Partition member for total heat exchange element, total heat exchange element, production method of partition member for total heat exchange element, and coating liquid
A hydrophobic porous substrate with a coating layer of chemically modified fine cellulose fibers and a cellulose derivative binder addresses the challenge of achieving gas barrier, moisture permeability, and water resistance in thinner partition members for total heat exchange elements, enhancing heat exchange efficiency.
Patent Information
- Application Number
- JP2025087770
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-05-30
- Filing Date
- 2025-05-27
- Publication Date
- 2025-12-11
AI Technical Summary
Existing partition members for total heat exchange elements struggle to achieve both gas barrier properties and moisture permeability, especially when reduced in thickness, and often lack sufficient water resistance.
A partition member comprising a hydrophobic porous substrate with a coating layer containing chemically modified fine cellulose fibers and a cellulose derivative binder, with a fiber width of 1 to 1000 nm, providing excellent gas barrier and moisture permeability, and enhanced water resistance.
The partition member achieves high gas barrier properties, moisture permeability, and water resistance, enabling efficient heat exchange even under condensation conditions, allowing for thinner and more layers in the total heat exchange element.
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Figure 2025181742000001_ABST
Abstract
Description
[Technical Field]
[0001] The present invention relates to a partition member for a total heat exchange element, a total heat exchange element, a method for manufacturing a partition member for a total heat exchange element, and a coating liquid. [Background technology]
[0002] Conventionally, heat exchange ventilation devices (total heat exchangers) that exchange heat between intake air and exhaust air during ventilation have been proposed as devices that can ventilate without impairing the effectiveness of cooling or heating. These total heat exchangers are widely used, in which multiple partition members (liners) are stacked with spacing members to separate an intake air path that introduces outdoor air into the room and an exhaust air path that exhausts indoor air to the outside, and a total heat exchange element is incorporated to exchange sensible heat (temperature) and latent heat (humidity) at the same time.
[0003] For example, in winter, outdoor air as supply air and indoor air as exhaust air are guided into each flow path separated by a spacing member. At this time, the supply air and exhaust air exchange temperature and humidity through the partition member. The partition member through which heat exchange occurs has moisture permeability, allowing water vapor to pass through but not air. The partition member also has gas barrier properties by isolating the supply air from the exhaust air. As a result, the supply air is heated and humidified before being supplied indoors, and the exhaust air is cooled and dehumidified before being discharged outdoors. The partition member has both moisture permeability and gas barrier properties, thereby achieving ventilation through total heat exchange. Such partition members must have both heat conductivity and moisture permeability, and therefore in many cases, paper containing natural pulp as a main component, such as glassine paper, is used (Patent Document 1).
[0004] Furthermore, in recent years, attempts have been made to apply cellulose nanofibers, which have gas barrier properties, to partition members (Patent Document 2). [Prior art documents] [Patent documents]
[0005] [Patent Document 1] Patent No. 4252892 [Patent Document 2] Patent Publication No. 2021-155865 Summary of the Invention [Problem to be solved by the invention]
[0006] In the face of growing demands for global warming and energy conservation, total heat exchange elements are attracting attention. In order to further improve the heat exchange efficiency of total heat exchange elements, it is believed that it would be effective to make the partition members thinner than ever before and to increase the number of stacked layers of the total heat exchange element. However, this has been difficult to achieve with the partition members described in Patent Documents 1 and 2.
[0007] Furthermore, if the thickness of the partition member is reduced, it becomes difficult to achieve both gas barrier properties and moisture permeability. Furthermore, water resistance is sometimes required for the partition member for a total heat exchange element, and there has been a demand for improved water resistance. [Means for solving the problem]
[0008] Examples of specific embodiments of the present invention are given below. <1> A partition member for a total heat exchange element, comprising a hydrophobic porous substrate and a coating layer on at least one surface thereof, the coating layer containing at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm and a cellulose derivative as a binder. <2> The fine fibers are chemically modified fine cellulose fibers. <1> The partition member for a total heat exchange element according to claim 1. <3> The hydrophobic porous substrate has an Oken air permeability of 1000 seconds or less. <1> or <2> The partition member for a total heat exchange element according to claim 1. <4> The coating weight of the coating layer is 0.03 g / m 2 More than 3g / m 2 Below is the <1> ~ <3> 10. The partition member for a total heat exchange element according to claim 9. <5> The binder is at least one selected from carboxymethyl cellulose and its salts. <1> ~ <4> 10. The partition member for a total heat exchange element according to claim 9. <6> <1> ~ <5> and a plurality of partition members for a total heat exchange element according to any one of the above items. a spacing member disposed between the total heat exchange element partition members to maintain a spacing between the adjacent total heat exchange element partition members; A total heat exchange element in which first air flow paths and second air flow paths are alternately formed with the total heat exchange element partition member interposed therebetween.
[0009] <7> A method for producing a partition member for a total heat exchange element, comprising the steps of applying a coating liquid containing at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm, a cellulose derivative as a binder, and water to at least one surface of a hydrophobic porous substrate, and drying the coating liquid. <8> The fine fibers are chemically modified fine cellulose fibers. <7> A method for manufacturing the partition member for a total heat exchange element according to claim 1. <9> The binder is at least one selected from carboxymethyl cellulose and its salts. <7> or <8> A method for manufacturing the partition member for a total heat exchange element according to claim 1. <10> The binder is an ammonium salt of carboxymethyl cellulose. <7> ~ <9> 10. A method for producing the partition member for a total heat exchange element according to any one of claims 1 to 9. <11> The drying temperature in the drying step is 70°C or higher and 130°C or lower. <7> ~ <10> 10. A method for producing the partition member for a total heat exchange element according to any one of claims 1 to 9.
[0010] <12> A coating liquid for producing a partition member for a total heat exchange element, comprising at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm, a cellulose derivative as a binder, and water. <13> The fiber width of the fine fibers is 1 to 100 nm. <12> The coating liquid for manufacturing a partition member for a total heat exchange element according to claim 1. <14> The binder is at least one selected from carboxymethyl cellulose and its salts. <12> or <13> The coating liquid for manufacturing a partition member for a total heat exchange element according to claim 1. <15> 2. The method of claim 1, wherein the binder is an ammonium salt of carboxymethyl cellulose. <12> ~ <14> 2. The coating liquid for manufacturing a partition member for a total heat exchange element according to claim 1 . [Effects of the Invention]
[0011] According to the present invention, there is provided a partition member for a total heat exchange element that has both excellent gas barrier properties and moisture permeability, and that also has excellent water resistance. [Brief explanation of the drawings]
[0012] [Figure 1] FIG. 1 is a schematic diagram illustrating the structure of a total heat exchange element. DETAILED DESCRIPTION OF THE INVENTION
[0013] [Partition material for total heat exchange element] The partition member for a total heat exchange element of the present invention has a configuration in which a coating layer is provided on at least one surface of a hydrophobic porous substrate. The Oken air permeability of the partition member for a total heat exchange element is preferably 10,000 seconds or more, more preferably 50,000 seconds or more, even more preferably 80,000 seconds or more, and particularly preferably 99,999 seconds or more. The air permeability of the partition member for a total heat exchange element of the present invention is preferably 150,000 seconds or less. Thus, the partition member for a total heat exchange element of the present invention has excellent gas barrier properties, and also has excellent moisture permeability because a porous substrate is used as the substrate.
[0014] The partition member for a total heat exchange element of the present invention is characterized by having a coating layer containing at least fine polymeric polysaccharide fibers having a fiber width of 1 to 1000 nm and a cellulose derivative as a binder on at least one surface of a hydrophobic porous substrate. In the present invention, by blending both fine polymeric polysaccharide fibers having a fiber width of 1 to 1000 nm and a cellulose derivative as a binder in the coating layer, a partition member for a total heat exchange element having excellent water resistance can be obtained.
[0015] The Oken air permeability of a partition member for a total heat exchange element is a value measured under conditions of 20°C and a relative humidity of 65% in accordance with the Oken air permeability method of JAPAN TAPPI Paper and Pulp Testing Method No. 5-2: 2000. The larger the Oken air permeability value of a partition member for a total heat exchange element, the better the gas barrier properties of the partition member for a total heat exchange element can be determined to be.
[0016] The Oken air permeability of the partition member for a total heat exchange element of the present invention after the water immersion test described below, at 20°C and 65% relative humidity, is preferably 10,000 seconds or more, more preferably 20,000 seconds or more, even more preferably 30,000 seconds or more, even more preferably 50,000 seconds or more, and particularly preferably 80,000 seconds or more. Furthermore, the Oken air permeability of the partition member for a total heat exchange element after the water immersion test described below, at 20°C and 65% relative humidity, is preferably 150,000 seconds or less. The Oken air permeability after the water immersion test is a value measured at 20°C and 65% relative humidity in accordance with the Oken air permeability method of JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000. The Oken air permeability of the partition member for a total heat exchange element after the water immersion test can be controlled, for example, by appropriately adjusting the composition and physical properties of the coating layer.
[0017] "Water immersion test" A sample prepared by cutting a partition member for a total heat exchange element into an A4 size is immersed in 30 liters of tap water, and after 10 minutes, the sample is taken out and air-dried at room temperature until no water droplets remain on the film surface.
[0018] A partition member for a total heat exchange element may be exposed to water due to condensation or the like. If the above physical properties are satisfied, the partition member can maintain its function as a partition member for a total heat exchange element even when exposed to water. In this way, the present invention can provide a partition member for a total heat exchange element that has excellent water resistance. A partition member for a total heat exchange element that has excellent water resistance can be obtained, for example, by providing a coating layer as described below.
[0019] The moisture permeability of the partition material for the total heat exchange element at a temperature of 20°C and a relative humidity of 65% is 2500g / m 224 hours or more is preferable, 2800g / m 2 24 hours or more is more preferable, and 3000g / m 2 The moisture permeability of the partition member for a total heat exchange element at a temperature of 20°C and a relative humidity of 65% is 3800 g / m 2 Preferably, it is 24 hours or less. The moisture permeability of the partition member for a total heat exchange element can be controlled, for example, by appropriately adjusting the composition and physical properties of the coating layer. The moisture permeability of the partition member for a total heat exchange element is measured in accordance with JIS Z 0208:1976. A higher moisture permeability value indicates better heat exchange efficiency.
[0020] The basis weight of the partition material for the total heat exchange element is 5 g / m 2 It is preferable that the content is 6 g / m or more. 2 More preferably, it is 7 g / m or more. 2 The basis weight of the partition member for a total heat exchange element is more preferably 30 g / m or more. 2 Preferably, it is 25 g / m or less. 2 The basis weight of the partition member for the total heat exchange element is preferably 1 / 2 m or less. 2 The basis weight is the mass per unit area, and is measured in accordance with JIS P 8124: 2011. The basis weight of the partition member for a total heat exchange element can be controlled, for example, by using a hydrophobic porous substrate with a low basis weight and a coating layer with a low coating weight.
[0021] The partition member for a total heat exchange element of the present invention has excellent gas barrier properties and moisture permeability despite being lightweight and having a thin basis weight, and can be used as a partition member with excellent heat exchange efficiency.
[0022] "Hydrophobic porous substrate" The hydrophobic porous substrate is not particularly limited, but a thickness of 5 μm to 30 μm is preferred, and a thickness of 10 μm to 25 μm is even more preferred. By setting the thickness at or above the lower limit, the strength as a partition member is maintained, while by setting the thickness at or below the upper limit, the heat exchange efficiency of sensible heat (temperature) is improved and weight reduction is possible. The thickness is measured in accordance with JIS P 8118:2014.
[0023] The surface density of the hydrophobic porous substrate is 29 g / m 2 It is preferable that the content is 25 g / m or less, and more preferably 25 g / m 2 More preferably, it is 20 g / m or less. 2 The lower limit is not particularly limited, and is 2 g / m or less. 2 It is preferable that the density is 5 g / m or more, and more preferably 5 g / m 2 The areal density of the hydrophobic porous substrate can be calculated by dividing the weight of a film cut to a predetermined area by that area.
[0024] The hydrophobic porous substrate needs to be hydrophobic. By making the substrate hydrophobic, it is possible to reduce the weight. For example, by making the substrate hydrophobic, it is not necessary to apply a large amount of fine fibers of polymeric polysaccharides to improve gas barrier properties, and as a result, it is easy to reduce the weight.
[0025] Furthermore, since the substrate is porous with an Oken air permeability of 1000 seconds or less, heat exchange of latent heat (humidity) is possible. The Oken air permeability of the hydrophobic porous substrate is preferably 1000 seconds or less, more preferably 500 seconds or less. The lower limit of the Oken air permeability of the hydrophobic porous substrate is not particularly limited, but is preferably 10 seconds or more, more preferably 30 seconds or more, and even more preferably 50 seconds or more.
[0026] The hydrophobic porous substrate may be, for example, a film or nonwoven fabric made of a thermoplastic resin such as polyolefin or polyester, with an Oken air permeability of 1000 seconds or less, preferably 500 seconds or less. The Oken air permeability is a value measured in accordance with the Oken air permeability method of JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000.
[0027] "Coating layer" In order to enhance gas barrier properties, the partition member for a total heat exchange element of the present invention has a coating layer containing at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1,000 nm and a cellulose derivative as a binder, provided at least in the pore portions of the hydrophobic porous substrate. The Oken air permeability of the partition member for a total heat exchange element thus obtained is preferably 10,000 seconds or more, more preferably 50,000 seconds or more, even more preferably 80,000 seconds or more, and particularly preferably 99,999 seconds or more.
[0028] Furthermore, the moisture permeability of the partition member for a total heat exchange element of the present invention at a temperature of 20°C and a relative humidity of 65% is 2500 g / m 2 The moisture permeability is measured in accordance with JIS Z 0208:1976. A higher moisture permeability value indicates better heat exchange efficiency. The preferred moisture permeability is 2800 g / m 2 24 hours or more, the preferred moisture permeability is 3000g / m 2 24 hours or more. The preferred moisture permeability is 3800 g / m 2 - Less than 24 hours.
[0029] In the present invention, a coating layer containing at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm and a cellulose derivative as a binder is provided on at least one surface of a hydrophobic porous substrate so as to satisfy the above physical properties. The amount of the coating layer applied to the hydrophobic porous substrate is not particularly limited, but it is preferably 0.03 g / m. 2 More than 3g / m 2 It is preferable that the content is 0.03 g / m or less, and more preferably 0.03 g / m 2 More than 2g / m 2By coating, the pores of the substrate can be blocked with a hydrophilic material, which results in suppressing the decrease in moisture permeability. As the coating amount increases, the gas barrier property improves, but moisture permeability tends to decrease. 2 On the other hand, if the coating amount is too small, the pores will not be sufficiently covered and sufficient gas barrier properties will not be obtained. 2 It is preferable that this is equal to or greater than this.
[0030] "Microfibers of polymeric polysaccharides" The polymer polysaccharide fine fibers are not particularly limited as long as they are water-insoluble and can form a film on a hydrophobic porous substrate and exhibit gas barrier properties. Examples include polymer polysaccharides such as cellulose, chitin, and chitosan. Polymer polysaccharides have a molecular structure with many hydroxyl groups (-OH), which allows them to absorb moisture, and the film they form has gas barrier properties. The coating layer preferably contains polymer polysaccharide fine fibers with a fiber width of 1 to 1,000 nm. In particular, from the viewpoint of gas barrier properties, a fiber width of 1 to 500 nm is preferred, a fiber width of 1 to 100 nm is more preferred, and a fiber width of 1 to 30 nm is particularly preferred. In particular, the polymer polysaccharide fine fibers are preferably fine cellulose fibers, which are preferred because they form a dense structure when coated and dried, resulting in excellent gas barrier properties.
[0031] As the fine cellulose fibers, it is preferable to use fine cellulose fibers having a fiber width of 1 to 1,000 nm. Among these, from the viewpoint of gas barrier properties, a fiber width of 1 to 500 nm is preferred, a fiber width of 1 to 100 nm is more preferred, a fiber width of 1 to 30 nm is even more preferred, and a fiber width of 1 to 10 nm is particularly preferred. By making the fiber width of the fine cellulose fibers 1 nm or more, dissolution of the cellulose molecules in water is suppressed, and the effect of improving the air permeability and moisture permeability of the fine cellulose fibers is easily achieved. Furthermore, by making the fiber width of the fine cellulose fibers equal to or less than the above upper limit, the gas barrier properties and moisture permeability can be further improved.
[0032] The fiber width of the fine cellulose fibers is measured using an electron microscope as follows. First, an aqueous suspension of fine cellulose fibers with a concentration of 0.05% by mass to 0.1% by mass is prepared, and this suspension is cast onto a hydrophilized carbon film-coated grid to prepare a sample for TEM observation. If the sample contains wide fibers, it may be cast onto a glass plate and the surface may be observed by SEM. Next, the image is observed using an electron microscope at a magnification of 1,000x, 5,000x, 10,000x, or 50,000x depending on the width of the fiber to be observed. However, the sample, observation conditions, and magnification should be adjusted to meet the following conditions. (1) Draw a line X at any point in the observed image, and 20 or more fibers intersect with the line X. (2) Draw a line Y that intersects the line perpendicularly within the same image, and 20 or more fibers intersect the line Y. For observation images that satisfy the above conditions, the widths of the fibers intersecting with lines X and Y are visually read. In this way, three or more sets of observation images of at least the surface portions that do not overlap each other are obtained. Next, for each image, the widths of the fibers intersecting with lines X and Y are read. In this way, the fiber widths of at least 20 fibers x 2 x 3 = 120 fibers are read. The average fiber width is the average value of the fiber widths of the read fine cellulose fibers.
[0033] The fiber length of the fine cellulose fibers is not particularly limited, but is preferably 0.1 μm or more, and preferably 1,000 μm or less, more preferably 800 μm or less, and even more preferably 600 μm or less. By setting the fiber length of the fine cellulose fibers within the above range, destruction of the crystalline regions of the fine cellulose fibers can be suppressed. In addition, it is possible to set the slurry viscosity of the fine cellulose fibers within an appropriate range, making it easier to form a fiber layer. The fiber length of the fine cellulose fibers can be determined by image analysis using, for example, TEM, SEM, or AFM.
[0034] The axial ratio (fiber length / fiber width) of the fine cellulose fibers is not particularly limited, but is preferably at least 20, more preferably at least 50, and is preferably at most 10,000, more preferably at most 1,000. By setting the axial ratio within the above range, a slurry viscosity suitable for forming a fiber layer can be obtained.
[0035] In the present invention, the fine cellulose fibers are preferably chemically modified fine cellulose fibers. Specifically, it is preferable that at least one type of group selected from ionic groups and nonionic groups is introduced into the fine cellulose fibers. Furthermore, it is preferable that the ionic groups and nonionic groups are hydrophilic groups. From the viewpoint of improving the dispersibility of the fibers in the dispersion medium and increasing the defibration efficiency in the defibration treatment, it is more preferable that the fine cellulose fibers have ionic groups. The ionic groups may include either or both of anionic groups and cationic groups. In the present invention, it is particularly preferable that the ionic groups include anionic groups. The anionic group is preferably at least one selected from a phosphate group, a group derived from a phosphate group, a phosphite group, a group derived from a phosphite group, a carboxy group, a group derived from a carboxy group, a sulfonic acid group, and a group derived from a sulfonic acid group.
[0036] "binder" The coating layer contains a binder in addition to the fine fibers of polymeric polysaccharides. The binder enhances the adhesion of the fine fibers of polymeric polysaccharides to the hydrophobic porous substrate, thereby improving the gas barrier properties of the coating layer. Cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxymethyl cellulose (excluding the fine cellulose fibers described above) are preferably used as the binder. They can be used alone or in combination as needed. Cellulose derivatives have a structure similar to that of the fine fibers of polymeric polysaccharides, and after film formation, they provide a coating layer with excellent moisture permeability. The cellulose derivative preferably contains at least one selected from the group consisting of carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxymethyl cellulose, or at least one selected from salts thereof. It is more preferable to contain at least one selected from carboxymethyl cellulose and its salts, and it is particularly preferable to contain an ammonium salt of carboxymethyl cellulose. A coating layer using at least one selected from carboxymethyl cellulose and its salts is preferred because it can achieve both gas barrier properties and high moisture permeability. Note that binders other than cellulose derivatives may be used in combination as long as they do not impair the effects of the present invention.
[0037] The coating layer of the partition member for a total heat exchange element of the present invention contains both fine polymeric polysaccharide fibers having a fiber width of 1 to 1000 nm and a cellulose derivative. The blending ratio of the two is not particularly limited, but is preferably 50 to 200 parts by mass, preferably 60 to 180 parts by mass, more preferably 70 to 160 parts by mass of the solid content of the cellulose derivative per 100 parts by mass of the solid content of the fine polymeric polysaccharide fibers having a fiber width of 1 to 1000 nm.
[0038] The partition member for a total heat exchange element of the present invention has high air permeability and moisture permeability, and is suitable for use as a partition member for a total heat exchange element with excellent carbon dioxide barrier properties. Furthermore, since a hydrophobic porous substrate is used, the mechanical strength is less likely to decrease even if condensation occurs. Furthermore, since the partition member is lightweight, it is possible to increase the number of stacked layers of a total heat exchange element.
[0039] [Method for manufacturing partition member for total heat exchange element] The present invention provides a method for producing a partition member for a total heat exchange element, which comprises applying a coating liquid containing at least water, fine polymeric polysaccharide fibers having a fiber width of 1 to 1000 nm, a cellulose derivative as a binder, and water to at least one surface of a hydrophobic porous substrate, followed by drying. The coating liquid preferably contains fine polymeric polysaccharide fibers having a fiber width of 1 to 1000 nm, a binder, and water. Details of the hydrophobic porous substrate, fine polymeric polysaccharide fibers, and binder are as described above.
[0040] Details of the hydrophobic porous substrate, polymer polysaccharide fine fibers, and binder are as described above. The polymer polysaccharide fine fibers and binder are preferably prepared in the form of an aqueous dispersion and an aqueous solution, respectively, and then mixed together to form a coating liquid. Depending on the environment in which the total heat exchange element is used, condensation may occur, and the coating layer formed may also need to be water-resistant. A water-resistant agent may be added to impart water resistance, but water resistance can be improved by using an ammonium salt of carboxymethyl cellulose as the cellulose derivative. This is thought to be because the ammonium salt of carboxymethyl cellulose evaporates as ammonium during drying, thereby improving the water resistance of the coating layer itself.
[0041] The coating layer can be formed, for example, by applying a coating liquid containing the above components to a hydrophobic porous substrate and drying it. Known coating machines can be used for the coating method, and are not particularly limited. Examples include blade coaters, bar coaters, curtain coaters, die coaters, air knife coaters, and roll coaters. Blade coaters and bar coaters are preferred because the pressing force of the blade or bar during coating allows the coating liquid to penetrate into the pores of the porous substrate. For drying, a dryer attached to the coating machine can be used. The drying temperature is preferably 65°C or higher, more preferably 70°C or higher, even more preferably 75°C or higher, even more preferably 80°C or higher, even more preferably 85°C or higher, and particularly preferably 90°C or higher. The drying temperature is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. By setting the drying temperature at or above the lower limit, the water resistance of the coating layer can be more effectively improved. Furthermore, by setting the drying temperature to the above upper limit or less, it is possible to suppress a decrease in strength of the hydrophobic porous substrate due to drying.
[0042] The amount of coating liquid applied to the hydrophobic porous substrate is not particularly limited, but is preferably 0.03 g / m 2 More than 3g / m 2 It is preferable that the content is 0.03 g / m or less, and more preferably 0.03 g / m 2 More than 2g / m 2 As the coating weight increases, the gas barrier property improves, but the moisture permeability tends to decrease. 2 On the other hand, if the coating amount is too small, the pores will not be sufficiently covered and sufficient gas barrier properties will not be obtained. 2 The coating amount of the coating liquid is preferably 0.03 g / m or more. 2 More than 3g / m 2When the thickness is less than 100 μm, a uniform coating film can be formed, and the pores of the substrate can be blocked with the hydrophilic material, thereby suppressing a decrease in moisture permeability. In the present invention, it is preferable to incorporate fine fibers of polymeric polysaccharides into the coating layer, since the fine fibers of polymeric polysaccharides penetrate not only the surface of the hydrophobic porous substrate but also into the interior of the pores, thereby more effectively increasing the moisture permeability.
[0043] When applying a coating solution containing fine fibers of polymeric polysaccharides to a hydrophobic porous substrate, if the substrate repels the coating solution, it is recommended to subject the substrate to a surface hydrophilization treatment such as corona discharge treatment in advance. Furthermore, adding a surfactant (e.g., a wetting agent or leveling agent) to the coating solution improves film-forming properties and allows for the production of a partition member for a total heat exchange element with high air permeability, which is preferable. It is preferable to use a surfactant with reduced foaming properties.
[0044] Since the coating amount of the coating layer in the partition member of the present invention is small, heat exchange of latent heat (humidity) occurs even without the application of a moisture absorbent. However, a moisture absorbent may be blended to further increase moisture permeability. Examples of moisture absorbents include inorganic acid salts, organic acid salts, polyhydric alcohols, and ureas. For example, examples of inorganic acid salts include lithium chloride, calcium chloride, and magnesium chloride. Examples of organic acid salts include sodium lactate, calcium lactate, and sodium pyrrolidone carboxylate. Examples of polyhydric alcohols include glycerin, ethylene glycol, triethylene glycol, and polyglycerin. Examples of ureas include urea and hydroxyethyl urea.
[0045] Furthermore, the coating liquid may contain auxiliary agents such as water-resistant agents, preservatives, mildew-proofing agents, flame retardants, viscosity adjusters, pH adjusters, colorants, storage stability improvers, polymer resins, and antiblocking agents, as long as the effects of the present invention are not impaired.
[0046] When applying the coating liquid containing fine fibers of high molecular weight polysaccharides, the amount of coating is adjusted so that the resulting partition member for a total heat exchange element has an Oken air permeability of 10,000 seconds or more. 2It is preferable to adjust the coating amount so that the coating time is 24 hours or more.
[0047] [Total heat exchange element] The total heat exchange element of the present invention comprises a plurality of the above-mentioned partition members for the total heat exchange element, and also comprises spacing members arranged between the partition members for the total heat exchange element to maintain the spacing between adjacent partition members for the total heat exchange element, and is a total heat exchange element in which first air flow paths and second air flow paths are formed alternately on either side of the partition members for the total heat exchange element.
[0048] The total heat exchange element will be described below with reference to FIG. 1, but the present invention is not limited to the total heat exchange element having the structure of FIG. FIG. 1 is a schematic diagram illustrating the structure of a total heat exchange element 10. As shown in FIG. 1, the total heat exchange element 10 is composed of a plurality of partition members 1 and a plurality of spacing members 2 that form air flow paths between the plurality of partition members 1 and maintain the spacing between the partition members 1. The partition members 1 are flat plates that are shaped like squares, diamonds, or the like, and the spacing members 2 maintain the spacing between the partition members 1 and are, for example, corrugated plates formed into waveforms such as sawtooth waves or sine waves whose projected planar shape matches the shape of the partition members 1. The spacing members 2 are shaped, for example, like the core of cardboard and are formed by corrugating.
[0049] The spacing member 2 is not particularly limited as long as it maintains the distance between the partition members. The spacing member maintains the distance between the partition members, thereby forming air flow paths between the partition members. The spacing member is not limited to a corrugated material such as a paper substrate, film, or nonwoven fabric, but may also be a resin rib. Of these, a paper substrate is preferred. Because a paper substrate has the function of regulating moisture, it can compensate for the reduced moisture-regulating function of partition members using a hydrophobic porous substrate.
[0050] The spacing member 2 has a shape similar to the core of cardboard, for example, and is formed by corrugating. The ridges and valleys of the waveforms of the spacing member 2 are joined to the partition member 1 with an adhesive or the like. The spacing member 2 is joined to the partition member 1 on one side with the partition member 1 in between, with the ridges of the waveforms extending in a first direction (for example, the vertical direction), and on the other side with the ridges of the waveforms extending in a second direction (for example, the horizontal direction). In other words, two spacing members 2 adjacent to each other with the partition member 1 in between are stacked alternately so that the direction of the ridges of the waveforms on one side and the direction of the ridges of the waveforms on the other side are perpendicular to each other.
[0051] Between the spacing member 2, whose ridge lines of the waveforms are oriented in a first direction (for example, the vertical direction), and the partition members 1 on both sides, a plurality of first air flow paths 4 are formed along the first direction. Furthermore, between the spacing member 2, whose ridge lines of the waveforms are oriented in a second direction (for example, the horizontal direction), and the partition members 1 on both sides, a plurality of second air flow paths 5 are formed along the second direction. Note that arrow 6 in FIG. 1 indicates the direction of air flow in the first air flow paths 4, and arrow 7 in FIG. 1 indicates the direction of air flow in the second air flow paths 5.
[0052] Spacing members 2 whose corrugated ridgelines are oriented in a first direction and spacing members 2 whose corrugated ridgelines are oriented in a second direction are alternately stacked with the partition member 1 in between so that the ridge directions are perpendicular to each other, and therefore the first air flow paths 4 and the second air flow paths 5 are also formed so that the extension directions are perpendicular to each other. For example, supply air flows through the first air flow path 4 and exhaust air flows through the second air flow path 5, and heat exchange occurs between the supply air and exhaust air via the partition member 1 and spacing members 2.
[0053] The method for joining the partition member and the spacing member can be a known method such as a method using an adhesive or a thermal bonding method without using an adhesive. Among these, a method using an adhesive is preferable because it can firmly bond the spacing member and the partition member. Known adhesives such as polyvinyl alcohol adhesives and ethylene vinyl acetate adhesives can be used as the adhesive.
[0054] [Coating fluid] The coating liquid of the present invention is a coating liquid for producing a partition member for a total heat exchange element, which contains at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm, a cellulose derivative as a binder, and water. The binder is preferably at least one selected from carboxymethylcellulose and its salts, and more preferably an ammonium salt of carboxymethylcellulose.
[0055] The coating solution of the present invention contains fine polymeric polysaccharide fibers with a fiber width of 1 to 1,000 nm and a cellulose derivative with a similar structure as a binder, thereby improving adhesion, cohesion, and water resistance while taking advantage of the advantages of the fine polymeric polysaccharide fibers. The coating solution of the present invention is expected to have a variety of applications in addition to the coating layer of partition members for heat exchange elements. For example, it can be used for a variety of applications, such as gas barrier sheets, packaging materials, shoji paper, and wallpaper. [Example]
[0056] The features of the present invention will be explained in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0057] <Preparing the substrate> Substrate: A 16 μm thick polypropylene film (product name: SD216301, manufactured by Shenzhen Senior Technology Material Co., Ltd.) was prepared as a hydrophobic porous substrate. The surface density was 9.4 g / m. 2 The Oken air permeability was 305 seconds.
[0058] <Preparation of fine cellulose fibers> (Phosphate group introduction step) The raw pulp used was softwood kraft pulp (solid content 93% by mass, basis weight 210 g / m) manufactured by Oji Paper Co., Ltd. 2 A sheet-like product with a Canadian Standard Freeness (CSF) of 690 ml when disintegrated and measured in accordance with JIS P 8121:2012 was used. This raw pulp was subjected to phosphorylation treatment as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea was added to the raw pulp to adjust the ratio of 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, and 150 parts by mass of water per 100 parts by mass (bone dry mass) of raw pulp to obtain a chemical-impregnated pulp. The obtained chemical-impregnated pulp was then heated in a hot air dryer at 165°C for 200 seconds to introduce phosphate groups into the cellulose in the pulp, thereby obtaining a phosphorylated pulp.
[0059] (Cleaning process) The resulting phosphorylated pulp was then subjected to a washing treatment. The washing process was carried out by pouring 10 L of ion-exchanged water over 100 g of phosphorylated pulp (bone dry mass), stirring to uniformly disperse the pulp, and then repeatedly filtering and dehydrating the pulp. The washing was completed when the electrical conductivity of the filtrate reached 100 μS / cm or less.
[0060] (Alkali treatment process) Next, the washed phosphorylated pulp was subjected to an alkali treatment (neutralization treatment) as follows. First, the washed phosphorylated pulp was diluted with 10 L of ion-exchanged water, and then a 1 N aqueous solution of sodium hydroxide was added little by little while stirring to obtain a phosphorylated pulp slurry with a pH of 12 to 13. Next, the phosphorylated pulp slurry was dehydrated to obtain phosphorylated pulp that had been subjected to an alkali treatment (neutralization treatment). Next, the phosphorylated pulp after the alkali treatment was subjected to the above-mentioned washing treatment. The infrared absorption spectrum of the resulting alkali-treated phosphorylated pulp was measured using FT-IR. The absorption peak at 1230 cm-1 was due to phosphate groups, confirming the addition of phosphate groups to the pulp. The amount of phosphate groups (strong acid groups) measured using the aforementioned method was 1.45 mmol / g. In addition, the obtained phosphorylated pulp was analyzed using an X-ray diffractometer, and typical peaks for cellulose type I crystals were confirmed at two positions, around 2θ = 14° to 17° and around 2θ = 22° to 23°, confirming the presence of cellulose type I crystals.
[0061] (Defibrillation process) Ion-exchanged water was added to the phosphorylated pulp obtained through the alkali treatment step to prepare a slurry with a solids concentration of 2% by mass. This slurry was treated three times at a pressure of 200 MPa using a wet pulverization device (Starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a microfibrillated cellulose fiber dispersion containing microfibrillated cellulose fibers. X-ray diffraction confirmed that the microfibrillated cellulose fibers maintained cellulose type I crystals. Furthermore, the fiber width of the microfibrillated cellulose fibers was measured using a transmission electron microscope and found to be 3 to 5 nm. Furthermore, the yield of the microfibrillated cellulose fibers obtained was measured according to the method described above, and was found to be 99.2%.
[0062] (Comparative Example 1) <Manufacturing of partition members for total heat exchange elements> A polyether surfactant (product name: SN Wet 985, manufactured by San Nopco, 76% aqueous dispersion) and water were added to the 0.5% aqueous dispersion of fine cellulose fibers obtained above to prepare a coating liquid. The composition is shown in Table 1 as the amount of adhesion of each component. The concentration of the coating liquid was 0.7%. After corona discharge treatment was performed on one side of the substrate, the coating solution was applied with a Mayer bar to a coating weight of 0.37 g / m after drying. 2 The mixture was dried at 70°C for 10 minutes to obtain a partition member for a total heat exchange element.
[0063] Example 1 To the 0.5% aqueous dispersion of fine cellulose fibers obtained above, carboxymethyl cellulose ammonium salt (trade name: DN-10L, manufactured by Daicel Millize Co., Ltd., 3% solution) and a polyether surfactant (trade name: SN Wet 985, manufactured by San Nopco Co., Ltd., 76% aqueous dispersion) were added to obtain a coating solution. The formulation is shown in Table 1 as the amount of adhesion of each component. The concentration of the coating solution was 0.8%. One side of the substrate was subjected to a corona discharge treatment, and then the coating weight after drying was measured using a Mayer bar. 2 The mixture was dried at 70°C for 10 minutes to obtain a partition member for a total heat exchange element.
[0064] Example 2 To the 0.5% aqueous dispersion of fine cellulose fibers obtained above, carboxymethyl cellulose ammonium salt (trade name: DN-10L, manufactured by Daicel Millize Co., Ltd., 3% solution) and a polyether surfactant (trade name: SN Wet 985, manufactured by San Nopco Co., Ltd., 76% aqueous dispersion) were added to obtain a coating solution. The formulation is shown in Table 1 as the amount of adhesion of each component. The concentration of the coating solution was 0.8%. One side of the substrate was subjected to a corona discharge treatment, and then the coating weight after drying was 0.38 g / m using a Mayer bar. 2 The mixture was dried at 105°C for 10 minutes to obtain a partition member for a total heat exchange element. (evaluation) The moisture permeability and Oken air permeability of the partition members for total heat exchange elements obtained in the examples and comparative examples were measured. Table 1 also shows the Oken air permeability after immersion in water and the presence or absence of peeling. "Moisture permeability" Measurements were carried out under conditions of 20°C and 65% RH in accordance with JIS Z0208, with calculations being carried out using the following formula: Moisture permeability=(a+b) / 2 where a = mass increase after 1 hour of measurement b = Mass increase per hour from 1 hour after the start of measurement to 2 hours after the start of measurement
[0065] "Ouken style air permeability" Measurement was performed in accordance with the Oken air permeability method of JAPAN TAPPI Paper and Pulp Test Method No. 5-2:2000.
[0066] "Water immersion test" A sample of a partition member for a total heat exchange element cut to A4 size was immersed in 30 liters of tap water. A 120 g weight was attached to the sample to prevent it from floating. After 10 minutes, the sample was removed and air-dried at room temperature until no water droplets remained on the film surface. (peeling) Observe the surface of the dried sample to check if the coating layer has peeled off. (Oken style air permeability (after immersion in water)) The Oken air permeability of the dried sample was measured in accordance with the Oken air permeability method of JAPAN TAPPI Paper Pulp Test Method No. 5-2:2000.
[0067] "Basic weight" The basis weight of the partition member for a total heat exchange element was calculated from the area and mass of the test piece in accordance with JIS P8124:2011.
[0068] [Table 1]
[0069] The partition members for total heat exchange elements obtained in the examples had high air permeability and moisture permeability, and also had high air permeability after water immersion. When the examples containing a cellulose derivative were subjected to a water immersion test, no peeling occurred in the coating layer, and although the air permeability decreased, it did not fall below 10,000 seconds. In particular, Example 2, in which the drying temperature was increased, also had high air permeability after water immersion. When such a partition member for a total heat exchange element is used as a total heat exchange element, it can be fully applied even in harsh environments where condensation is frequent. On the other hand, when Comparative Example 1, which did not contain a cellulose derivative, was subjected to a water immersion test, peeling occurred in the coating layer and the air permeability also decreased significantly. It was found that a coating layer formed from a coating liquid containing fine cellulose fibers and a cellulose derivative has high adhesion to a hydrophobic porous substrate and also has excellent water resistance without impairing the performance of the fine cellulose fibers. [Explanation of symbols]
[0070] 1 Partition member 2 Spacing members 4 First air flow path 5 Second Air Flow Path 10 Total heat exchange element
Claims
1. A partition member for a total heat exchange element, comprising a hydrophobic porous substrate and a coating layer on at least one surface thereof, the coating layer containing at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm and a cellulose derivative as a binder.
2. 2. The partition member for a total heat exchange element according to claim 1, wherein the fine fibers are chemically modified fine cellulose fibers.
3. 2. The partition member for a total heat exchange element according to claim 1, wherein the hydrophobic porous substrate has an Oken air permeability of 1000 seconds or less.
4. The coating amount of the coating layer is 0.03 g / m 2 3g / m or more 2 The partition member for a total heat exchange element according to claim 1 , wherein:
5. 2. The partition member for a total heat exchange element according to claim 1, wherein the binder is at least one selected from the group consisting of carboxymethyl cellulose and salts thereof.
6. A heat exchanger according to any one of claims 1 to 5, a spacing member disposed between the total heat exchange element partition members to maintain a spacing between the adjacent total heat exchange element partition members; A total heat exchange element, in which first air flow paths and second air flow paths are formed alternately with the partition member for the total heat exchange element sandwiched therebetween.
7. A method for producing a partition member for a total heat exchange element, comprising the steps of applying a coating liquid containing at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm, a cellulose derivative as a binder, and water to at least one surface of a hydrophobic porous substrate, and drying the coating liquid.
8. The method for producing a partition member for a total heat exchange element according to claim 7, wherein the fine fibers are chemically modified fine cellulose fibers.
9. 9. The method for producing a partition member for a total heat exchange element according to claim 7 or 8, wherein the binder is at least one selected from the group consisting of carboxymethyl cellulose and salts thereof.
10. 9. The method for producing a partition member for a total heat exchange element according to claim 7 or 8, wherein the binder is an ammonium salt of carboxymethyl cellulose.
11. The method for manufacturing a partition member for a total heat exchange element according to claim 7 or 8, wherein the drying temperature in the drying step is 70°C or higher and 130°C or lower.
12. A coating liquid for producing a partition member for a total heat exchange element, comprising at least fine fibers of a polymeric polysaccharide having a fiber width of 1 to 1000 nm, a cellulose derivative as a binder, and water.
13. The coating liquid for manufacturing a partition member for a total heat exchange element according to claim 12, wherein the fine fibers have a fiber width of 1 to 100 nm.
14. The coating liquid for producing a partition member for a total heat exchange element according to claim 12 or 13, wherein the binder is at least one selected from the group consisting of carboxymethyl cellulose and salts thereof.
15. The coating liquid for producing a partition member for a total heat exchange element according to claim 12 or 13, wherein the binder is an ammonium salt of carboxymethyl cellulose.
Citation Information
Patent Citations
Total heat exchange device paper
JP2021155865A
Total heat exchange element paper
JP4252892B2