addition, the new moisture-permeable membrane was tested for the ability to block ammonia, which is a water-soluble odor substance, under conditions of moisture permeability and high temperature and humidity.

(1) Preparation of sheet for total heat exchange element The moisture permeable membrane used in the experiment in Example 2 was a cellulose film having a film thickness of 60 μm, a half paper having a film thickness of 65 μm, and a gelatin contained in this half paper. Gelatin film with a thickness of 85 μm, agar film with a thickness of 90 μm containing agar in the half paper, a salt-supported gelatin film with a thickness of 85 μm in which lithium chloride as a hygroscopic material is supported on the gelatin film, and chloride on the agar film A salt-supported agar film having a thickness of 90 μm on which lithium is supported. The half paper used in the present Example 2 is Kuretake's half paper, “Kuretake Bokuki Half Paper (Part No .: LA17-2)”.

  Gelatin and agar were formed by impregnating a substrate with a gelatin aqueous solution or agar aqueous solution having a concentration of 1% by weight and drying it at room temperature. The gelatin used in this Example 2 is “Gelatin Leaf 300”, a plate gelatin manufactured by Yasu Chemical Co., Ltd. Moreover, the salt-carrying gelatin and the salt-carrying agar were carried by spraying the gelatin film and the agar film with about 5% by weight of lithium chloride aqueous solution on the surface by bottle spray and drying.

(2) About moisture permeability
The moisture permeability of each moisture permeable membrane was measured, and each moisture permeability was examined. The measurement of moisture permeability P was performed according to JIS L 1099 A-1 as in Example 1 (1). The temperature during measurement is 40 ° C. and the relative humidity is 90%.

  The measured results are shown in FIG. It was shown that the gelatin film and the agar film containing gelatin and agar have the same moisture permeability as the moisture permeability of the conventional cellulose film. Moreover, the salt-carrying gelatin membrane carrying lithium chloride and the salt-carrying agar membrane carrying lithium chloride showed higher moisture permeability than the cellulose membrane, and improved moisture permeability by about 10 to 20%.

(3) About the odor transferability of ammonia As in Example 1 (3), change the water vapor pressure in the chamber, measure the odor transfer rate η with respect to ammonia of each moisture permeable membrane, and examine the odor transferability of ammonia. went.

  FIG. 16 shows the results of measuring the odor transfer rate η with respect to each water vapor pressure in the chamber. As described in Example 1 (3), the cellulose membrane, which is a conventional product, has a high odor transfer rate η up to about 0.9 under the condition of a high water vapor pressure of about 6500 Pa, and has a performance of blocking the odor transfer of ammonia. Remarkably reduced.

  On the other hand, the odor transfer rate η of the gelatin film and the agar film increases as the water vapor pressure increases, as in the case of the odor transfer rate η of the cellulose film, so that the odor transfer blocking performance decreases. However, the decrease in the odor transfer blocking performance is always more gradual than the cellulose membrane. For example, under the condition of a high water vapor pressure of about 6500 Pa, the odor transfer rate η of the gelatin film is 0.49 and the odor transfer rate η of the agar film is 0.67. The value was lower than 9. In addition, the gelatin film showed about 0.1 even under high temperature and high humidity conditions with a water vapor pressure of about 4400 pa, which is higher than the summer outdoor air condition, and it was found that the performance of blocking the odor transfer of ammonia was extremely high. In addition, it was shown that the salt-carrying gelatin film supporting lithium chloride has a lower ammonia blocking performance than the non-supporting gelatin film.

  FIGS. 17 and 18 show changes in ammonia concentration in the moisture permeable cup when a cellulose membrane and a gelatin membrane are used as the lid of the moisture permeable cup under the condition where the water vapor pressure is about 6500 Pa.

  As shown in FIG. 17, in the case of the cellulose membrane, the ammonia concentration in the moisture permeable cup increased rapidly, and the odor transfer rate η reached a value of about 0.9 in about 2 minutes. On the other hand, as shown in FIG. 18, in the case of the gelatin film, the increase in ammonia concentration in the moisture permeable cup was gradual, and ammonia was hardly transferred in a short time of about 2 minutes.

  Therefore, it was found that the gelatin film has a higher performance of suppressing the odor transfer of water-soluble odor substances such as ammonia than the conventional cellulose film.

(4) Concentration of aqueous solution and moisture permeability when producing gelatin film and agar film The relationship between the concentration of aqueous solution and moisture permeability when producing gelatin film and agar film was examined. The base material used and tracing paper moisture permeability 103g / ^{m 2} · h, and a tracing paper moisture permeability 53g / ^{m 2} · h. The gelatin film was formed by infiltrating each tracing paper with a gelatin aqueous solution having a concentration of 0.5 wt%, 1 wt%, 5 wt%, and 10 wt%. The agar film was formed by infiltrating each tracing paper with an agar aqueous solution having a concentration of 0.5 wt%, 1 wt%, and 5 wt%.

The moisture permeability of each gelatin film and each agar film was measured, and each moisture permeability was examined. The measurement of moisture permeability P was performed according to JIS L 1099 A-1 as in Example 1 (1). The temperature during measurement is 40 ° C. and the relative humidity is 90%. The measured results are shown in Table 4 below.
[Table 4]

  As shown in Table 4, the moisture permeability of the tracing paper as the base material, the gelatin film and the agar film showed substantially the same value. From this, it was confirmed that the gelatin film and the agar film depend on the moisture permeability of the substrate.

  Therefore, it is considered that the aqueous solution concentration in producing the gelatin film and the agar film does not need to be increased more than necessary in consideration of a decrease in moisture permeability and an increase in raw material cost. Therefore, it is considered that the aqueous solution concentration is preferably about 1 to 5% by weight.

(5) About the moisture permeability of a base material Next, the relationship between the moisture permeability of a base material and the moisture permeability of a gelatin film and an agar film was examined. As shown in Table 4, the moisture permeability of the gelatin film and the agar film is high when the moisture permeability of the tracing paper as a base material is high, and the moisture permeability of the gelatin film and the agar film is low when the moisture permeability of the tracing paper is low. Also showed a low value. Similarly, as shown in FIG. 19, when semi-paper with high moisture permeability was used as the base material, the moisture permeability of the gelatin film and the agar film also showed a value that was comparable.

  Therefore, it was found that the moisture permeability of the gelatin film and the agar film depends on the moisture permeability of the base material, and a high moisture permeability performance comparable to that of the cellulose film can be obtained.

"Examination of additives"
As shown in Example 2 (2), the salt-carrying gelatin membrane carrying lithium chloride had higher moisture permeability than the gelatin membrane not carried, but as shown in the same (3), ammonia There was a problem that the blocking performance of the odor transfer of the deteriorated. Further, in the case of the gelatin film in which gelatin is contained in the paper as the base material in Example 2, there is a problem that it is difficult to uniformly contain the necessary amount in the base material because the viscosity of the gelatin aqueous solution is low. In Example 3, in order to solve these problems, studies were made on additives and the like.

(1) Thickening material First, a thickening material was examined in order to contain a gelatin aqueous solution in a uniform thickness in a base material. As a result, methylcellulose was selected as the thickening material, and further experiments were conducted with respect to the gelatin content and the addition amount of methylcellulose to be added, based on the moisture permeability and air blocking performance as evaluation criteria. The gelatin used in Example 3 is the same as that used in Example 2. Moreover, the base material used in the present Example 3 is “Shirai”, a high-quality paper (non-coated paper) of Nippon Paper Industries Co., Ltd., having a basis weight of 52.3 g / m ² and a paper thickness of 66 μm. In the actual measurement value, the paper thickness of the base material was about 62 μm.

  In Example 3, methylcellulose was added to an aqueous gelatin solution, which was coated on one side of a substrate with a roll coater and dried to form a gelatin film.

The loading amount of gelatin in each gelatin film, based on experimental results of Example 2 (4), as shown in Table 5 ^below, was ^{3g / m 2, 4g / m} 2, 5g / m 2. Further, the supported amount of methylcellulose, respectively 0.3 g ^/ m 2, was ^{0.5g / m 2, 1g / m} 2, was about 0.06 to 0.33 times the weight ratio of the gelatin supported amount.
[Table 5]

One of the most important performances that a total heat exchange element must have is to require less CO ₂ migration. Therefore, first, the CO ₂ migration rate was measured. As shown in FIG. 20, the measurement of the CO ₂ migration rate was performed with an apparatus having a container 1, a container 2 communicating with the container 1, and a constant temperature and humidity chamber containing the container 1 and the container 2. A CO ₂ cylinder is connected to the container 1 so that CO ₂ can be supplied into the container 1. Further, the container 1 and the container 2 are communicated with each other through a gelatin film, and CO ₂ supplied to the container 1 can be transferred to the container 2 through the gelatin film. A part of the container 2 is opened, and the CO ₂ transferred to the container 2 is filled in the constant temperature and humidity chamber.

Further, a CO ₂ sensor and a temperature / humidity sensor are arranged in the container 1 and the constant temperature and humidity chamber, respectively, connected to the data logger, respectively, and the CO ₂ concentration in the container 1 and the constant temperature and humidity chamber, Temporal changes in temperature and humidity in the container 1 and in the constant temperature and humidity chamber are recorded.

In Example 3, the CO ₂ migration rate was calculated using the following formula 3.
[Formula 3]
CO ₂ transfer rate = C _{60 min} −C _OA / (C ₀ −C _OA )
Here, _{C 0} is the initial concentration of CO ₂ in the container 1 _{(ppm), C 60min} the CO ₂ concentration after 60 minutes elapse in the container 1 _{(ppm), C OA} is CO ₂ concentration in the constant temperature and humidity chamber ( ppm).

As shown in Table 5, the CO ₂ migration rate of the paper that is the base material is 99% and does not have the ability to block the ventilation. On the other hand, each gelatin film supporting methylcellulose has a CO ₂ migration rate of 3 to 11%, and the cellulose membrane (viscose coated paper) of the conventional product has a CO ₂ migration rate of 15%. Even so, it was found that the ability to block high ventilation could be obtained. This is because the addition of methylcellulose to the gelatin aqueous solution increases the viscosity and prevents dripping, in addition to the performance of blocking the airflow of gelatin. It is considered that the performance of blocking the flow is improved.

  Next, the measurement of moisture permeability was performed according to JIS L 1099 A-1 as in Example 1 (1) and Example 2 (2). The temperature during the experiment was 25 ° C., and the humidity was about 90% RH.

Results of measurement of moisture permeability, moisture permeability of the paper is the substrate whereas a ^{88g / (m 2 · h)} , was reduced by about 20% and ^{65~73g / (m 2 · h)} . Moreover, it decreased about 30% with respect to the moisture permeability of 104 g / (m ² · h) of the cellulose membrane.

  From the above, it was found that by adding an appropriate amount of methylcellulose to the gelatin aqueous solution, the viscosity of the gelatin aqueous solution increases, and by preventing dripping at the time of coating on the substrate, the air blocking performance is improved. On the other hand, it was found that when methylcellulose was added to the gelatin aqueous solution, the moisture permeability was slightly lowered.

(2) Hygroscopic material As shown in Example 3 (1), when an appropriate amount of methylcellulose is added to the gelatin aqueous solution, the moisture permeability performance is slightly lowered, so that the moisture absorbent material that improves the moisture permeability performance is supported. Tried. In Example 3, 5 wt% of lithium chloride as a hygroscopic material is added to gelatin aqueous solution together with methylcellulose, and the aqueous solution is applied to the base paper to form a salt-carrying gelatin film supporting lithium chloride. did.

Then, was measured moisture permeability salts carrying gelatin film, the moisture permeability was almost same value and 104g / ^(m 2 · h) of 100g / ^(m 2 · h), and the cellulose membrane. Therefore, it was found that moisture permeability is improved by supporting lithium chloride even when methylcellulose is added to an aqueous gelatin solution.

However, when the CO ₂ migration rate of the salt-carrying gelatin membrane was measured, the CO ₂ migration rate was 88% compared to 12% for the cellulose membrane. In other words, it was found that the air blocking performance is significantly lowered by supporting lithium chloride.

  Moreover, as shown in Example 2 (3), it is known that the addition of lithium chloride reduces the effect of suppressing the odor transfer of ammonia.

  The reason why the performance of blocking the ventilation and the performance of blocking the odor transfer of ammonia is reduced is that lithium chloride destroys part of the polymer network structure in gelatin and gelatin contained in the gaps of the base material It is inferred that a microscopic defect occurred.

(3) Cross-linking material Therefore, in order to solve the problem of destruction of the macromolecular structure of gelatin by the hygroscopic material, a cross-linking material that stabilizes the macromolecular structure of gelatin is studied and used as a modifier for aqueous polymers. It has been found that bisvinylsulfone compounds are effective.

In addition, lithium chloride was considered to destroy part of the polymer structure in the process of applying an aqueous gelatin solution to a substrate and then drying it. Therefore, the process for preventing the polymer structure from being destroyed in the manufacturing method was considered as follows.
1) First, several percent of a bisvinylsulfone compound is added as a cross-linking material to a 3 to 5% aqueous gelatin solution and several percent of methylcellulose as a thickening agent is added to the aqueous gelatin solution as a thickener.
2) Next, it is uniformly coated on the surface of the substrate with a roll coater or spray, and is supported at about 2 to 6 g / m ² when completely dried.
3) Further, as a subsequent step, dipping into an aqueous lithium chloride solution or spraying and drying an aqueous lithium chloride solution is performed. At this time, the supported amount of lithium chloride is about 5 to 10 g / m ² when completely dry.

(4) Addition amount of bisvinylsulfone compound Next, suitable values for the addition amount of the bisvinylsulfone compound were examined. The bisvinylsulfone compound used in Example 3 is N, N′-bis (vinylsulfonylacetyl) trimethylenediamine represented by the above structural formula 1. In Example 3, as shown in Table 6 below, 5% by weight of the bisvinylsulfone compound was added to 0.5% by weight of methylcellulose in an aqueous solution containing about 3 to 5% by weight of gelatin. Added (No. 2-1), added by 3% by weight (No. 2-2), added by 0.5% by weight (No. 2-3), and added by 0.1% by weight The coated product (No. 2-4) was applied to the surface of the substrate and dried to carry 5 g / m ^{2 of} lithium chloride (LiCl).
[Table 6]

The moisture permeability and CO ₂ migration rate were measured for each cellulose membrane. As a result, as shown in Table 6, it was found that the smaller the amount of the bisvinylsulfone compound added, the higher the moisture permeability, but the higher the CO ₂ migration rate (lowering the ventilation blocking performance).

Therefore, the moisture permeability and the CO ₂ migration rate are summarized as shown in Table 7 below by comparison with the moisture permeability and the CO ₂ migration rate of a cellulose film (viscose coated paper) which is a conventional product.
[Table 7]

That is, when the addition amount of the bisvinylsulfone compound as the cross-linking material is 0.1% by weight with respect to the dry weight of gelatin, as shown in Table 7, the moisture permeability is 100 g / (m ² · h). Compared with the moisture permeability of 104 g / (m ² · h) of the cellulose membrane, the same performance was exhibited. On the other hand, the CO ₂ migration rate is 82%, which is significantly lower than 15% of the cellulose membrane, and it is considered that sufficient performance cannot be obtained as a sheet for a total heat exchange element.

Further, when the additive amount of the bis-vinyl sulfone compound is 0.5% by weight based on the dry weight of gelatin, moisture permeability, 85 g / moisture permeability of ^(m 2 · h) a is cellulose membrane 104g / ^{(m 2} · Although it is slightly inferior to h), it was an acceptable performance as a sheet for a total heat exchange element. In addition, the CO ₂ migration rate was 12%, which was equivalent to or better than 15% of the cellulose membrane.

Further, when the addition amount of the bisvinylsulfone compound is 3% by weight with respect to the dry weight of gelatin, the moisture permeability is 78 g / (m ² · h), and the moisture permeability of the cellulose membrane is 104 g / (m ² · h). Although it was inferior to the above, it was acceptable performance as a sheet for a total heat exchange element. Further, the CO ₂ migration rate was 3%, and extremely excellent performance was obtained as compared with 15% of the cellulose membrane.

Furthermore, when the addition amount of the bisvinylsulfone compound is 5% by weight with respect to the dry weight of gelatin, the moisture permeability is 67 g / (m ² · h), and the moisture permeability of the cellulose membrane is 104 g / (m ² · h). However, it was acceptable performance as a sheet for a total heat exchange element. Further, the CO ₂ migration rate was 1%, and extremely superior performance was obtained as compared with 15% of the cellulose membrane.

From the above, it was found that by adding about 0.5 to 5% by weight of the bisvinylsulfone compound with respect to the dry weight of gelatin, sufficient performance with respect to the CO ₂ migration rate can be obtained as a sheet for a total heat exchange element. .

Therefore, in order to obtain a moisture permeability equal to or higher than that of the conventional cellulose membrane, the supported amount of lithium chloride was increased to 8 to 10 g / m ^{2 as} shown in Table 8 below.
[Table 8]

◎：ビスコース塗工紙と比較して110%〜以上の性能
○：ビスコース塗工紙と比較して80〜100%の性能
△：ビスコース塗工紙と比較して60〜80%の性能
×：ビスコース塗工紙と比較して0〜60%の性能Table 9 below shows the moisture permeability, CO ₂ migration rate, and ammonia (NH ₃ ) migration rate when the supported amount of lithium chloride is increased to 8 to 10 g / m ² together with other moisture permeable membranes in Table 8. Show.
[Table 9]

◎: 110% or more performance compared to viscose coated paper ○: 80 to 100% performance compared to viscose coated paper △: 60-80% compared to viscose coated paper Performance x: 0-60% performance compared to viscose coated paper

As shown in Table 9, the paper substrate had a moisture permeability of 88 g / (m ² · h), which was sufficient as a performance as a sheet for a total heat exchange element. On the other hand, the CO ₂ migration rate was 99%, and the performance to block ventilation was insufficient.

In the case where only methylcellulose was added to gelatin, the moisture permeability was 67 g / (m ² · h), which was an acceptable range for performance as a sheet for a total heat exchange element. Further, the CO ₂ migration rate was 2%, and the performance of blocking aeration was very excellent. Furthermore, although the ammonia transfer rate is 0 in Table 9, it is a value that cannot be measured by the measuring instrument, and the odor transfer of ammonia can be blocked almost completely.

When methylcellulose was added to gelatin and lithium chloride was supported thereon, the moisture permeability was 100 g / (m ² · h), and the same performance as viscose-coated paper was obtained. On the other hand, the CO ₂ migration rate was reduced to 88%, and the performance of blocking the ventilation was insufficient.

When methylcellulose and a bisvinylsulfone compound were added to gelatin and lithium chloride was further supported, the moisture permeability was 108 g / (m ² · h), and the same or better performance as viscose coated paper was obtained. . Further, the CO ₂ migration rate was 9%, and the performance of blocking ventilation was superior to that of viscose coated paper. Furthermore, the transfer of ammonia odor was almost completely blocked.

(5) Summary As described above, in the sheet for a total heat exchange element in which gelatin is contained in the base material, by adding an additive, the air-blocking performance, moisture-permeable performance, and water-soluble odor substances such as ammonia It was found that the performance of blocking the odor transfer of can be improved.

  For example, when methylcellulose is added, the moisture permeability performance is slightly lowered, but the gelatin aqueous solution can be uniformly applied to the base material. Further, the ability to block ventilation and the presence of water-soluble odorous substances such as ammonia It was found that the performance of blocking odor transfer was higher than that of the conventional cellulose film (viscose coated paper). The methyl cellulose is preferably added in an amount of about 0.5% by weight or more based on the aqueous solution containing about 3 to 5% by weight of gelatin. It has been found that the addition is more preferable.

In addition, when bisvinylsulfone compound is added and lithium chloride is supported on the surface after drying, moisture permeability is improved by the hygroscopicity of lithium chloride, and the polymer structure of gelatin is stabilized by bisvinylsulfone compound. Therefore, it has been found that the air blocking performance can be maintained or improved. In addition, it was found that the timing for loading lithium chloride in the production process may be carried after the gelatin aqueous solution added with the bisvinylsulfone compound is applied to the substrate and dried. Further, about 0.5 to 1% by weight of methylcellulose and about 0.5 to 5% by weight of a bisvinylsulfone compound based on the dry weight of the gelatin are added to an aqueous solution containing about 3 to 5% by weight of gelatin. After adding and drying, it was found that it is preferable to dipping or spraying an aqueous solution of lithium chloride and then drying to carry the lithium chloride at about 5 to 10 g / m ² .

"Examination of dynamic performance of sheet for total heat exchange element"
In Examples 1 to 3, experiments were performed under so-called static conditions in which gases such as air and ammonia move by diffusion. However, considering the case where the sheet for total heat exchange element containing gelatin or agar examined in Example 2 and Example 3 is applied as the total heat exchange element of the total heat exchanger, air containing pollutants It is necessary to investigate the performance regarding the odor transferability of water-soluble odorous substances such as ammonia under conditions of ventilation.

  Therefore, in Example 4, the odor transferability was examined using an experimental apparatus that can continuously supply ammonia. As shown in FIG. 21, the experimental apparatus was configured by placing an acrylic container in a constant temperature and humidity chamber. This acrylic container is divided into two spaces by a moisture permeable membrane. In one space, a permeator for continuously generating ammonia gas and an adsorbent for adsorbing ammonia are connected. A flow rate pump is connected to the other space so that air is ventilated at a constant flow rate. Each divided space is provided with an ammonia sensor, and the time change of the ammonia concentration in each space can be recorded by a data logger.

  Moreover, methylcellulose and a bisvinylsulfone compound are added to the cellulose membrane (viscose coated paper), which is a conventional product, and the gelatin according to the present invention prepared in Example 3, and further lithium chloride is supported on the moisture permeable membrane. The total heat exchange element sheet was used.

The experimental conditions are as follows.
1) Temperature and relative humidity of the ventilated air: 25 ℃, 90% RH
2) Ammonia concentration in the ventilated air: 25ppm
3) Ventilated air flow rate: 100 mL / min (6 L / h)

  The measurement results are shown in FIG. 22 and FIG. As shown in FIG. 22, it can be seen that the viscose-coated paper has an ammonia concentration that increases from around 20 minutes after the ammonia gas starts to flow. Similar to the results of Example 2 and the like so far, it was confirmed that the performance of blocking the odor transfer of ammonia in the viscose-coated paper was low.

  In contrast, as shown in FIG. 23, the total heat exchange element sheet according to the present invention did not show any increase in ammonia gas concentration even after 2 hours from the start of measurement. Therefore, it was found that the sheet for total heat exchange element according to the present invention has a high performance for blocking the odor transfer of ammonia.

  From the above, it was found that the sheet for a total heat exchange element according to the present invention has a high performance for blocking the odor transfer of ammonia even in a practical ventilation environment used as a total heat exchange element.

  The total heat exchange element sheet and the total heat exchange element sheet manufacturing method according to the present invention are not limited to the above-described embodiment, and can be appropriately changed. For example, an antibacterial agent or an antifungal agent may be included as an additive to suppress the growth of fungi or the generation of mold. Moreover, a deodorizing agent or an odor substance decomposing agent may be contained to improve the deodorizing property. Furthermore, a flame retardant or a non-flammable material may be included to improve the flame retardancy or non-flammability.

DESCRIPTION OF SYMBOLS 1 Sheet | seat for total heat exchange elements 2 Base material 3 Gelatin 4 Agar 5 Thickener 6 Crosslinking material 7 Hygroscopic material 8 Total heat exchange element 81 Partition plate 82 Spacing plate 83 Ventilation layer 84 Air supply layer

Claims (6)

  A gelatin that suppresses the odor transfer of a water-soluble odor substance and a bisvinylsulfone compound that is added to the gelatin and stabilizes the polymer structure thereof are contained in a moisture-permeable film-like base material, A sheet for a total heat exchange element, on which lithium chloride for improving hygroscopicity is supported. The bisvinylsulfone compound is contained at 0.5 to 5% by weight with respect to the dry weight of the gelatin, and the lithium chloride is supported at 5 to 10 g / m ² . Sheet for total heat exchange element.   The sheet for total heat exchange elements according to claim 1 or 2, wherein methylcellulose as a thickener is contained in a weight ratio of 0.1 to 0.3 times the gelatin.   A method for producing a sheet for a total heat exchange element, comprising: adding a thickener for increasing the viscosity of an aqueous solution of gelatin; and allowing the aqueous solution to be contained in a film-like substrate having moisture permeability and drying.   A thickener that increases the viscosity of the aqueous solution and a cross-linking material that stabilizes the polymer structure of the gelatin are added to the aqueous gelatin solution, and the aqueous solution is contained in the substrate and dried. The method for producing a sheet for a total heat exchange element according to claim 4, wherein the hygroscopic material aqueous solution to be improved is dried after dipping or spraying to support the hygroscopic material. To an aqueous solution containing 3 to 5% by weight of gelatin, 0.5 to 1% by weight of methylcellulose and 0.5 to 5% by weight of a bisvinylsulfone compound based on the dry weight of the gelatin are added, The aqueous solution is contained in the base material and dried, and then the aqueous solution of lithium chloride is dried after dipping or spraying to support the lithium chloride at 5 to 10 g / m ² . Total heat exchange element sheet manufacturing method.

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