multilayer structure, energy recovery ventilation sheet, method for producing the multilayer structu

专利摘要:
MULTILAYER STRUCTURE, ENERGY RECOVERY VENTILATION SHEET, METHOD TO PRODUCE THE MULTILAYER STRUCTURE, ENERGY RECOVERY VENTILATION ELEMENT, AND, ENERGY RECOVERY FAN. A multilayer structure is provided comprising at least one layer of thin cellulose fiber non-woven fabric made of a thin cellulose fiber, wherein the multilayer structure is characterized in that the average fiber diameter of the thin cellulose fiber forming the layer of thin cellulose fiber non-woven fabric is 0.005 to 0.5 (MI) and the average thickness of the multilayer structure is 10 to 200 μm, its density is 0, 10 to 0.90 g / cm 3, and its resistance to permeability is 2000 s / 100 ml or more. An energy recovery ventilation sheet made of this multilayer structure is also provided, an energy recovery ventilation element using this energy recovery ventilation sheet as a dividing material to divide two types of air flow of different temperature and / or moisture, and an energy recovery fan using this energy recovery ventilation element.
公开号:BR112015000927B1
申请号:R112015000927-1
申请日:2013-07-19
公开日:2021-01-12
发明作者:Hirofumi Ono；Shuji Takasu；Atsushi Horii；Satoru Yoshida
申请人:Asahi Kasei Fibers Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a multilayer structure comprising at least one layer of fine cellulose fiber nonwoven fabric, an energy recovery ventilation sheet composed of the multilayer structure, an energy recovery ventilation element which uses the energy recovery ventilation sheet 10 as a divider material that divides two types of airflow of different temperature, different humidity or both, and an energy recovery fan that uses the energy recovery ventilation element. BACKGROUND ART
[002] Air conditioning equipment is responsible for the largest proportion of the energy consumed by common office buildings and other architectural structures (approximately 38%). Since 30% to 40% of this amount cannot be ventilated from outside, the reduction of energy loss from air conditioning attributable to ventilation can be considered an important issue 20 for energy conservation in office buildings. In addition, the so-called "sick home syndrome", which is caused by volatile organic compounds dissipated by building materials, household items, and the like, is also becoming problematic. Examples of the causes of these problems include the increased air tightness of buildings, increased difficulty in circulating air due to the proliferation of air conditioners, and the ease of accumulation of volatile organic compounds within buildings. In view of these circumstances, buildings in Japan are required to install ventilation equipment in accordance with the revised Civil Construction Standards in July 2003. In addition, attempts have also been made to add ventilation functions to domestic air conditioners. , and such efforts were not limited to Japan, with the ventilation of buildings being promoted worldwide.
[003] However, when attempts are made to promote the ventilation of buildings, it becomes difficult to maintain the heating of buildings, even if air conditioning is employed, thus resulting in excessively high energy consumption. Consequently, attention is being paid to total heat exchangers that are able to reduce energy consumption, making it difficult for heat or cold to be released outside, even if ventilation is employed.
[004] Examples of these energy recovery fans include rotary energy recovery fans, which recover heat from the exhaust air to the intake air by rotating a hygroscopic rotor, and static energy recovery fans, As shown in Figure 1, In these static-type energy recovery fans (fixed type), a gas-impermeable energy recovery ventilation element arranged in a wavy shape allows sensitive heat to migrate, while dividing into fresh air supplied from outside that it had been exchanged for ventilation and air discharged into the contaminated interior, while simultaneously letting water retaining latent heat pass from the discharged air to the supplied air by allowing moisture to permeate, thereby reducing the release of heat or cold to the outside.
[005] Since the energy recovery ventilation sheets used in the energy recovery ventilation elements of the energy recovery fan of static type not only allow the migration of sensitive heat, but also allow the migration of latent heat to the allowing the passage of moist air, increases the efficiency of energy recovery. Examples of such sheets include energy recovery ventilation sheets using flame retardant paper made from Japanese paper or pulp, mixed paper from glass fibers, mixed paper containing inorganic powder, and microporous film, paper and composite non-woven fabric of synthetic polymers. However, since air also ends up penetrating the sheet in the case of using a common microporous film, paper or non-woven fabric, the energy recovery ventilation sheets have been reported to have undergone a surface treatment, such as application of a polymer coating on its surface. For example, Patent Document 1, indicated below, describes an energy recovery ventilation sheet obtained by coating a polyurethane-based resin containing oxyethylene groups on a porous sheet that uses polytetrafluoroethylene for its material, whereas the Document Patent 2 indicated below describes an energy recovery ventilation sheet composed of polyester and polyethylene or polypropylene. In both of these cases, once a hydrophobic polymer is used for the base material, adequate moisture permeability cannot be obtained and, as a result, sufficient thermal conductivity is unable to be obtained for use as a recovery vent sheet. power.
[006] Patent document 3 indicated below describes an energy recovery ventilation filter obtained by coating viscose on hydrophilic fibers in the form of a non-woven fabric of rayon paste. The coating with hydrophilic rayon fibers is described as allowing the production of a sheet having moisture permeability of 6900 g / m2 / 24 hours or more and resistance to permeability of 10,000 s / 100 ml or more. However, due to inadequate moisture permeability, sufficient performance for use as an energy recovery ventilation sheet cannot be achieved.
[007] On the other hand, the inventors of the present invention have reported a structure of nonwoven fabric containing a layer of thin cellulose composed of thin cellulose fibers in Patent Document 4 indicated below. However, the non-woven multilayer structure described in Patent Document 4 was not suitable for use as an energy recovery ventilation sheet due to the high air permeability (resistance to permeability of 2000 s / 100 ml or less). PREVIOUS ART DOCUMENT
[008] PATENT DOCUMENTS Patent document 1: JP patent publication not examined No. H6-194093 Patent document 2: JP patent publication not examined No. 2003-287387 Patent document 3: JP patent publication not examined No 2008-14623 Patent document 4: JP patent publication unexamined No. 2010-115574 DESCRIPTION OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[009] A problem to be solved by the present invention is to provide a multilayer structure having a high resistance to air permeability and high moisture permeability which is highly suitable for use as an energy recovery ventilation sheet. MEANS TO SOLVE PROBLEMS
[0010] As a result of focusing on the fact that a thin cellulose fiber non-woven fabric contained in a multilayer structure of non-woven fabric has an extremely small fiber diameter, proceeding with studies on the formation of a uniformly layer dense and thin having a low base weight by using the property of a prominent increase in density resulting from lamination according to a papermaking method from an aqueous dispersion followed by drying and shrinkage in the thickness direction during drying, and still conducting extensive studies to solve the above problems, the inventors of the present invention have achieved obtaining a multilayer structure in the form of a sheet material capable of not only being used as an energy recovery ventilation sheet, but also used in a wide range of application fields requiring both high permeability resistance and high moisture permeability , thus leading to the conclusion of the present invention.
[0011] That is, the present invention is as described below.
[0012] [1] A multilayer structure comprising at least one layer of thin cellulose fiber non-woven fabric composed of thin cellulose fibers, wherein said thin cellulose fibers forming the layer of thin cellulose fiber non-woven fabric have an average fiber diameter of 0.005 μm to 0.5 μm, and this multilayer structure has an average thickness of 10 μm to 200 μm, a density of 0.10 g / cm3 to 0.90 g / cm3, and a resistance permeability of 5 2000 s / 100 ml or more.
[0013] [2] The multilayer structure described in [1] above, which is a two-layer structure, the average thickness of the multilayer structure is 10 μm to 150 μm, the density is 0.30 g / cm3 to 0.80 g / cm3 and the resistance to permeability is 3000 s / 100 ml or more. 10
[0014] [3] The multilayer structure described in [1] or [2] above, wherein the proportion of thin cellulose fibers contained in the thin cellulose fiber non-woven layer is 50% by weight to 100% in Weight.
[0015] [4] The multilayer structure described in any one of [1] to [3] above, in which the total sum of the base weight of the thin cellulose fiber nonwoven layer is 1 g / m2 at 15 g / m2 and the total sum of the thickness is 0.5 μm to 15 μm.
[0016] [5] The multilayer structure described in any one of [1] to [4] above, wherein a layer of the multilayer structure is a layer of non-woven fabric and / or porous film and / or fabric composed of one or a combination of a plurality of fibers selected from the group consisting of regenerated cellulose fibers, natural cellulose fibers, nylon fibers, polyester fibers and polyolefin fibers.
[0017] [6] The multilayer structure described from any one of [1] to [4] above, wherein a layer of the multilayer structure is a layer of non-woven fabric composed of continuous long fibers of regenerated cellulose.
[0018] [7] The multilayer structure described from any one of [1] to [6] above, in which the multilayer structure was subjected to a waterproof treatment.
[0019] [8] The multilayer structure described from any one of [1] to [7] 30 above, in which the multilayer structure has been subjected to a hydrophilic treatment.
[0020] [9] An energy recovery ventilation sheet composed of the multilayer structure described in any one of [1] to [8] above.
[0021] [10] The energy recovery ventilation sheet described in [9] above, where the average thickness of the multilayer structure is 10 μm to 70 μm. 5
[0022] [11] The energy recovery ventilation sheet described in [10] above, where the average thickness of the multilayer structure is 10 μm to 30 μm.
[0023] [12] The energy recovery ventilation sheet described in any one of [9] to [11] above, in which the multilayer structure was subjected to flame retardant treatment. 10
[0024] [13] The energy recovery ventilation sheet described in any one of [9] to [12] above, in which the proportion of cellulose fibers in the material that makes up the multilayer structure is 90% by weight or more .
[0025] [14] A method for producing the multilayer structure described in any one of [1] to [6] above, comprising the following steps: 15 a step for laminating and forming a layer of fine cellulose fiber nonwoven fabric having an average fiber diameter of 0.005 μm to 0.5 μm over a layer of nonwoven fabric by a papermaking method, and a step to dry the resulting laminated nonwoven fabric.
[0026] [15] The method described in [14] above, still comprising a heat treatment step after the drying step.
[0027] [16] The method for producing the multilayer structure described in [14] above, comprising: a step to form a hydrophilic coating layer by coating on one side or both sides of the multilayer structure described 25 on either of [ 1] to [6] above.
[0028] [17] An energy recovery ventilation element in which the energy recovery ventilation sheet described in any one of [9] to [13] above is used as a dividing material that divides two types of energy flow air of different temperature, humidity or both.
[0029] [18] An energy recovery fan using the energy recovery ventilation element described in [17] above. EFFECTS OF THE INVENTION
[0030] Although the multilayer structure of the present invention can preferably be used in all applications requiring resistance to high permeability and high permeability to moisture as a result of demonstrating both of these physical properties, it can be particularly preferably used as a dividing material (element total heat exchange) that divides two types of air having different temperature, humidity or both in energy recovery fans for office air conditioners or home and similar use. That is, because this energy recovery ventilation element is more permeable to moist air than conventional energy recovery ventilation sheets due to the thin closed portions that divide the air, it is highly effective in retaining moisture. In addition, because the multilayer structure provided by the present invention also has superior durability, the use of this structure in an energy recovery fan makes it possible to provide an energy recovery fan that demonstrates extremely high moisture exchange efficiency and total recovery effectiveness of energy over a long period of time. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 is a schematic diagram showing the structure of a static energy recovery fan.
[0032] Figure 2 is a SEM image (Example 1, magnification factor: 1000X) of the top surface (thin cellulose fiber layer) of the multilayer structure of the present invention.
[0033] Figure 3 is an SEM image (Example 1, magnification factor: 1000X) of the back surface (support layer) of the multilayer structure of the invention.
[0034] Figure 4 is an SEM image (Example 6, magnification factor: 1000 X) of a cross section of the multilayer structure of the present invention. CARRYING OUT WAYS TO CARRY OUT THE INVENTION
[0035] The multilayer structure of the present invention comprises at least one layer or multiple layers of thin cellulose fiber non-woven fabric composed of thin cellulose fibers. Resistance to permeability, moisture permeability and desired durability are unable to be achieved unless the structure is composed of thin cellulose fibers.
[0036] The thin cellulose fiber material that makes up the thin cellulose fiber non-woven fabric layer preferably contains 50% by weight to 100% by weight of pure cellulose fibers composed of cellulose, such as coniferous wood pulp, pulp deciduous wood, cotton-derived pulp, hemp-derived pulp (such as abaca hemp or sisal hemp), kenaf-derived pulp, bamboo-derived pulp, bagasse-derived hemp, bacterial cellulose, rayon, cupra or lyocell or fibers derived from cellulose, such as cellulose acetate, cellulose acetate propionate, cellulose butyrate acetate, carboxymethyl cellulose, carboxyethyl cellulose, nitrocellulose or methyl cellulose. If its content is less than 50% by weight, resistance to sufficiently high permeability is not acquired when the layer of non-woven fabric is formed, thus making it undesirable. Furthermore, from the point of view of resistance to high permeability, which is one of the characteristics of the multilayer structure of the present invention, the proportion of fine cellulose fibers in the fiber material that makes up the thin cellulose fiber nonwoven layer is preferably 70% by weight, and from the point of view of forming a layer having greater resistance to air permeability, the proportion of fine fibers of pure cellulose is more preferably 80% by weight or more and most preferably 90% by weight or most. As a result, a high resistance to permeability can preferably be achieved while, at the same time, achieving a high permeability to moisture. However, other fine fibers can also be mixed as long as the cellulose fiber content range is 50% by weight or more, and fine fibers, such as heat-melt polyethylene fibers, polypropylene fibers, polyketone fibers or fibers polyester can be contained in order to improve strength, for example.
[0037] The thin cellulose fibers that make up the thin cellulose fiber non-woven fabric layer are preferably cellulose microfibrils. Here, cellulose microfibrils refer to cellulose fibers and / or bundles thereof, having a fiber diameter of several nm to 200 nm, composed of natural cellulose or regenerated cellulose. More specifically, cellulose microfibrils refer to independent microfibrils, or thin fibers obtained by bundling them, pulled out from a fiber surface, which are obtained by performing a microfibrillation treatment with a device that applies a high degree of shear force, such as a high pressure homogenizer, ultra-high pressure homogenizer or crusher, on cellulose produced by acetic acid bacteria or other bacteria referred to as bacterial cellulose, or plant-derived cellulose, such as cellulose derived from pulp or animal, such as hoya cellulose collectively referred to as microfibrillated cellulose. In the present invention, microfibrillated cellulose in particular is preferably used as a raw material from the point of view of cost and quality control. In addition, yarn cut from regenerated cellulose fibers having a diameter of fine fibers, yarn cut from cellulose derived fibers having a diameter of fine fiber, regenerated cellulose obtained by electrospinning, or yarn cut from ultrafine yarn from cellulose derivatives can also be used as fine cellulose fibers.
[0038] The average fiber diameter of the thin cellulose fibers of the present invention is 0.005 μm to 0.5 μm. Here, the average fiber diameter of fine cellulose fibers refers to the average fiber diameter in number, as determined from the SEM images or TEM images of the surface, and conforms to the assessment means described in the Publication International No. WO 2006/4012. In general, non-woven fabric composed of cellulose fibers is said to tend to demonstrate an increase in thermal conductivity, as the diameter of the fiber becomes narrower, under conditions such that the porosity remains constant. As the fiber diameter increases, the density of the network of the fiber network that occupies a fixed space decreases, and since the efficiency of surface conduction, which contributes, as is thought, to thermal conduction, worsens, the thermal conductivity eventually decreases. The inventors of the present invention have found that by taking the fiber diameter of cellulose fibers to be 0.5 pm or less, an extremely dense layer, having a high resistance to permeability can be formed as a layer of nonwoven fabric at a weight low base, and since the nonwoven layer can be designed to have constituent fibers having a narrow fiber diameter and low base weight, a sheet having a relatively large thermal conductivity can be produced. On the other hand, since it is difficult to stably produce thin cellulose fibers with a fiber diameter of less than 0.005 pm, the fiber diameter of cellulose fibers is preferably 0.008 to 0.4 pm and more preferred 0.015 pm to 0.3 pm .
[0039] The thin cellulose fiber non-woven layer can be composed with a thin cellulose fiber non-woven fabric composed of thin cellulose fibers having a degree of polymerization (DP) of 100 to 12,000. Degree of polymerization is the number of repetitions of glucose rings that form the molecular chain of cellulose. By bringing the degree of polymerization to 100 or more, the tensile strength and elastic modulus of the fibers per se improves, and as a result, the strength of the non-woven fabric structure improves, and the ease of handling when fixing the an energy recovery ventilation element as well as quality stability when using an energy recovery fan improves. Although there is no particular upper limit on the degree of polymerization of thin cellulose fibers, it is substantially difficult to acquire cellulose having a degree of polymerization in excess of 12,000 and these cannot be used industrially. From the point of view of ease of handling and industrial applicability, the degree of polymerization of the cellulose fibers is preferably 150 to 8,000 and more preferably 300 to 6,000.
[0040] The surface or interior of the thin cellulosic fibers that make up the thin cellulose fiber nonwoven layer can be chemically modified. For example, fibers, in which some or most of the hydroxyl groups present on the surface of thin cellulose fibers (cellulose microfibrils) have been esterified, including acetic acid esters, nitric acid esters and sulfuric acid esters, fibers etherified compounds including alkyl ethers represented by methyl ether, carboxy ethers represented by carboxymethyl ether and cyanoethyl ethers, or fibers in which the hydroxyl groups in position 6 have been oxidized by a TEMPO oxidation catalyst (as a 2,2,6,6-tetramethylpiperidine radical) oxy) and converted to carboxyl groups (including acid forms and salt forms), can also be included.
[0041] The thin cellulose fiber nonwoven layer in the multilayer structure of the present invention has a low base weight, and as a result of this, it is important that the thickness of a layer is thin. In the present invention, because a dense thin layer, having a small pore diameter is formed, which is substantially composed of fine cellulose fibers, it can be designed to have a high permeability resistance and high moisture permeability. This is because, in addition to being able to be designed to have short water vapor permeation paths due to the thickness of the thin layer, since the layer is composed of thin fibers, the surface area of the fibers present within the layer becomes high, and the density of the migration path by area of water vapor unit that migrates through the interfaces between the fibers can be designed to be high, and as a result, permeability to high humidity can be demonstrated .
[0042] At the same time, due to the non-thick size of the thin, dense and non-thick cellulose fiber non-woven layer, together with the high density in which the constituent fine fibers are present per unit area (that is, internal interfacial area), the thermal conductivity of the surface at fiber interfaces can be protected, thus allowing the layer to be retained a high thermal conductivity.
[0043] The base weight (weight per unit area) of the thin cellulose fiber non-woven fabric layer in the multilayer structure of the present invention as the total sum thereof is within the range of 1 g / m2 to 15 g / m2 , preferably within the range of 2 g / m2 to 10 g / m2, and more preferably within the range of 3 g / m2 to 8 g / m2. Within these ranges, the three properties of resistance to permeability, moisture permeability and thermal conductivity can be demonstrated with appropriate balance. If the total sum of the base weight is less than 1 g / m2, it becomes difficult to uniformly maintain the permeability resistance at 2000 s / 100 ml 5 or more, whereas if the total sum of the base weight exceeds 15 g / m2, moisture permeability tends to decrease, thus making both cases undesirable. In addition, the "total base weight sum" refers to that determined by adding the base weight of each layer if the non-woven fabric consists of two or more layers. For example, in the case of coating the thin cellulose dispersion 10 over the nonwoven fabric by immersion coating, the resulting structure has three layers with a support located in the central layer (and comprising two layers of thin cellulose fiber nonwoven fabric) ). In addition, if the total sum of the thickness of the thin cellulose fiber nonwoven layer is 0.5 μm to 15 μm, more preferably 1 μm to 12 μm and most preferably 1.5 μm to 8 15 μm, the three properties of resistance to permeability, moisture permeability and thermal conductivity can be demonstrated in proper balance. If the total sum of layer thickness is less than 0.5 μm, it becomes evenly difficult to maintain the permeability resistance at 2000 s / 100 ml, whereas if the total sum of the layer thickness exceeds 15 μm, permeability at 20 humidity tends to decrease, thus making both cases undesirable. Here, the thickness of the thin cellulose fiber non-woven fabric layer refers to the value obtained by observing a SEM image in cross section of the multilayer structure of the present invention.
[0044] In the present invention as described above, although it is important to design the layers (s) of the thin cellulose fiber nonwoven fabric to be not thick and have a low base weight, because it becomes difficult to maintain a level of mechanical strength that allows manipulation as a sheet material over time with the thin cellulose fiber nonwoven layer alone, in the present invention, another porous sheet is used as a support, and one or more of the 30 layers are laminated over it to obtain a multilayer structure. The average thickness of the multilayer structure of the present invention, including the backing layer, is 10 μm to 200 μm, preferably 10 μm to 150 μm, more preferably 10 μm to 70 μm and even more preferably 10 μm to 30 μm. If the average thickness of the multilayer structure of the present invention is less than 10 μm, it becomes difficult to design the multilayer structure so as to have mechanical strength that does not present a problem in terms of handling, whereas if the average thickness exceeds 200 μm, the stiffness becomes excessively high for use as a sheet, which again results in problems in terms of handling, thus making this undesirable.
[0045] The total sum of the base weight (total weight per unit area) of the multilayer structure of the present invention is preferably 10 g / m2 to 100 g / m2. If the total base weight sum is less than 10 g / m2, resistance to air permeation and mechanical resistance are not obtainable. The structure of non-woven fabric having a base weight in excess of 100 g / m2 results in difficulty in obtaining an appropriate moisture permeability, while at the same time being disadvantageous from the point of view of thermal conductivity. The total sum of the base weight is preferably 12 g / m2 to 80 g / m2 and more preferably 14 g / m2 to 60 g / m2. Particularly in the case of the multilayer structure of the present invention being a multilayer structure having a two layer structure consisting of a backing layer and a layer of thin cellulose fiber non-woven fabric composed of thin cellulose fibers having an average fiber diameter of 0.005 μm to 0.5 μm, from the point of view of the appropriate balance between permeability resistance and moisture permeability and economic reasons, if the base weight of the thin cellulose fiber nonwoven layer is designed to be 1 g / m2 to 15 g / m2 and the base weight of the backing layer is designed to be 9 g / m2 to 99 g / m2, more preferably the base weight of the thin cellulose fiber nonwoven layer is designed to be 2 g / m2 to 10 g / m2 and the base weight of the backing layer is designed to be 10 g / m2 to 78 g / m2, and most preferably the base weight of the nonwoven layer fine cellulose fiber is designed to be 3 g / m2 to 8 g / m2 and the base weight of the backing layer is designed to be 11 g / m2 to 57 g / m2, high performance can be achieved as the multilayer structure previously described.
[0046] The density of the multilayer structure of the present invention is 0.10 g / cm3 to 0.90 g / cm3 and more preferably 0.30 g / cm3 to 0.80 g / cm3. Because the multilayer structure of the present invention has a structure in which a dense layer of thin cellulose fiber is laminated on a porous support, despite having an overall resistance to high permeability, it is also characterized by having low density like this type of material of leaf. If the density is less than 0.10 g / cm3, mechanical strength as a sheet material cannot be safe, thus making this undesirable, whereas in order to obtain a high density greater than 0.90 g / cm3 , the permeability resistance of not only the thin cellulose fiber layer but also of the backing layer becomes high and density increases, thus making this undesirable because it becomes difficult to demonstrate the effect of the present invention in the form of high moisture permeability. Here, density can be determined according to the following relational expression using the measured global base weight W (g / m2) and average global thickness D (μm) of the multilayer structure: Density (g / cm3) = W x (W2 ) 2 (g / cm2) / (D x 10'4) (cm) = W / D
[0047] In addition, the permeability resistance of the multilayer structure of the present invention (measured in accordance with a Japan Technical Association of Pulp and Paper Industry (TAPPI) pulp test method) is 2000 s / 100 ml or more . If the resistance to permeability is less than 2000 s / 100 ml, in the case of applying the multilayer structure of the present invention as an energy recovery ventilation sheet, for example, because not only moisture but also air will leak when air passes through the energy recovery ventilation sheet, hot air and cold air end up mixing, thus preventing the ventilation function from being demonstrated. In order to demonstrate the function as an energy recovery fan, resistance to permeability is preferably 3000 s / 100 ml or more, and in the case of using such an energy recovery ventilation sheet, resistance to permeability is preferably 4000 s / 100 ml or more. Although preferably the upper limit of resistance to permeability is the higher the better (bigger is better), it is preferably 10 million s / 100 ml or less because this is the detection limit of the measuring instruments.
[0048] As previously described, the proportion of fine cellulose fibers contained in the thin cellulose fiber nonwoven layer is 50% by weight to 100% by weight and preferably 70% by weight to 100% by weight. Although examples of other materials contained in the layer include fibrous materials composed of materials other than cellulose, inorganic fillers, polymers and inorganic particles, any such material can be contained, as long as the material allows a uniform and dense layer to form. to maintain resistance to permeability at 2000 s / 100 ml or more. If the proportion of thin cellulose fibers in the layer is less than 50% by weight, it becomes difficult to design a layer to have a permeability resistance of 2000 s / 100 ml or more, thus making this undesirable.
[0049] In the multilayer structure of the present invention, if a layer is a layer of non-woven fabric and / or porous film and / or fabric composed of one or a combination of a plurality of fibers selected from the group consisting of regenerated cellulose fibers , natural cellulose fibers, nylon fibers, polyester fibers and polyolefin fibers, high strength as a sheet material can be achieved without affecting the important elements of the present invention in the form of fine size and high moisture permeability of the fabric layer nonwoven of fine cellulose fiber. Examples of porous films include, but are not limited to, porous films composed of a polyolefin-based resin such as polyethylene or polypropylene, a nylon-based resin, such as polysulfone, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polycarbonate , nylon 6 or nylon 6.6, an acrylic resin such as poly (methyl methacrylate), polyketone and polyether ether ketone. Examples of fabrics include, but are not limited to, fabrics composed of cellulose fibers (including fibers from cellulose derivatives), nylon fibers, polyester fibers, polyurethane fibers and mixed yarns thereof. High humidity permeability is easily demonstrated if the resistance to permeability in the event of overlapping of all layers of nonwoven fabrics, porous films and other fabrics other than the thin cellulose fiber nonwoven layer used in the present multilayer structure invention (or a single layer in the case of a single layer) is 200 s / 100 ml, or less, and preferably 100 s / 100 ml or less.
[0050] The multilayer structure of the present invention preferably contains a nonwoven fabric, such as a layer other than a layer of fine cellulose fiber nonwoven fabric. From the point of view of resistance to moisture and, in particular, hydrophilic treatment, a non-woven fabric, composed of a material having hydroxyl groups or amide groups with reaction activity with cellulose or nylon and the like is preferable, and if the layer nonwoven fabric layer is a layer of nonwoven fabric consisting of regenerated cellulose fibers and / or a layer of nonwoven fabric composed of natural cellulose fibers (ie, a paper based material), the layer can be designed to have a high adhesive strength with the thin cellulose fiber nonwoven layer, thus making it preferable. Between these two types or a mixture thereof, a layer of nonwoven fabric composed of regenerated cellulose fibers having high hydrophilicity is most preferably selected as a layer from the point of view of improving moisture permeability.
[0051] Examples of the nonwoven fabric layer material composed of regenerated cellulose fibers used in the present invention include a type of two or more types selected from the group consisting of regenerated cellulose fibers, such as cupra, viscose rayon or polysonic rayon and refined cellulose obtained by spinning the solution. In addition, although short fibers or long fibers can be used for the shape of the fibers, long fibers are preferable and long continuous fibers are more preferable. In addition, although a short fiber nonwoven layer composed of natural cellulose fibers may be contained as a layer of the nonwoven structure in the present invention, examples of the material of the nonwoven layer in this case include wood pulp coniferous, deciduous wood pulp, cotton derived pulp, hemp derived pulp (such as abaca hemp or sisal hemp), kenaf derived pulp, bamboo derived pulp, bagasse derived hemp.
[0052] Here, in the case of selecting a non-woven fabric composed of regenerated cellulose fibers, a specific example of continuous long fibers is that of continuous long fibers of regenerated cellulose obtained by continuously spinning an undiluted cuprammonium rayon solution over a net according to a spinning method with downstream stretching, entangling the fibers by self-adhesion of the fibers per se, and hydro-entangling, as necessary, followed by formation in a non-woven fabric. A specific example of this is Bemliese® (Asahi Kasei Fibers Corp.). Because the continuous long fibers of regenerated cellulose (Bemliese) have a higher thermal conductivity and greater hygroscopicity than regenerated cellulose fibers such as rayon, they are used particularly preferably as a layer of the nonwoven fabric structure because they allow for a larger design. moisture absorption due to latent heat exchange. Because a large number of continuous long fibers that make up Bemliese self-adhere while coagulating in the spin bath, adequate strength can be achieved as a non-woven fabric even without entangling with high pressure water, as in the case of fabrics short fiber nonwovens, which is also preferable in terms of use as a layer of a nonwoven fabric structure.
[0053] Although long continuous fibers can be applied within a fineness range of 0.1 dtex to 3 dtex, in the case of use in the form of a fiber composite with fine cellulose fibers, the fineness is preferably within the range from 0.1 dtex to 1.0 dtex from the point of view of being able to maintain the entanglement resistance with thin cellulose fibers and reduce air permeability.
[0054] From the point of view of improving the efficiency of the manufacturing process, the multilayer structure of the present invention is preferably the two-layer structure consisting of a layer of thin cellulose fiber non-woven fabric composed of thin cellulose fibers and a support in the form of a layer of non-woven fabric or porous film, and for the additional reasons previously described, it is preferably a two-layer structure in the form of a non-woven fabric structure consisting of a layer of non-woven fiber fabric. thin cellulose composed of thin cellulose fibers and a layer of non-woven fabric composed of cellulose fibers regenerated from the point of view of being able to favorably demonstrate performance as an energy recovery ventilation sheet. In addition, from the point of view of retaining strength, the layer of nonwoven fabric composed of regenerated cellulose fibers is preferably a layer of nonwoven fabric composed of continuous long fibers of regenerated cellulose.
[0055] The tensile strength of the multilayer structure of the present invention is preferably 0.3 kg / 15 mm to 4.0 kg / 15 mm. If the tensile strength is less than 0.3 kg / 15 mm, because, for example, problems occur with tearing the sheet in one step to produce an energy recovery ventilation element using such a recovery recovery ventilation sheet. energy in the energy recovery fan production process, or the possibility of tearing during use increases, there is a risk that the multilayer structure will no longer function as an energy recovery ventilation sheet. Although the maximum tensile strength of this non-woven fabric structure is 4.0 kg / 15 mm, there is no particular upper limit for tensile strength, and the higher the tensile strength, the better it will be in terms of applying the multilayer structure for various applications. The tensile strength is more preferably 0.5 kg / 15 mm or more and even more preferably 0.8 kg / 15 mm or more.
[0056] In addition, the multilayer structure according to the present invention can preferably be used in applications requiring durability when undergoing waterproof treatment. Examples of waterproofing treatment means include the addition of an internally added additive such as sizing agent, wetting agent or crosslinking agent during the production of the multilayer structure and the coating of the waterproofing agent. during post-processing.
[0057] Examples of internally added waterproofing agents include, but are not limited to, sizing agents such as resin pitch soap, alkyl ketene dimers, succinic alkenyl anhydrides or polyvinyl alcohol, wetting agents, such as urea-formaldehyde resins, melamine formaldehyde or polyvinylamines resins, and crosslinking agents, such as polyamidoamine epichlorohydrin (PAE) or polyfunctional block isocyanates (BI). Among these, waterproofing agents, of the cross-linking type, in the form of PAE or BI are particularly preferred since they demonstrate extremely potent waterproofing effects and, when considering the negative zeta potential on the surface of fine cellulose fibers , the use of cationic BI or the PAE cationic compound is preferable since it allows the waterproofing effects to be demonstrated efficiently. Regarding waterproofing agents of the crosslinking type, since covalent bonds are formed with multifunctional isocyanates formed from BI when a support is used that is composed of cellulose (hydroxyl groups) or nylon (amide groups) having crosslinking reaction sites, the adhesive strength between the support and the thin cellulose fiber nonwoven layer can be increased, thus making it preferable. In addition, BI is a compound that provides stability in water by protecting polyfunctional isocyanates with agglomeration groups (such as amidoxima or ε-caprolactam) and as a result of being able to disperse stably in a used papermaking dispersion in a papermaking process, to be subsequently described, and by performing drying and heat treatment (usually at 130 ° C or higher) after papermaking, the agglomeration groups are eliminated and isocyanates are formed, resulting in a compound which reacts with surrounding reaction sites (hydroxyl groups or amide groups).
[0058] Examples of waterproof treatment carried out after processing include, but are not limited to, treatment with the diisocyanate crosslinking agent, such as hexamethylene diisocyanate or 4,4'-methylenebisphenyl diisocyanate in an organic solvent, and treatment in an aqueous medium with a melamine resin or a crosslinking agent such as diglycidyl ethylene glycol.
[0059] In addition, moisture permeability can be further improved if the multilayer structure of the present invention is subjected to hydrophilic treatment according to the purpose of use. For example, in order to improve the latent heat exchange rate in an energy recovery ventilation sheet, the performance of the hydrophilic treatment makes it possible to design a sheet to have a higher moisture permeability, thus being preferable. Exemplary means of hydrophilic treatment include a method consisting of imparting a high hydrophilicity to the surface and / or interior of a thin cellulose fiber layer by internal addition method, and a method consisting of introducing a hydrophilic compound into the surface layer of the structure multilayer by post-processing.
[0060] With respect to the internal addition method, a hygroscopic hydrophilic compound, which is cationic in a paper-making dispersion of fine cellulose fibers, can be added and adsorbed using the above-mentioned negative cellulose zeta potential, followed by formation dispersion of paper and lamination on a support to make a thin cellulose layer non-woven fabric more hydrophilic. This method is effective because it leads to the immobilization of the hydrophilic compound on the surface and / or interior of the thin cellulose nonwoven layer simultaneously to combine the use of a crosslinking agent in the above-mentioned waterproof treatment, internally add a hydrophilic compound, form a paper after it has adsorbed and is immobilized on the surface of the thin cellulose fibers and laminate on a support, and simultaneously obtaining the impermeability by progressing a crosslinking reaction attributable to the heat treatment. The hydrophilic compound used for this purpose is preferably a hydrophilic compound containing sites that react with the crosslinking agent in its molecular framework. In the case of using cationic BI for the waterproofing agent, examples of hydrophilic compounds having hydroxyl groups, amine groups or amide groups, and the like having reactivity with isocyanates include, but are not limited to, anionic and cationic polyvinyl alcohols (copolymers of vinyl alcohol and an anionic or cationic monomer vinyl).
[0061] Examples of post-processing methods include a method consisting of coating or spraying a solution or dispersion of a hydrophilic compound having high hydrophilicity over the multilayer structure, and a method consisting of immersing the multilayer structure in a solution of a hydrophilic compound followed by drying.
[0062] Examples of the hydrophilic compounds capable of being used in the aforementioned hydrophilic treatment include salts of inorganic acids, salts of organic acids, inorganic fillers, polyvalent alcohols, ureas and hydroscopic polymers (moisture absorber) (water-soluble polymers and hydrophilic polymers, capable of forming a hydrogel), and examples of moisture absorbers include salts of inorganic acids such as lithium chloride, calcium chloride or magnesium chloride, salts of organic acids such as sodium lactate, calcium lactate or sodium pyrrolidone carboxylate, inorganic fillers such as aluminum hydroxide, calcium carbonate, aluminum silicate, magnesium silicate, talc, clay, zeolite, diatomaceous earth, sepiolite, silica gel and activated carbon, examples of polyvalent alcohols include glycerin, ethylene -glycol, triethylene glycol or polyglycerin, ureas, such as urea or hydroxyethylurea, and hydroscopic polymers (absorber water), such as aspartic acid, polyacrylic acid, polyglutamic acid, polylysine, alginic acid, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyalkyl cellulose and salts or cross-linked products thereof, carrageenan, pectin, gellan gum, agar, xanthan gum, acid hyaluronic, guar gum, arabic gum, starch and cross-linked products thereof, polyethylene glycol, polypropylene glycol, collagen, acrylonitrile-based polymer saponification products, starch / acrylonitrile graft copolymers, acrylate / acrylamide copolymers, alcohol copolymers polyvinyl / maleic anhydride or polysaccharide / acrylate graft self-crosslinking products, and are used, selecting the type and quantity adhered to the purpose of use, as an extender or volume forming agent, in addition to use as an absorber of moisture. In addition, the inorganic fillers mentioned above refer to inorganic minerals or inorganic salts and the like, which are used as extenders or volume forming agents in addition to moisture absorption. There are also cases where it is effective to have a water-soluble polymer, including those described in the above description, salt of an inorganic acid and salt of organic acid present for the purpose of solidifying the moisture absorber (so that the water absorber humidity does not migrate during high humidity).
[0063] In addition, the present multilayer structure may also contain arbitrary additives in addition to the waterproofing agents mentioned above and hydrophilic compound within a range that does not affect the moisture permeability or air permeation resistance of the multilayer structure of the present invention.
[0064] Although additives other than waterproof agents and hydrophilic compounds (such as flame retardants in a total heat exchanger sheet) can be appropriately used to improve the performance of the multilayer structure of the present invention as previously described, its total content is preferably maintained at 30% by weight or less, more preferably 20% by weight or less and even more preferably 10% by weight or less of the total weight of the energy recovery ventilation sheet. When within these ranges, a high performance multilayer structure of the present invention can be provided. Because many of these types of additives are highly active as chemical substances instead of demonstrating effects for various purposes, if their total content exceeds 30% by weight, the durability of the base material in the form of the multilayer structure sheet of non-woven fabric from the present invention is significantly impaired, thus making it undesirable.
[0065] Because the multilayer structure of the present invention demonstrates high moisture permeability and high thermal conductivity, when the nonwoven fabric is used as an energy recovery ventilation sheet, for example, energy recovery efficiency can be significantly improved. More specifically, the nonwoven fabric structure of the energy recovery ventilation sheet of the present invention is able to demonstrate moisture permeability (as measured according to JIS L 1099 Method A-1) of preferably 5000 g / m2 / 24 h or more, more preferably 7000 g / m2 / 24 h or more and less, more preferably 8000 g / m2 / 24 h. the moisture permeability is preferably as high as possible when using as an energy recovery ventilation sheet.
[0066] Furthermore, although the multilayer structure according to the present invention is capable of achieving a comparatively high thermal conductivity within the range of 0.0100 W / (m K) to 0.1000 W / (mK), in the case to use the multilayer structure of the present invention as an energy recovery ventilation sheet, for example, as previously described, because thermal conductivity is substantially governed by the dense nonwoven layer of fine cellulose fiber serving as a resistant layer air, as a result of making this layer thin, high thermal conduction efficiency, ie a high sensitive heat exchange rate, can be demonstrated to be equal to or greater than the thermal conductivity value of the indicated multilayer structures in the examples.
[0067] As a result, the multilayer structure of the present invention can be applied in all applications that take advantage of high moisture permeability, high permeability resistance and comparatively high thermal conductivity in addition to the aforementioned energy recovery ventilation sheet . Examples of its applications include, but are not limited to, water treatment films such as those used in membrane distillation requiring high water vapor permeability, and clothing materials, requiring low water permeability (equivalent to high resistance permeability) and low water vapor permeability.
[0068] As previously described in part, the multilayer of the present invention is capable of imparting a high energy exchange rate when used as an energy recovery ventilation sheet. That is, in Figure 1 showing the structure of an energy recovery ventilation element (laminated cartridge referred to as an element) used in a particular type energy recovery fan, the multilayer structure of the present invention can preferably be used as a dividing material that divides the exhaust air and intake air due to the high resistance to permeability, high permeability to moisture and comparatively high thermal conductivity of the same.
[0069] The thin sheet is preferably used for the energy recovery ventilation sheet of the present invention based on requirements to reduce the size and improve the thermal conductivity of the energy recovery ventilation element, and the average total thickness thereof. is 10 μm to 200 μm, preferably 10 μm to 120 μm, more preferably 10 μm to 70 μm and even more preferably 10 μm to 30 μm. It becomes technically difficult to produce a sheet having an average thickness of less than 10 μm, while a sheet having an average thickness in excess of 120 μm suffers a considerable decrease in thermal conductivity, thus making this undesirable.
[0070] The energy recovery ventilation sheet of the present invention can also be designed to undergo flame retardation treatment. In particular, in the case of using this energy recovery ventilation sheet according to the present invention in an energy recovery fan installed in a building, it preferably has an incombustibility which is approved in the Incombustibility classification 2 or Incombustibility classification 3 of the Test Method for Incombustibility of Fine Materials for Construction (JIAA 1322). In addition, it most preferably has incombustibility which passes an incombustibility rating 2 or incombustibility rating 1. An example of this flame retardant treatment is a method consisting of coating a flame retardant on the aforementioned nonwoven fabric structure, and more specifically, it includes a method consisting of coating or spraying a flame retardant on the surface of the flame retardant structure. nonwoven fabric and a method consisting of immersing the nonwoven fabric structure in a flame retardant solution.
[0071] Examples of flame retardants that can be used in the present invention include inorganic flame retardants, inorganic phosphorus-based compounds, nitrogen-containing compounds, chlorine-based compounds, antimony trioxide, ammonium phosphate and compounds based on bromine, flame retardants that can be dispersed in water or an aqueous solution, such as antimony trioxide, ammonium phosphate, ammonium polyphosphate, ammonium sulfaminate, guanidine sulfaminate, guanidine phosphate, phosphoric amides, chlorinated polyolefins, ammonium bromide or cyclic polybromine compounds not based on ether.
[0072] The content of the aforementioned flame retardants is preferably 1% by weight to 15% by weight of the total heat exchanger sheet. If its content is less than 1% by weight, it is difficult to demonstrate the flame retardant effects. If the flame retardant is contained in excess of 15% by weight, moisture permeability and energy recovery efficiency decrease. The content of the flame retardant is more preferably 2% by weight to 10% by weight and more preferably 3% by weight to 8% by weight.
[0073] The following provides an explanation of an example of a method for producing the multilayer structure of the present invention.
[0074] The multilayer structure containing a layer of fine cellulose fiber non-woven fabric used in the present invention can be produced by first preparing an aqueous dispersion of thin cellulose fibers followed by deposition in the form of a film according to a method below using the aqueous dispersion.
[0075] All types of cellulose pulp, such as coniferous wood pulp or deciduous wood pulp, can be used as a raw material in the production of fine cellulose fibers. Examples of non-wood pulp include cotton-derived pulp, including cotton linter pulp, hemp-derived pulp, bagasse-derived pulp, kenaf-derived pulp, bamboo-derived cellulose and straw-derived pulp. The cotton-derived pulp, bamboo-derived pulp, bagasse-derived pulp, kenaf-derived pulp, bamboo-derived pulp and straw-derived pulp refer, respectively, to the refined pulp obtained by subjecting raw materials, such as linter cotton or cotton flakes, hemp Manila based on hemp (often produced in Ecuador or the Philippines), sisal, bagasse, kenaf, bamboo or straw for a refining stage or bleaching stage, as a delignification by digestion treatment. In addition, the paste derived from algae or cellulose based on refined ascidians can also be used as a raw material. In addition, cut yarns from refined cellulose fibers and cut yarns from cellulose-derived fibers can also be used as a raw material, and regenerated cellulose obtained by electrospinning, cut yarns from ultrafine cellulose derivatives, as well as raw materials from cellulose fibers. thin cellulose and thin cellulose fibers alone and can also be used as raw materials.
[0076] The following describes a method for reducing the diameter of cellulose fibers.
[0077] The reduction in the diameter of cellulose fibers is preferably carried out by passing through a pretreatment step, a batting treatment step and a size reduction step.
[0078] In the pre-treatment step, it is efficient to put the raw material paste in a state that facilitates the reduction of size by treatment in an autoclave by impregnation with water at a temperature of 100 ° C to 150 ° C, treatment with enzyme or a combination of them. Because this pretreatment not only reduces the burden of the downsizing treatment, but also the effect of causing impurities such as lignin or hemicellulose present on the surface in the gaps in the microfibrils comprising the cellulose fibers to be discharged in an aqueous phase, it thus results in an improvement of the a-cellulose purity of the resulting fibers, and the treatment is extremely effective in improving the heat resistance of thin cellulose fiber nonwoven.
[0079] In the batting treatment step, the raw material paste is dispersed in water in a solids concentration of 0.5% by weight to 4% by weight, preferably 0.8% by weight to 3% by weight, and more preferably 1.0% by weight to 2.5% by weight, and a high level of fibrillation is promoted with a beater device in the mode of a beater or disc refiner (double disc refiner). In the case of using a disc refiner, if treatment is carried out while fixing the gap between the discs to be as narrow as possible, (for example, 0.1 mm or less), because an extremely high degree of batting (fibrillation) occurs , there are cases where this is effective because the conditions of the downsizing treatment using a
[0080] The preferred degree of batting treatment is determined in the manner as indicated below.
[0081] In studies conducted by the inventors of the present invention, the value of the cut displaced fiber (CSF) (which indicates the degree of cellulose batting, and is assessed with the standard Canadian release test for pulp, as defined in the JIS document P 8121) decreased over time as the batting treatment progressed, and after temporarily approaching zero, it was confirmed to demonstrate a trend that causes it to increase again as the batting treatment continues, and in order to prepare the fine cellulose fibers that serve as raw materials for the structure of the non-woven fabric of the present invention, it has been determined that it is preferable to perform the pretreatment in the form of a batting treatment until the CSF value temporarily approaches zero followed by continuing the batting treatment until the CSF value starts to rise again. In the present invention, the CSF value, during the course of the CSF value decreasing from before the batting, is represented by *** Φ, while the CSF value that tends to increase after reaching zero is represented by * ** T. During the batting treatment, the CSF value is preferably at least zero and more preferably CSF 30T. In an aqueous dispersion (to be referred to as a slurry) prepared for this degree of batting, fibrillation progresses considerably so that it is simultaneously able to provide a filter medium, which does not contain coarse cellulose fibers having a maximum diameter fiber in excess of 2500 nm, the filter medium, being composed of a thin cellulose fiber non-woven fabric obtained from the slurry, tends to demonstrate an improved tensile strength perhaps from an increase in the number of stitches contact between cellulose microfibrils. In addition, a slurry that has been beaten to a high degree, having a CSF value of at least zero or subsequently having a value of *** T, demonstrates increased uniformity, while offering the advantage of an efficiency of improved production, where it is able to reduce clogging during the size reduction treatment attributable to the subsequent and similar high pressure homogenizer.
[0082] In order to produce fine cellulose fibers, the size reduction treatment is preferably carried out with a high pressure homogenizer, ultra high pressure homogenizer or crusher and similar after the aforementioned blending step. The concentration of solids in the aqueous dispersion at this time is 0.5% by weight to 4% by weight, preferably 0.8% by weight to 3% by weight, and more preferably 1.0% by weight to 2.5% in weight, according to the aforementioned batting treatment. The use of such a concentration of solids prevents clogging and allows an effective size reduction treatment to be achieved.
[0083] Examples of high pressure homogenizers used include the NS model high pressure homogenizer, manufactured by GEA Niro Soavi, the linear type high pressure homogenizer (Model R) manufactured by SMT Co., Ltd., and the homogenizer high pressure pumps manufactured by Sanwa Machinery Trading Co., Ltd., and devices other than those listed above can also be used as long as they are capable of reducing the size using almost the same mechanism as these devices. Ultra-high pressure homogenizers refer to high-pressure collision type micronization treatment machines, such as the microfluidizer manufactured by Mizuho Industrial Co., Ltd., the nanomizer, manufactured by Yoshida Kikai Co., Ltd. and the Ultimaizer device manufactured by Sugino Machine Ltd., and devices other than those listed above can also be used as long as they are capable of reducing the size using almost the same mechanism as these devices. Although examples of crusher-type micronization devices include mill crushers, exemplified by a Pure Fine Mill-type device manufactured by Kurita Machinery Mfg. Co., Ltd. and the Super Mass Colloider type devices manufactured by Masuko Sangyo Co., Ltd., devices other than those listed above can also be used as long as they are capable of reducing the size using almost the same mechanism as these devices. The thin cellulose fibers obtained in this way are commonly referred to as microfibrillated cellulose (MFC).
[0084] The fiber diameter of fine cellulose fibers can be controlled according to conditions during size reduction treatment using a similar high pressure homogenizer (such as the selected device, operating pressure and number of passes), or the conditions during pretreatment (treatment such as autoclave, enzymatic treatment or batting treatment) before the size reduction treatment.
[0085] In addition, the fine cellulose-based fibers obtained by subjecting the MFC produced according to the aforementioned process to chemical surface treatment and the thin cellulose-based fibers in which the hydroxyl groups in position 6 have been oxidized and converted to carboxyl groups (including acidic and basic types) with a TEMPO oxidation catalyst can also be used as thin cellulose fibers capable of being used in the present invention. In the case of the former, by carrying out various types of chemical surface treatment corresponding to a specific purpose, esterified forms, including acetic acid esters, nitric acid esters and sulfuric acid esters in which a portion or a greater part of the groups hydroxyls present on the surface of fine cellulose fibers (cellulose microfibrils) are esterified, or etherified forms, including alkyl ethers, represented by methyl ether, carboxy ethers represented by carboxymethyl ether and cyanoethyl ether, can be conveniently prepared and used. In addition, in preparing the first, that is, thin cellulose in which the hydroxyl groups in position 6 have been oxidized with a TEMPO oxidation catalyst, a dispersion of thin cellulose can be obtained without necessarily requiring the use of a size reduction device requiring the use of a lot of energy as a high pressure homogenizer. As described in the literature (A. Isogai, et al., Biomacromolecules, 7, 1687-1691 (2006)), for example, by adding an oxidizing agent in the form of hypochlorous acid to an aqueous dispersion of natural cellulose in the presence of a catalyst referred to as a TEMPO catalyst as a 2,2,6,6-tetramethyl piperidine oxide radical and alkyl halide allowing the reaction to proceed for a fixed period of time, a dispersion of fine cellulose fibers can be obtained with extreme ease of a refining treatment, such as rinsing with water, followed by treatment in a common mixer. Carboxyl groups are known to be introduced to the surface of thin cellulose fibers obtained with a TEMPO catalyst, and due to this high hydrophilicity, high moisture permeability is also achieved using these thin cellulose fibers as a raw material of the present invention.
[0086] In the following, a description is given of a method (membrane obtaining method) for forming a multilayer structure containing thin cellulose fibers and the support layer used in the present invention.
[0087] The multilayer structure is preferably produced using a papermaking method for the membrane obtaining method. Although the multilayer structure can also be formed using a coating method, film deposition according to the papermaking method is preferable from the point of view of proper entanglement in the nonwoven fabric or other support layer and being able to deposit a film with extremely few defects. In either method, an aqueous dispersion of fine cellulose fibers is spread or coated on various types of substrates, as previously described followed by lamination.
[0088] The following provides an explanation of the method for forming a layer of nonwoven fabric composed of thin cellulose fibers contained in the multilayer structure using a papermaking method.
[0089] This method is a method for producing a multilayer structure comprising the three steps of (1) a preparation step to prepare an aqueous dispersion containing 0.05% by weight to 0.5% by weight of fine cellulose fibers and 85% by weight to 99.5% by weight of water, (2) a papermaking step to obtain the concentrated composition in which the concentration of fine cellulose fibers has been increased in addition to the aqueous dispersion by dehydrating a portion of the water that makes up the aqueous dispersion on a support placed on a paper-making machine, and (3) a drying step to evaporate and remove a portion of the water from the concentrated composition by heating the concentrated composition. The multilayer structure of the present invention can be produced preferably using the papermaking method in step (2).
[0090] The method for forming a layer of thin cellulose fiber nonwoven fabric by a papermaking method using the aforementioned aqueous dispersion is to deposit a continuous strip of wet paper on a support in the form of a nonwoven fabric. , porous film or fabric having the contents described above on wires or filter paper by a papermaking method from a determined aqueous dispersion of fine cellulose fibers, produce a continuous strip of wet paper having a laminated structure by laminating the same depending on the case, and then drying the wet paper strip (drying the complete wet paper strip laminate in the case of a laminate).
[0091] The following provides a detailed explanation of the three steps mentioned above.
[0092] The aqueous dispersion of the thin cellulose fibers used in the preparation step is preferably an aqueous dispersion containing 0.01% to 0.5% by weight of thin cellulose fibers and 85% by weight to 99.99% by weight of water.
[0093] The concentration of fine cellulose fibers in the aqueous dispersion for papermaking is preferably 0.01% by weight to 0.5% by weight and more preferably 0.03% by weight to 0.35% by weight. If within these ranges, papermaking can be performed stably. If the concentration of fine cellulose fibers in the aqueous dispersion is below 0.01% by weight, the filtering time becomes extremely long and the productivity becomes extremely low, while at the same time, the uniformity of the film quality is makes it extremely low, thus making it undesirable. In addition, if the concentration of the thin cellulose fibers is greater than 0.5% by weight, the viscosity of the dispersion increases excessively and uniform film deposition becomes difficult, thus also making this undesirable.
[0094] Although the solvent in the papermaking dispersion of fine cellulose fibers may be just water, it is also effective to add various types of compounds in order to control physical properties such as moisture permeability or resistance to permeability depending on particular case.
[0095] In the case of designing the thin cellulose fiber non-woven fabric layer to have a comparatively high porosity in order to improve moisture permeability, add a solvent in the form of an organic solvent that dissolves in water or an organic solvent hydrophobic which does not dissolve in water to form an aqueous solution of the organic solvent or emulsion of the organic solvent, respectively, can be effective. Examples of organic solvents that dissolve in water include, but are not limited to, ethanol, methanol, isopropanol and celosolves such as methyl celosolve, while examples of hydrophobic organic solvents that do not dissolve in water include, but are not limited to, hydrocarbons such as n- decane or toluene and long-chain alcohols, such as 1-hexanol. When assuming that the used organic solvent will be removed in a drying step to be subsequently described, the organic solvent preferably has a boiling point of 160 ° C or lower. In addition, the amount of organic solvent used out of the total amount of solvent in the composition is preferably 10% by weight or less and more preferably 3% by weight or less for economic reasons. In these ranges, the multilayer structure of the present invention can be obtained comparatively inexpensively.
[0096] In this papermaking method, there are cases in which resistance to moisture and greater hydrophilicity can preferably be conferred if the waterproofing agents and hydrophilic compounds mentioned above, that is, waterproofing agents such as sizing, wetting agents or crosslinking agents, and hydrophilic compounds, such as salts of inorganic acids, salts of organic acids, inorganic fillers, polyvalent alcohols, ureas or (moisture absorber) hygroscopic polymers (water-soluble polymers and polymers hydrophilic, capable of forming a hydrogel), are added to the papermaking dispersion in order to increase moisture permeability. Although it is only necessary to add waterproof agents and / or hydrophilic compounds in the amounts in which they are effective, they are preferably added within a range that does not impair the stability of the undiluted paper-making solution. For example, in the case of the addition of a hygroscopic polymer (moisture absorber), the hygroscopic polymer (moisture absorber) improves moisture permeability while, at the same time, acting effectively as a reinforcement binder while remaining efficient on the cellulose surface. Moisture permeability can be increased by dissolving or finely dispersing a hygroscopic polymer (moisture absorber) in the aqueous phase of the aqueous dispersion used in the present papermaking method, and which contains a water-soluble polymer in the non-woven layer fine fiber fabric. The concentration of hygroscopic polymer (moisture absorber) is preferably from 0.003% by weight to 0.3% by weight, more preferably 0.005% by weight to 0.08% by weight, and even more preferably 0.006% by weight at 0, 07% by weight. If it falls within these ranges, simultaneously with the fact that it is easy to obtain the fine cellulose fiber non-woven fabric used in the present invention, there are many cases where the state of the aqueous dispersion is stabilized, thus making this preferable. If the concentration is less than 0.003% by weight, it is difficult to demonstrate the effect of adding the hygroscopic polymer (moisture absorber), thus making this undesirable, whereas, if the concentration is greater than 0.3% by weight, note there is an increased susceptibility to the occurrence of negative effects, such as foaming that accompanies the increase in the amount added, thus making this undesirable. In addition, a surfactant may be contained in the hygroscopic polymer (moisture absorber) in the aqueous dispersion in order to stabilize the aqueous dispersion provided that the total amount of water-soluble polymer mentioned above is specified within the above mentioned range.
[0097] Examples of surfactants in this include anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl sulfate ester salts, alkyl benzene sulfonates or α-olefin sulfonates, cationic surfactants such as trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride or chloride of ammonium chloride benzalkonium, amphoteric surfactants such as trimethylglycine, alkyl dimethyl betaine aminoacetate or alkyl amidodimethyl betaine aminoacetate, and nonionic surfactants such as alkyl polyoxyethylene ethers or glycerol fatty acid esters, although not limited to them.
[0098] In addition, several additives can be added to the aqueous dispersion corresponding to the specific use. For example, in addition to additives added for waterproofing or flame retardancy purposes, particulate inorganic compounds in the form of silica particles, alumina particles, titanium oxide particles or calcium carbonate particles, fine resin particles, various types of organic salts or solvents, to a degree that does not impair the stability of the aqueous dispersion, can be added within a range (in terms of selection of the type of additive and selection of the composition) that has no detrimental effect on the production of the structure multilayer of the present invention. In addition, short fiber materials, other than fine cellulose fibers in the form of fiber materials, such as polyester fibers, nylon fibers, acrylic fibers, aramid fibers or cellulose acetate fibers, or fillers, such as titanium oxide, zinc oxide wires, glass fibers or carbon fibers can also be contained in the aqueous dispersion.
[0099] The weight percentage of water in the aqueous dispersion is such that the thin cellulose fibers are dissolved or dispersed in the water in a composition containing 85% by weight to 99.99% by weight, preferably 90% by weight to 99, 98% by weight and more preferably 92% by weight to 99.97% by weight of water. If the amount of water in the aqueous dispersion is less than 85% by weight, there are many cases where the viscosity increases, making it difficult to uniformly disperse the slurry in the dispersion while also making it difficult to obtain a layer of nonwoven fabric composed of fibers thin cellulose having a uniform structure, thus making this undesirable. In addition, if the amount of water in the aqueous dispersion exceeds 99.99% by weight, the cellulose content of the composition in which it is incorporated decreases and the water drainage during papermaking becomes extremely low, which has a detrimental effect on productivity, thus making this undesirable.
[00100] Preparation of the aqueous dispersion is carried out by mixing all the additives in water to obtain an aqueous dispersion of slurry by an appropriate dispersion method, or by mixing an aqueous solution preliminarily containing additives with an aqueous dispersion prepared separately from fine cellulose fibers for obtain an aqueous dispersion. At this time, low-speed or high-speed agitation with a (domestic) mixer or disperser having disper-type blades, or using a high pressure homogenizer under appropriately controlled conditions, is preferably used for mixing and dispersing methods.
[00101] The second step of obtaining a membrane carried out by a papermaking method is the papermaking step consisting of filtering the fine cellulose fibers on a support by dehydrating the aqueous dispersion prepared in the first step with the papermaking machine. paper and concentrating the aqueous dispersion to laminate the support layer and concentrated layer or integrate in a single unit. The papermaking step can be basically performed by any type of device as long as it is a device that uses a filter or filter fabric (also referred to as wires in the technical papermaking field) so that the water is dehydrated from of the water-containing dispersion and the thin cellulose fibers remain on the support layer.
[00102] The use of a device in the form of an inclined wire-type paper making machine, fourdrinier paper making machine or cylinder paper making machine for the paper making machine allows obtaining a multilayer structure containing a layer of thin sheet-type cellulose fiber nonwoven preferable having few defects. The paper making machine can be of the continuous or discontinuous type and each type can be used corresponding to the particular purpose.
[00103] Although dehydration is carried out by the papermaking step using the aqueous dispersion (for papermaking) obtained in the aforementioned preparation step, because the papermaking step is a step to filter a soft cellulose aggregate fine and similar dispersed in the aqueous dispersion using wires or filter fabric, even if the support layer is interposed therein, the opening size of the wires or filter fabric is important. In the present invention, any filter wires or fabrics can be used provided that the aqueous dispersion for papermaking, prepared in accordance with the conditions mentioned above, can be substantially manufactured on paper in a percentage yield of water-insoluble components, including cellulose, contained in the dispersion of 70% by weight or more, 15 preferably 95% by weight or more and more preferably 99% by weight or more. In the production of the multilayer structure of the present application, a support in the form of a non-woven fabric and / or porous film and / or fabric is provided for the lower layer, and because papermaking is performed on it, depending on the support , the support alone can retain a high percentage of yield of fine cellulose fibers. In such cases, a metal mesh or plastic thread used in the manufacture of plain paper can be used.
[00104] However, even if the percentage of pulp and similar yield is 70% by weight or more, papermaking takes considerable time unless drainage is high, and because the efficiency of production is 25 makes it remarkably weak, the amount of water permeation of the wires or filter fabric at 25 ° C and atmospheric pressure is preferably 0.005 ml / cm2 s or more, and more preferably 0.01 ml / cm2 s or more. If the amount of permeation water is within these ranges, preferable papermaking is possible from the point of view of productivity. If the yield percentage of the water-insoluble components mentioned above is lower than 70% by weight, not only does the productivity decrease considerably, but the cellulose and water-insoluble components end up clogging the inside of the wires and filter fabric used, and the ability to detach the multilayer structure after deposition becomes remarkably weak.
[00105] Here, the amount of water permeation of the wires or filter fabric at atmospheric pressure is evaluated in the manner described below.
[00106] When installing the wires or filter fabric to be evaluated on a batch-type papermaking machine (such as an automated square sheet machine, manufactured by Kumagai Riki Kogyo Co., Ltd.), in the case of wires, wires are used as such, while in the case of a filter fabric, the filter fabric is placed on a metal mesh of 80 to 120 mesh (having hardly any resistance to water filtration), an appropriate amount of water (indicated as y ml) is poured into the papermaking machine having a papermaking area of x cm2, and the drain time is measured in atmospheric pressure. The amount of water permeation in the case of a drain time of z s (seconds) is defined as y / (xz) (ml / cm2 s).
[00107] Examples of filters or filter cloth that can be used for extremely thin cellulose fibers include, but are not limited to, Tetexmono DLW07-8435-SK010 (made from PET) manufactured by Sefar AG (Switzerland), and NT20 ( made of a mixture of PET and nylon) manufactured by Shikishima Canvas Co., Ltd. The multilayer structure of the present invention can also preferably be produced using an endless filter type, as described in the unexamined JP Patent Publication No. 2011- 042903 as a wire belt. However, because there are cases where the support itself has the ability to be used as a filter fabric as previously described, the use is not limited to that described above.
[00108] During the dehydration of the papermaking stage, a fine cellulose fiber concentrate in the form of a continuous wet paper strip is obtained by increasing the solids content on the preliminarily inserted support layer or inside the support layer. The solids content of the continuous wet paper strip is adjusted so that the solids concentration is preferably 6% by weight to 60% by weight and more preferably 10% by weight to 50% by control of the suction pressure during papermaking (both wet and dry suction) and the degree of dehydration in the pressing stage. If the solids concentration is such that the solids content is lower than 6% by weight, a large amount of energy is required for drying, making this disadvantageous in terms of production costs. In addition, vacuum dehydration requiring a considerable amount of energy is required to dehydrate at a concentration where the solids content of the continuous wet paper strip exceeds 60% by weight, thus making this unrealistic.
[00109] In addition, a method can also be used which consists of making paper on filter fabric, and replacing the water in the resulting wet paper strip with an organic solvent in an organic solvent replacement step followed by drying. Although this method is effective if it is expected to have a high porosity in order to improve the permeability to moisture, because the resistance to permeability decreases compared to the case of not replacing with an organic solvent, the type and composition of the organic solvent are determined based on the balance between the two. Its details are in accordance with International Publication No. W02006 / 004012.
[00110] That is, when placing the support on a papermaking machine installed with wires or filter fabric, dehydrating a portion of the water that makes up the aqueous dispersion on the support (papermaking), laminating the continuous strip of paper wet of the thin cellulose fiber non-woven fabric composed of thin cellulose fibers on the support, and integrating in a single unit, a laminated sheet can be produced, which is composed of at least two layers of multilayer structures. A support having two or more layers of multilayer structures is used to produce a laminated sheet having three or more layers. In addition, a multilayer sheet having three or more layers can also be obtained by performing paper making in multiple stages on the thin cellulose fiber nonwoven fabric of the present invention having two or more layers on a support. After the multilayer structure of the present invention has been produced by papermaking, it is laminated with a different support (non-woven fabric, porous membrane or fabric) or the multilayer structure of the present invention separately produced by treatment with hot pressing and the like and integrated into a single unit.
[00111] Here, in the case of a typical papermaking method for an aqueous dispersion, the aqueous dispersion is sprayed on the wires at room temperature. By setting the papermaking temperature at a temperature of 30 ° C to 80 ° C, which is higher than the normal temperature, in particular, a multilayer structure can be produced more stably which combines high resistance to permeability , high moisture permeability and comparatively high thermal conductivity. In particular, if the papermaking temperature is 40 ° C or higher, due to the high degree of swelling of each thin cellulose fiber, the surface tension between the fibers during papermaking becomes stronger, it becomes easier to adopt a densely packed structure extending into the structure of the non-woven structure and, as a result thereof, the multilayer structure is designed to demonstrate a high resistance to permeability and comparatively high thermal conductivity. Although a structure similar to that of the present invention can be produced even if the temperature exceeds 80 ° C, the quality is no longer stable because the moisture in the dispersion ends up evaporating.
[00112] The multilayer structure of the present invention is obtained from the continuous wet paper strip obtained in the papermaking step by evaporating a portion of the water in the drying step that is carried out by heating. If a type of fixed-length drying dryer such as a drum dryer device is used in the papermaking step it is used in the drying step, which is able to dry the water while keeping the width at a constant length with the continuous strip of damp paper sandwiched between the dryer surface and the felt, a multilayer structure having high resistance to permeability can be obtained in a stable manner, thus making this preferable. Although the drying temperature is appropriately selected according to the conditions, it is preferably within the range of 80 ° C to 180 ° C and more preferably within the range of 90 ° C to 150 ° C. If within these ranges, the multilayer structure of the present invention can preferably be produced. If the drying temperature is lower than 80 ° C, because the rate of water evaporation is excessively slow in many cases, the appropriate productivity is unable to be fixed, thus making this undesirable, whereas if the drying temperature exceeds 180 ° C, there are cases where the hydrophilic polymer that makes up the multilayer structure ends up suffering thermal denaturation and the energy efficiency, which has an effect on cost, also decreases, thus making this undesirable. Depending on the case, drying in stable multiples can also be carried out where the initial drying is carried out at a low drying temperature of 100 ° C or lower followed by a temperature of 100 ° C or higher in the next stage, and this is also effective in obtaining a highly uniform multilayer structure.
[00113] In addition, in the case of incorporating a crosslinking agent in the papermaking dispersion as an internally added additive in order to be waterproof, as previously described, it is important to provide a heat treatment step separate from the drying step mentioned above to let the crosslinking reaction proceed. Although it is naturally preferable to set the appropriate reaction temperature of the crosslinking agent, because many crosslinking agents used as internally added additives react with hydroxyl groups on the surface, and the like, in an atmosphere where water has been removed, the temperature of the heat treatment is 100 ° C or greater, and in consideration of completing the reaction, the temperature of the heat treatment is 120 ° C or greater, and preferably 130 ° C or greater.
[00114] A post-processing step in the form of a coating treatment or chemical treatment step and / or a calender treatment step to adjust the average thickness (which is normally performed for the purpose of reducing the thickness) are performed , as necessary, for the multilayer structure of the present invention obtained in the steps mentioned above.
[00115] The post-processing step is performed to provide the necessary functions by post-processing instead of internal addition. For example, in the case of producing an energy recovery ventilation sheet, a liquid coating of a prescribed moisture permeability agent or flame retardant having the previously described levels (which may consist of an aqueous system or organic solvent system ) is prepared followed by spray coating or one-step coating employing a printing method or coating method and the like and drying. In the case of chemical treatment, the reaction is allowed to proceed by carrying out the heat treatment in the same way as an internal addition method after the drying step.
[00116] In addition, if a calendering treatment step is provided for smoothing or reducing the thickness of the multilayer structure obtained in the aforementioned drying step with a calendering device, a multilayer structure having an average thickness of 15 μm to 30 μm it can be produced stably as a preferred embodiment of the present invention. That is, by including a step to carry out the smoothing treatment on the multilayer structure after drying with the calendering device, the thickness of the multilayer structure can be reduced and the multilayer structure of the present invention can be obtained comprising a layer of non-woven fabric. thin cellulose fiber fabric having the combination of medium thickness, air permeability and resistance over a wide range. For example, a multilayer structure can easily be produced having an average thickness of 30 μm or less (lower limit of about 3 μm) when attached to an overall base weight of 30 g / m2 or less. As a result of the calendering treatment step, extremely tiny holes in the layer composed of fine cellulose fibers of the present invention are filled, pore size diameter is averaged, and air permeation performances in terms of permeability and resistance moisture permeability are significantly stabilized. In addition to common calendering devices using a single press roller, supercalendering devices having a structure in which they are arranged in multiple stages can also be used for the calendering device. A multilayer structure having superior performance as an energy recovery ventilation sheet can be obtained by selecting these devices corresponding to the particular purpose together with the materials (according to the material hardness) on both sides of the rollers and the linear pressure during the calendering treatment. For example, a multilayer structure having an average thickness within the ranges previously described can preferably be produced by combining a metal roller and a plastic roller of high hardness, a metal roller and a cotton roller, and a metal roller and a rubber roller. aramid for roller materials.
[00117] In meeting the conditions mentioned above, a multilayer structure comprising a layer of nonwoven fabric composed of fine cellulose fibers can be provided, and an energy recovery ventilation sheet can be provided, which is composed of the multilayer structure .
[00118] As a result of an energy recovery fan using an energy recovery ventilation element, wherein the energy recovery ventilation sheet of the present invention is used as a dividing material that divides two types of air from different temperature, humidity or both, easily conducting sensitive heat due to the high moisture permeability and thermal conductivity of an energy recovery ventilation sheet of the present invention, not being covered with a thick film, and only dividing air with a fabric structure nonwoven that has only a thin film or holes that are full, it demonstrates a superior heat exchange capacity. In addition, because split closed portions are thin, moist air is able to permeate more easily than conventional energy recovery ventilation sheets, thereby enhancing the moisture retention effect.
[00119] An example of a specific method using the energy recovery ventilation element mentioned above is an energy recovery fan that combines the energy recovery ventilation element with a supply fan and a discharge fan. The air fed in the form of external air and the like is sucked into the energy recovery ventilation element by the power fan where it contacts the energy recovery ventilation sheet incorporated within the energy recovery ventilation element. On the other hand, the air discharged in the form of internal air and the like is sucked into the energy recovery ventilation element by the discharge fan where it similarly contacts the energy recovery ventilation sheet.
[00120] The fed and discharged air that made contact through the energy recovery ventilation sheet undergo a heat exchange when they demonstrate the behavior of either feeding or discharging corresponding to temperature and humidity. The fed air that has undergone heat exchange is blown into the supply fan and is carried into a room, or example. On the other hand, the discharged air that has undergone heat exchange is blown into the discharge fan and is discharged outside, for example.
[00121] When heat exchange is carried out using a heat exchanger provided over one or a plurality of energy recovery ventilation elements in the form of an energy recovery ventilation element using the multilayer nonwoven fabric of the present invention for energy recovery ventilation sheet, heat exchange can be carried out efficiently, and the effectiveness of an energy recovery fan that maintains thermal effects by cooling and heating can be further enhanced while suppressing the discharge of heat or cold inside of the building and performing ventilation by discharging indoor air containing volatile organic compounds and having increased levels of carbon dioxide. EXAMPLES
[00122] The following presents a detailed explanation of the present invention by listing its examples.
[00123] In addition, the main measured values of physical properties were measured using the methods indicated below. (1) Average fiber diameter of fine cellulose fibers
[00124] Three locations on the surface of the multilayer structure composed of thin cellulose fibers are observed randomly with a scanning electron microscope (SEM) with an enlargement factor equivalent to 10000x to 100000X corresponding to the fiber diameter of the fine fibers. The lines are drawn on the screen horizontally and vertically for the resulting SEM images, and the fiber diameters of the fibers intersecting with the lines are measured from enlarged images followed by counting the number of fibers that intersect and the fiber diameter each fiber. The average fiber diameter in number is then calculated using the results of two sets of measurements in the vertical and horizontal directions for each image, and the results for a total of three images are averaged and used as the average fiber diameter of the sample. target. (2) Base weight (weight per unit area)
[00125] Evaluation of base weight W (g / m2) of the multilayer structure is calculated according to JIS P-8124. (3) Average thickness (μm)
[00126] A humidified multilayer structure was measured for thickness at 10 locations in the direction of width for each of the sheets with an automatic micrometer manufactured by Hi-Bridge Co., Ltd. followed by using the average value of the same as the average thickness of the multilayer structure (4) Density (g / cm3)
[00127] Density of the multilayer structure was calculated according to the following equation from the base weight W and the average thickness D mentioned above. Density (g / cm3) = W / D (5) Resistance to permeability (s / ml)
[00128] The area of a multilayer structure measuring 25 cm on one side was divided into 10 equal portions and the permeability resistance was measured using an Oken permeability resistance tester (Model EG01, Asahi Seiko Co., Ltd. ) for the 10 divisions followed by averaging 10 locations and using the resulting value as the air permeability resistance of the sample. (6) Tensile strength
[00129] Tensile strength was assessed according to the method defined in JIS P 8113, and 10 samples having a width of 15 mm were measured using the horizontal table tensile tester (No. 2000) manufactured by Kumagai Riki Kogyo Co., Ltd. followed by using the resulting average value as the tensile strength value. (7) Permeability to moisture
[00130] Resistance to humidity (g / m2-24 h) for 24 hours, as determined by measuring relative humidity at 90% (RH) in an environment where air was circulated at 40 ° C according to Method A-1 described in JIS L 1099, was measured as initial moisture permeability for each multilayer structure. (8) Thermal conductivity (W / m / K)
[00131] The non-woven fabric structures respectively cut to a size of 100 mm x 100 mm were placed between test plates (50 mm x 50 mm) at a temperature of 29.9 ° C for the upper plate and a temperature of 22.3 ° C for the bottom plate in an atmosphere at an ambient temperature of 20 ° C and a relative humidity of 65%, followed by measuring the heat flow of 60 seconds using the K ES- high-speed thermal property measurement system F7 Thermo Labo II manufactured by Kato Tech Co., Ltd. and calculating the thermal conductivity from this value. (9) Durability
[00132] After measuring the moisture permeability of the multilayer structure, the multilayer structure was maintained for 1 hour at 25 ° C and 50% RH followed by placing the multilayer structure in a fixed-length frame and storing the multilayer structure for 48 hours in a desiccator set at a temperature of 30 ° C and humidity of 99% or more for a fixed area. Subsequently, after maintaining for 1 hour at 25 ° C and 50% RH for each fixed-length frame, the multilayer structure was removed from the fixed-length frame, moisture permeability was measured following the same procedure as described in (7) above , and moisture permeability after high temperature hysteresis was used as an indicator to evaluate the moisture permeability durability of the energy recovery ventilation sheet. [Example 1]
[00133] Cotton linter paste was immersed in water at a concentration of 10% by weight followed by undergoing heat treatment for 4 hours in an autoclave at 130 ° C and repeatedly rinsing the resulting swollen paste with water to obtain immersed swollen paste in water.
[00134] The swollen pulp was dispersed in water at a solids content of 1.5% by weight to obtain an aqueous dispersion (400 L) followed by continuation with a beat treatment for 20 minutes in 400 L of the aqueous dispersion using a refiner. disc in the form of SDR14 Labo refiner model (pressurized disc type) manufactured by Aikawa Iron Works Co., Ltd. at a disc clearance of 1 mm, and continuing with churn treatment under conditions so that the clearance was subsequently reduced to almost zero. When samples were taken with time and evaluated according to the Canadian standard release test (abbreviated CSF) for paste, as defined in JIS P 8121 to determine CSF values, CSF values were determined to decrease over time, and when batting treatment was still continued since the CSF values had approached zero, they were confirmed to demonstrate an increasing trend. The whipping treatment was further continued under the conditions mentioned above to obtain a whipped slurry having a CSF value of 73 mlT. The resulting beaten slurry was then subjected to five size reduction treatment cycles at an operating pressure of 100 M Pa using a high pressure homogenizer (Model NS015H manufactured by GEA Niro Soavi) to obtain aqueous M1 dispersion of cellulose fibers fine (solids concentration: 1.5% by weight). Next, M1 was diluted with water to lower the solids concentration by 0.1% by weight followed by dispersion for 4 minutes at room temperature with a household mixer to prepare the papermaking dispersion.
[00135] Cupra rayon nonwoven fabric (trade name: Bemliese® T N150, Asahi Kasei Fibers Corp., base weight: 15 g / m2, thickness: 50 μm, density: 0.28 g / cm3, fiber fineness single mean: 0.2 dtex) was used for the base material, and papermaking was carried out by laminating a thin cellulose fiber layer over it. That is, a simple blend of woven / nylon PET (NT20, Shikishima Canvas Co., Ltd., moisture permeation at 25 ° C: 0.03 ml / cm2 s) was placed as a filter fabric in a manufacturing machine batch type paper (automated square sheet machine, Kumagai Riki Kogyo Co., Ltd., papermaking area: 25 cm x 25 cm, 80 mesh), the aforementioned cupra rayon non-woven fabric was placed on the same, and the papermaking dispersion prepared as described above was added in an equivalent amount based on the formation of a layer of cellulose non-woven fabric having a base weight of 10 g / cm2 followed by performing the papermaking (dehydration) at a vacuum level of 4 K Pa relative to atmospheric pressure. The same filter fabric was placed on the resulting two-layer wet paper strip formed on filter fabric and with the wet paper strip pressed on both sides, the wet paper strip was pressed for 1 minute at a pressure of 1 kg / cm2, followed by contact with the drum surface of a drum dryer fixed at a surface temperature of 130 ° C while in the form of three layers consisting of the filter fabric, continuous strip of wet paper and the other filter fabric and drying for about 120 seconds. The filter fabrics were able to be easily detached from both sides of the resulting three-layer sheet to obtain a dried sample S1. Although S1 has a double layer structure, as previously described, the tensile strength when completely integrated in a single unit was 1.4 kg / 15 mm, thus indicating that it is a sheet-like structure having an appropriate strength ( base weight: 25 g / m2).
[00136] When the surface on the side of the S1 thin fiber layer was subjected to SEM image analysis at a magnification factor of 10000X, the average numerical fiber diameter of the thin cellulose fibers on the surface of the thin cellulose fibers was 104 nm. Figures 2 and 3 respectively show SEM images of the top surface (side of the thin fiber layer) and back surface (side of the support layer) of S1. Their patterns are clearly different, and a laminated structure has been determined to have been formed. In addition, the thickness of the thin cellulose fiber layer of S1 as determined from the SEM image of cross-section was 7.1 μm. An investigation of the physical properties of S1 and its suitability for use as an energy recovery ventilation sheet has revealed that it has a high performance (high moisture permeability and high durability) as an energy recovery ventilation sheet as indicated in the following Table 1. [Examples 2 to 4]
[00137] Papermaking and drying were carried out using the M1 aqueous dispersion slurry of fine cellulose fibers prepared in Example 1 and under exactly the same conditions as Example 1 with the exception of forming the thin cellulose fiber layer equivalent to a base weight of 5 g / m 2 on the cupra rayon nonwoven fabric used in Example 1 to obtain an integrated sheet type structure S2 (base weight: 20 g / m 2) having double layer structures (Example 2). Although S2 has a lower base weight of the thin cellulose fiber layer compared to S1, it has a tensile strength of 1.1 kg / 15 mm, indicating appropriate handling strength. The thickness of the thin cellulose non-woven layer of S2 as determined from the SEM image of cross-section was 3.6 μm.
[00138] Next, calendering treatment (using a roller press manufactured by Yuriroll Co., Ltd.) was carried out on S1 and S2 in an attempt to reduce the thickness. A metallic roller was used for the upper roller, an aramid roller (hardness: 129) was used for the lower roller, and calendering was carried out at a linear pressure of 2.0 tonnes / 20 cm and a travel speed of 2 m / min to obtain samples S3 (Example 3) and S4 (Example 4), respectively. The thicknesses of the thin cellulose non-woven layer of S3 and S4 were 6.9 μm and 3.5 μm, respectively. Research on the appropriateness of the energy recovery ventilation sheets S2 to S4 revealed that they had a high performance (high moisture permeability and high durability) in the energy recovery ventilation sheets as indicated in the following Table 1, In the cases of S3 and S4 in particular, because the calendering treatment resulted in increased resistance to permeability and improved fluctuations in physical properties, while also providing an improvement in thermal conductivity based on the reduction in membrane thickness, they were clearly determined to demonstrate greater appropriateness for use as energy recovery ventilation sheets. [Examples 5 and 6]
[00139] Abaca hemp paste was immersed in water at a concentration of 10% by weight followed by heat treatment for 4 hours at 130 ° C in an autoclave and repeatedly rinsing the resulting swollen paste with water to obtain an impregnated swollen paste. with water.
[00140] The swollen pulp was dispersed in water at a solids content of 1.5% by weight to obtain an aqueous dispersion (400 L) followed by the beating (beating at a CSF value of 588 mlT) and treatment of size reduction in the same manner as in Example 1 to obtain an aqueous M2 dispersion of fine cellulose fibers (solids concentration: 1.5% by weight). Subsequently, dilution with water from M2 and dispersion was performed using the same procedure as Example 1 to prepare a papermaking dispersion (percentage of solids content: 1.5% by weight) followed by papermaking. so that the base weight of the thin cellulose fiber layer on the cupra rayon base material was 5 g / m2, and pressing and drying in the same manner as in Example 1, to obtain a sample S5 (Example 5 ) having a tensile strength of 1.3 kg / 15 mm indicating an appropriate strength for handling.
[00141] In addition, calendering treatment was carried out on S5 under the same conditions as Example 3 and Example 4 to obtain an S6 sample (Example 5 6) having a tensile strength of 1.4 kg / 15 mm indicating appropriate strength for handling .
[00142] When the surface on the side of the thin fiber layer of S5 was subjected to SEM image analysis at a magnification factor of 10000X, the average numerical fiber diameter of the thin cellulose fibers on a surface 10 of the thin cellulose fibers was 45 nm. The thicknesses of the thin cellulose fiber layer of S5 and S6 were both 3.3 μm. Research on the appropriateness of S5 and S6 for use in energy recovery ventilation sheets revealed that their multi-layered structures have the high performance (high moisture permeability and high durability) of energy recovery ventilation sheets, such as indicated in the following Table 1, [Example 7]
[00143] The size reduction treatment, dispersion preparation, papermaking, drying and calendering treatment were carried out in the same way as in Example 6 with the exception of drying after replacing 20 of the organic solvent with isobutyl alcohol containing 50% water after pressing the wet strip of paper to obtain an S7 sample (Example 7). The thickness of the S7 thin cellulose nonwoven layer was 5.6 μm. S7 has high performance (high moisture permeability and high durability) as an energy recovery ventilation sheet as shown in the following Table 1, [Example 8]
[00144] After performing downsizing treatment and preparing the papermaking dispersion in the same manner as in Example 1 and stirring the dispersion for 10 minutes at 50 ° C, the dispersion was immediately poured into the papermaking machine. batch type used in Example 1 and pressing and drying treatment were carried out using the same procedures as Example 1 to obtain a multilayer structure S8 (Example 8). The thickness of the thin cellulose nonwoven layer of S8 was 6.9 μm, and the thickness of the thin cellulose fiber layer was slightly less than S1 obtained by making papermaking under the same conditions at room temperature. As indicated in the following Table 1, the multilayer structure was able to be properly used as an energy recovery ventilation sheet. Although S8 was manufactured under the same conditions as in Example 1 with the exception of the papermaking temperature, compared to S1 obtained in Example 1, it demonstrated greater resistance to permeability, greater permeability to moisture and had functions that were superior in terms of proper use as an energy recovery ventilation sheet. [Example 9]
[00145] First, a hydro-matted non-woven fabric having a base weight of 20 g / m2 was manufactured for use as a backing layer when submitting a semi-randomly cut continuous strip composed of rayon fibers having a fiber length 40 mm and fineness of 1.7 dtex in the hydro-entanglement treatment. The thickness of this short fiber non-woven rayon was 100 μm. The thin cellulose fiber layer was laminated to a base weight of 10 g / m2 on the short rayon nonwoven fabric under exactly the same conditions as in Example 1, with the exception of using the nonwoven fiber fabric short rayon instead of the cupra rayon nonwoven fabric used in Example 1, to obtain an S9 multilayer structure (Example 9) demonstrating superior handling as a result of having 1.2 kg / 15 mm tensile strength. The thickness of the thin cellulose non-woven layer of S9 was 7.2 μm. The multilayer structure was able to be properly used as an energy recovery ventilation sheet, as indicated in the following Table 1, [Example 10]
[00146] The slurry having a CSF value of 73 mlT obtained by whipping the linter paste in Example 1 was diluted with water to a fiber concentration of 0.08% by weight followed by undergoing dispersion treatment for 4 minutes at room temperature with a household mixer to obtain paper-making dispersion. Using this papermaking dispersion, papermaking was first performed at a designated base weight of 20 g / m2 using the same procedure as in Example 1, followed by pressing and drying treatment to first manufacture the nonwoven fiber fabric short composed of natural cellulose fibers. In addition, the thin cellulose fiber layer was laminated to a basis weight of 10 g / m2 on the short rayon non-woven fabric, under exactly the same conditions as in Example 1 with the exception of using the non-woven fabric. short fiber fabric composed of natural cellulose fibers instead of the cupra rayon nonwoven fabric used in Example 1 to obtain a S10 multilayer structure (Example 10) demonstrating superior handling as a result of having 0.9 kg / tensile strength 15 mm. The thickness of the thin cellulose non-woven layer of S10 was 7.1 μm. The multilayer structure was able to be properly used as an energy recovery ventilation sheet, as indicated in the following Table 1, [Examples 11 and 12]
[00147] The two types of multilayer structures S2 and S6 manufactured in Example 2 and Example 6 were respectively subjected to hydrophilic treatment to manufacture samples coated with lithium chloride. An appropriate amount of 5% by weight aqueous lithium chloride solution was uniformly spray-coated on the respective surfaces of the thin cellulose fiber layer of S2 and S6 followed by drying for 10 minutes in a 100% dryer. ° C while immobilized on a fixed-length frame. The multilayer structures coated with lithium chloride obtained from S2 and S6, respectively, were designated as S11 and S12. The adhered amounts of lithium chloride contained in S11 and S12 as calculated from the change in dry weight before and after the coating treatment were 5% by weight in both cases. Although S11 and S12 have two-layer laminated structures, their tensile strengths were 1.1 kg / 15 mm and 1.8 kg / 15 mm, respectively, and both were determined to be sheet-like structures, having appropriate strength (weight base: 23 g / m2, and 3 g / m2 of the base weight was attributable to the amount of lithium chloride and water contained in the coating layer). The resulting multilayer structures were able to be properly used as sheets of a total heat exchanger as indicated in the following Table 1, In particular, the samples subjected to hydrophilic treatment both demonstrated high levels of moisture permeability as compared to S2 and S6 that have not been subjected to hydrophilic treatment, and although they have demonstrated greater appropriateness (greater moisture permeability) for use as energy recovery ventilation sheets, they have also been determined to have problems from the viewpoint of permeability durability the water. [Example 13]
[00148] The hydrophilic treatment was carried out on S6 manufactured in Example 6 to manufacture a sample in which lithium chloride was dispersed and immobilized on a water-soluble polymer coating film. First, ultra high molecular weight polyethylene glycol in the form of Alkox E-60 manufactured by Meisei Chemical Works, Ltd. was used for the water soluble polymer, an aqueous solution was prepared having a lithium chloride concentration of 10% by weight and concentration of E-60 1% by weight, the S6 surface was immobilized on a glass plate so as to become a layer of fine cellulose fiber non-woven fabric, and the aqueous solution was appropriately coated on it using an applicator to obtain a S13 multilayer structure of the present invention by drying using the same procedure as in Example 11. The amounts of lithium chloride and E-60 contained in S13 as calculated from the change in weight in the dry state before and after hydrophilic treatment were 5% by weight and 0.5% by weight, respectively. Although S13 has a double layered structure, it was determined to be a sheet-like structure having appropriate strength as a result of having a tensile strength of 1.2 kg / 15 mm (base weight: 23 g / cm2, and 3 g / m2 of base weight was attributable to the amount of lithium chloride, E-60 and water contained in the coating layer). The resulting multilayer structure was able to be appropriately used as an energy recovery ventilation sheet as indicated in the following Table 1. In particular, each of the samples subjected to hydrophilic treatment demonstrated greater moisture permeability compared to S6 which was not subjected to hydrophilic treatment, and demonstrated greater suitability for use as an energy recovery ventilation sheet of the present invention. From the point of view of moisture permeability durability as well, S13 demonstrated an improved rate of reduction of moisture permeability as compared to S12 which was only coated with lithium chloride, and was determined to be a top sheet in terms of suitability for use as an energy recovery ventilation sheet compared to S12. [Examples 14 and 15]
[00149] The aqueous dispersion M1 prepared in Example 1 was diluted with water to bring the concentration of fine cellulose fibers to 0.1% by weight, and after dispersion for 4 minutes at room temperature with a domestic mixer, the appropriate amount of an emulsion-type aqueous dispersion of a blocked polyfunctional isocyanate (BI) in the form of Meikaneto W EB, manufactured by Meisei Chemical Works, Ltd. was added as a waterproofing agent (crosslinking agent) at a BI concentration of 0.005 % by weight followed by gentle stirring for 3 minutes to prepare the papermaking dispersion A. Similarly, the aqueous dispersion M2 prepared in Example 5 was diluted with water to a concentration of fine cellulose fiber of 0.1% by weight to prepare the dispersion, and after dispersing for 4 minutes at room temperature with a household mixer, the appropriate amount of Meikaneto W EB was added to a BI concentration of 0.005% by weight followed by gentle stirring for 3 m minutes to prepare the papermaking dispersion B. Papermaking and drying were respectively carried out on the papermaking dispersion A and papermaking dispersion B using the same procedure as indicated in Example 2, based on the formation of a layer of thin cellulose non-woven fabric having a basis weight of 5 g / m2 to obtain two types of dry leaves. Then, the two types of dry leaves were fixed to fixed-length frames and subjected to heat treatment for 2 minutes in an oven set at 160 ° C to allow a crosslinking reaction to proceed between hydroxyl groups on a cellulose surface by the isocyanate. After heat treatment, the sheets were removed from the fixed-length frames at room temperature to obtain two types of multilayer structures of the present invention. The multilayer structures respectively obtained from papermaking dispersion A and papermaking dispersion B were designated as S14 (Example 14) and S15 (Example 15), respectively. Although S14 and S15 have double layered structures, their tensile strengths were 1.6 kg / 15 mm and 1.8 kg / 15 mm, respectively, and both were sheet-type structures having appropriate strength (base weight: 21 g / m2 in both cases). The resulting two types of multilayer structures were able to be appropriately used as energy recovery ventilation sheets, as indicated in the following Table 1, In addition, in contrast to S2 and S6, which respectively correspond to samples from S14 and S15 that did not underwent waterproof treatment, with leaves that did not show resistance to moisture to such an extent that the structures easily collapsed in water, and so they were unable to be evaluated for resistance in the wet, when the resistance in the wet of S14 and S15 were evaluated by measuring the tensile strength of wet samples (according to (6)), their wet strengths were determined to be 0.52 kg / 15 mm and 0.59 kg / 15 mm, respectively, and were determined to be multi-layered structures of the present invention that are capable of being used even in humid environments. [Examples 16 and 17]
[00150] In the preparation of papermaking dispersion A in Example 14, a waterproof agent (crosslinking agent) in the form of BI was added and gently stirred for 3 minutes to obtain a hydrophilic agent followed by the addition of 0 , 01% by weight of trimethylglycine in the form of Aminocoat ™, manufactured by Asahi Kasei Chemicals Corp, and again with gentle agitation for 3 minutes to prepare the papermaking dispersion C. Subsequently, papermaking, drying and heat treatment were carried out according to exactly the same procedure as in Example 14 using papermaking dispersion C based on the formation of the thin cellulose nonwoven layer having a basis weight of 5 g / cm2 to obtain a S16 multilayer structure (Example 16) of the present invention.
[00151] Similarly, in the preparation of papermaking dispersion A in Example 14, a waterproof agent in the form of BI was added and gently stirred for 3 minutes to obtain a hydrophilic agent followed by the addition of 0.01% by weight of a water-soluble cationic polymer in the form of Aronfloc® C-508, manufactured by MT Aquapolymer Inc. and again gentle agitation for 3 minutes to prepare the papermaking dispersion D. Subsequently, papermaking, drying and treatment thermal treatments were carried out according to exactly the same procedure as in Example 14 using the papermaking dispersion D based on the formation of the thin cellulose nonwoven layer having a base weight of 5 g / cm2 to obtain a multilayer structure S17 (Example 17) of the present invention. Although S16 and S17 have double layered structures, their tensile strengths were 1.4 kg / 15 mm and 1.7 kg / 15 mm, respectively, and both were sheet-like structures having appropriate strength (base weight: 22 g / m2 (S16) and 23 g / m2 (S17)). The multilayer structures were able to be properly used as sheets of a complete heat exchanger, as indicated in the following Table 1. In particular, the two types of hydrophilic agents were considered to have accumulated on the surface of the thin cellulose fibers, and then became immobilized on the surface and inner layer of the thin cellulose fiber layer as a result of subsequent papermaking, thus resulting in increased moisture permeability and favorable durability, as compared to S14 which only on a single proof treatment of water. In addition, because the tensile strengths in the wet of S16 and S17 are 0.48 kg / 15 mm and 0.49 kg / 15 mm, respectively, they are both multilayer structures that also be used in wet environments. [Example 18]
[00152] A Tencel® cut fiber oily agent (length: 3 mm) supplied by Lenzing Fibers Corp., was washed several times in water containing a surfactant to properly remove the oily agent and obtain short crude fibers containing water.
[00153] The short crude fibers were dispersed in water at a concentration of 1.5% by weight to obtain an aqueous dispersion (400 L) followed by the beating (beating at a value of CSF 90 mlt) and reduction treatment similarly sized as Example 1 to obtain an aqueous M3 dispersion of fine cellulose fibers (solids concentration: 1.5% by weight). Next, dispersion M2 prepared in Example 5 and dispersion M3 were mixed so that the weight ratio of the thin cellulose fibers contained in dispersion M2 and the thin cellulose fibers contained in dispersion M3 was 50:50 followed by another dilution with water at a solids concentration of 0.15% by weight and dispersion for 4 minutes at room temperature with a household mixer to prepare the papermaking dispersion.
[00154] Papermaking was carried out so that the base weight of the thin cellulose fiber layer on the cupra rayon base material was 5 g / m2 followed by pressing and drying in the same manner as in Example 1 for obtain a sample S18 (Example 18) having appropriate strength for handling as a result of having a tensile strength of 1.1 kg / 15 mm.
[00155] When the surface on the side of the S18 thin fiber layer was subjected to SEM image analysis at a magnification factor of 10000X, the average numerical fiber diameter of the thin cellulose fibers on a surface of the thin cellulose fibers was 273 nm. The thickness of the thin cellulose non-woven layer of S18 was 6.2 μm. Research on the appropriateness of S18 as an energy recovery ventilation sheet revealed that the multilayer structure has high performance (high moisture permeability and high durability) as the energy recovery ventilation sheet as indicated in the following Table 1. [ Examples 19 and 20]
[00156] The multilayer structures S19 (Example 19) and S20 (Example 20) of the present invention were obtained according to exactly the same procedure as in Examples 14 and 16 with the exception of changing the support obtained by laminating the fabric layer fine cellulose fiber non-woven fabrics in Examples 14 and 16 of T N150 for Nylon Spunbond N05020 manufactured by Asahi Kasei Fibers Corp. Although S19 and S20 have double-layered structures, they were determined to be sheet-type structures (base weight: 21 g / m2 (S19), 22 g / m2 (S20)) having appropriate strength as a result of having resistance to traction of 2.0 kg / 15 mm and 1.9 kg / 15 mm, respectively. In addition, because the tensile strengths in the wet of S19 and S20 were 1.9 kg / 15 mm and 1.7 kg / 15 mm, respectively, they are both multilayer structures that can be used in wet environments. Both samples are capable of being used as energy recovery ventilation sheets, as shown in Table 1. [Example 21]
[00157] An energy recovery ventilation sheet subjected to flame retardant treatment and having a flame retardant content of 22.9% by weight was obtained by immersing the multilayer structure S4 obtained in Example 4 in an aqueous solution a 20% by weight of a flame retardant based on guanidine sulfaminate in the form of Apinon-101, manufactured by Sanwa Chemical Co., Ltd. and drying. As a result of conducting an incombustibility test on this sheet in accordance with the JIAA 1322 fine materials incombustibility testing method and measuring the remaining scorched, flame and gloss length, the sheet was determined to have classification incombustibility. 2. In addition, the physical properties of this sample 21 (Example 21) of a multilayer structure subjected to flame retardant treatment are shown in the following Table 1. S21 was able to be appropriately used as an energy recovery ventilation sheet. [Table 1]

[Comparative example 1 and 2]
[00158] The slurry having a CSF value of 73 mlT obtained by whipping the lining slurries of Example 1 in the same way as Example 10 was diluted with water to a fiber concentration of 0.08% by weight followed by carrying out the dispersion treatment for 4 minutes at room temperature with a household mixer to obtain the papermaking dispersion. Papermaking was first carried out using this papermaking dispersion at a designated base weight of 20 g / m2 using the same procedure as in Example 1 followed by pressing and drying treatment to obtain the short fiber nonwoven sample R1 (Comparative example 1) composed of natural cellulose fibers.
[00159] Next, calendering treatment was carried out on R1 under the same calendering treatment conditions as described in Example 3 to obtain a sample R2 (Comparative example 2). When an SEM image of the R1 surface was observed, a mixture of fibers having a fiber diameter of several μm to 10 μm or more and fibers having a fiber diameter of 200 nm or less was observed to be present, and values for diameter fiber average differed greatly for each image, thus making it difficult to make a quantitative determination. Furthermore, although R1 and R2 have tensile strengths of 0.9 kg / 15 mm and 1.1 kg / 15 mm, respectively, which allowed them to be manipulated, nor did they demonstrate the uniformity of the favorable sheet referred to as texture, and showed problems in terms of quality stability. The results indicated in the following Table 2 were obtained when evaluated for the appropriateness for the use of the energy recovery ventilation sheets. Because both R1 and R2 do not contain the determined layer composed of fine cellulose fibers, they have the problem of being unable to demonstrate resistance to high permeability, and even in the case of R2, resistance to permeability has been improved as a result of increasing density by calendering treatment, resistance to permeability was lower than in any of the examples. That is, both samples were clearly determined to be less than each of the samples indicated in Examples 1 to 20 mentioned above in terms of suitability for use in the energy recovery ventilation sheets. [Comparative example 3]
[00160] Three layers of cupra rayon nonwoven fabric used as a base material in Example 1 (Bemliese® T N150, Asahi Kasei Fibers Corp., base weight: 15 g / m2, thickness: 50 μm, density: 0 , 28 g / cm3, mean single fiber fineness: 0.2 dtex) were overlapped followed by calendering treatment under the same calendering treatment conditions as described in Example 3 to obtain a sample R3 (Comparative Example 3). When the suitability of R3 for use as an energy recovery ventilation sheet was assessed, the results shown in the following Table 2 were obtained. Because R3 does not contain a prescribed layer composed of thin cellulose fibers, it varies widely from the prescribed permeability resistance, and was unable to be properly used as an energy recovery ventilation sheet in terms of being able to separate the intake and exhaust vents. exhaust air. [Comparative example 4 and 5]
[00161] Coniferous kraft paste (NBKP) was dispersed in water at a concentration of 2.5% by weight to obtain an aqueous dispersion (400 L) followed by continuation with a whipping treatment for about 40 minutes over 400 L of the dispersion aqueous using a disc refiner in the form of the same SDR14 Labo refiner model (pressurized disc type) as used in Example 1 in a 0.8 mm disc gap to obtain a beaten slurry having a CSF value of 90 mlΦ. Papermaking was carried out using the same procedure as in Example 1 at a designated base weight of 40 g / m2 followed by pressing and drying treatment to obtain a paper sample composed of natural cellulose fibers. Calendering treatment was carried out on paper under the same calendering treatment conditions as described in Example 3 to obtain a sample R4 (Comparative example 4). The hydrophilic treatment was then carried out on R4 under the same lithium chloride coating conditions as described in Example 11 to obtain a sample R5 (Comparative Example 5) uniformly coated with lithium chloride in an amount of 1 g / m2. Although both R4 and R5 have appropriate strength as a result of having 1.6 kg / 15 mm tensile strengths, the results shown in the following Table 2 5 were obtained when assessed for appropriateness for use as energy recovery ventilation sheets. R4 was unable to achieve high permeability resistance or high moisture permeability (low permeability resistance), and although R5, in which permeability resistance increased slightly as a result of lithium chloride coating, 10 demonstrated high humidity permeability. Due to the effects of the humidifying agent, moisture permeability after high temperature hysteresis has decreased considerably, resulting in problems in terms of durability as well. That is, both samples were clearly determined to be less than each of the samples indicated in Examples 1 to 20 above 15 in terms of suitability for use as energy recovery ventilation sheets. [Table 2]

[00162] An energy recovery ventilation element was manufactured by laminating an S17 energy recovery ventilation sheet obtained in Example 17 and shot-molded satin kraft paper (Shiroyama Paper Co., Ltd., basis weight: 65 g / m2) followed by the manufacture of a total static heat exchanger with orthogonal flow (190 mm x 190 mm x 350 mm, 134 stages). When the heat exchange rate was measured according to J IS B 8626, the energy recovery efficiency was 81%. INDUSTRIAL APPLICABILITY
[00163] Because the multilayer structure of the present invention has a high permeability resistance, high humidity permeability and comparatively high thermal conductivity, it can preferably be used as a divider material (energy recovery ventilation element) for energy recovery fans energy for office air conditioners and energy recovery fans for home use. In addition, in the case of using, as an energy recovery ventilation sheet, the multilayer structure of the present invention not only demonstrates superior resistance to permeability, moisture permeability and thermal conductivity, but also demonstrates superior durability and, using this sheet in an energy recovery fan, an energy recovery fan can be provided which demonstrates extremely high humidity exchange efficiency and total energy recovery efficiency over a long period of time.

权利要求:
Claims (14)
[0001]
1. Multilayer structure, characterized by the fact that it comprises at least one layer of thin cellulose fiber non-woven fabric composed of thin cellulose fibers, in which said thin cellulose fibers that form the layer of non-woven fabric of thin cellulose fiber have an average fiber diameter of 0.005 μm to 0.5 μm, said multilayer structure has an average thickness of 10 μm to 200 μm, a density of 0.10 g / cm3 to 0.90 g / cm3, and a resistance to air permeability of 2000 s / 100 ml or more, where the proportion of fine cellulose fibers contained in the thin cellulose fiber non-woven layer is 50% by weight to 100% by weight, where the total sum of base weight of the thin cellulose fiber non-woven layer is 1 g / m2 to 15 g / m2 and the total thickness is 0.5 μm to 15 μm, and the multilayer structure has undergone a treatment waterproof using a crosslinking agent.
[0002]
2. Multilayer structure according to claim 1, characterized in that it is a two-layer structure, the average thickness of the multilayer structure is 10 μm to 150 μm, the density is 0.30 g / cm3 to 0.80 g / cm3 and the resistance to air permeability is 3000 s / 100 ml or more. .
[0003]
Multilayer structure according to either of claims 1 or 2, characterized in that a layer of the multilayer structure is a layer of non-woven fabric or porous film or layer of fabric, which is composed of one or a combination of one plurality of fibers selected from the group consisting of regenerated cellulose fibers, natural cellulose fibers, nylon fibers, polyester fibers and polyolefin fibers.
[0004]
4. Multilayer structure according to any one of claims 1 to 3, characterized by the fact that the multilayer structure has been subjected to a hydrophilic treatment.
[0005]
5. Energy recovery ventilation sheet, characterized by the fact that it is composed of the multilayer structure, according to any one of claims 1 to 4.
[0006]
6. Energy recovery ventilation sheet according to claim 5, characterized by the fact that the average thickness of the multilayer structure is 10 μm to 70 μm.
[0007]
7. Energy recovery ventilation sheet according to claim 6, characterized by the fact that the average thickness of the multilayer structure is 10 μm to 30 μm.
[0008]
Energy recovery ventilation sheet according to any one of claims 5 to 7, characterized by the fact that the multilayer structure has been subjected to flame retardant treatment.
[0009]
Energy recovery ventilation sheet according to any one of claims 5 to 8, characterized by the fact that the proportion of cellulose fibers in the material that makes up the multilayer structure is 90% by weight or more.
[0010]
10. Method for producing the multilayer structure according to any one of claims 1 to 3, characterized in that it comprises the following steps: a step for laminating and forming a layer of thin cellulose fiber non-woven fabric having an average diameter fiber from 0.005 μm to 0.5 μm over a layer of nonwoven fabric by a papermaking method, and a step to dry the resulting laminated nonwoven fabric.
[0011]
11. Method according to claim 10, characterized by the fact that it still comprises a heat treatment step after the drying step.
[0012]
12. Method for producing the multilayer structure according to claim 10, characterized in that it further comprises the following step: a step to form a layer of hydrophilic coating by coating on one side or both sides of the multilayer structure described in any one of claims 1 to 4.
[0013]
13. Energy recovery ventilation element, characterized in that the energy recovery ventilation sheet according to any one of claims 5 to 9 is used as a dividing material that divides two types of air flow of different temperature , humidity, or both.
[0014]
14. Energy recovery fan, characterized by the fact that it uses the energy recovery ventilation element according to claim 13.

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同族专利:

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公开号 | 公开日

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CA2879447A1|2014-01-23|

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---

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---

EP2875950A1|2015-05-27|

---

US20160194832A1|2016-07-07|

---

JP6189842B2|2017-08-30|

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BR112015000927A2|2017-06-27|

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JPWO2014014099A1|2016-07-07|

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EP2875950A4|2015-07-15|

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CN104470720A|2015-03-25|

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US20150167249A1|2015-06-18|

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CA2879447C|2018-02-06|

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CN104470720B|2016-08-24|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

JP2639303B2|1992-11-05|1997-08-13|三菱電機株式会社|Total heat exchanger|

---

GB2320261B|1996-11-11|2000-10-25|Nippon Kodoshi Corp|Method of manufacturing highly-airtight porous paper, highly airtight porous paper manufactured by the method, and non-aqueous battery using the paper|

---

JP3791726B2|1997-12-19|2006-06-28|特種製紙株式会社|Total heat exchanger paper and total heat exchanger element using the same|

---

AU2002304108B2|2001-06-01|2004-04-22|Mitsubishi Paper Mills Limited|Total heat exchange element-use paper|

---

JP4094318B2|2002-03-28|2008-06-04|松下エコシステムズ株式会社|Heat exchange membrane and heat exchange element|

---

DE10245125A1|2002-09-27|2004-01-22|Fibermark Gessner Gmbh & Co. Ohg|Filter for removal of particulates from gases e.g. building air-conditioning and air intake filters for engines, is a low thickness composite of coarse and fine filtration layers of synthetic and cellulosic fibres|

---

US7008465B2|2003-06-19|2006-03-07|Donaldson Company, Inc.|Cleanable high efficiency filter media structure and applications for use|

---

WO2006004012A1|2004-07-01|2006-01-12|Asahi Kasei Kabushiki Kaisha|Cellulose nonwoven fabric|

---

JP4980789B2|2006-06-05|2012-07-18|レンゴー株式会社|Total heat exchanger seat|

---

JP2008088589A|2006-09-29|2008-04-17|Mitsubishi Paper Mills Ltd|Base material of process paper for peeling|

---

FI20085760A|2008-08-04|2010-03-17|Teknillinen Korkeakoulu|Modified composite product and process for its preparation|

---

JP5130153B2|2008-08-26|2013-01-30|旭化成せんい株式会社|Method for producing bulky structure|

---

JP5502742B2|2008-10-17|2014-05-28|大王製紙株式会社|Water resistant and highly breathable composite sheet and method for producing the same|

---

JP2010115574A|2008-11-11|2010-05-27|Asahi Kasei Corp|Functional filter|

---

JP5551905B2|2009-08-21|2014-07-16|旭化成せんい株式会社|Apparatus and method for producing sheet containing fine fibers|

---

JP2011074535A|2009-09-30|2011-04-14|Nippon Paper Industries Co Ltd|Oil-resistant paper|

---

EP2532782B1|2010-02-01|2018-06-20|Oji Holdings Corporation|Method for producing cellulose-fiber flat structure|

---

JP2012000550A|2010-06-15|2012-01-05|Asahi Kasei Fibers Corp|Filter medium composed of cellulose fiber|

---

JP2012036529A|2010-08-06|2012-02-23|Asahi Kasei Fibers Corp|Cellulose sheet|

---

JP5697379B2|2010-08-26|2015-04-08|旭化成せんい株式会社|Water-resistant cellulose sheet|

---

AU2012208922B2|2011-01-21|2016-10-13|Fpinnovations|High aspect ratio cellulose nanofilaments and method for their production|

---

JP2012160877A|2011-01-31|2012-08-23|Konica Minolta Business Technologies Inc|Image processor|

---

JP5781321B2|2011-02-15|2015-09-16|旭化成せんい株式会社|Protein-adsorbing cellulose nonwoven fabric|

---

FI126055B|2012-05-14|2016-06-15|Upm Kymmene Corp|Process for the manufacture of a membrane of fibrill cellulose and fibrill cellulose membrane|

---

US9580873B2|2012-07-19|2017-02-28|Asahi Kasei Fibers Corporation|Multilayered structure comprising fine fiber cellulose layer|

---

WO2014164127A1|2013-03-09|2014-10-09|Donaldson Company, Inc.|Nonwoven filtration media including microfibrillated cellulose fibers|

---

FR3003580B1|2013-03-20|2015-07-03|Ahlstroem Oy|WET-NON-WOVEN COMPRISING CELLULOSE NANOFIBRILLES|

---

FR3003581B1|2013-03-20|2015-03-20|Ahlstroem Oy|FIBROUS MEDIUM BASED ON FIBERS AND NANOFIBRILS OF POLYSACCHARIDE|

---

CA2914146A1|2013-06-03|2014-12-11|Oji Holdings Corporation|Method for producing sheet containing fine fibers|

---

KR20160020524A|2013-07-19|2016-02-23|아사히 가세이 셍이 가부시키가이샤|Fine cellulose fiber sheet|US9580873B2|2012-07-19|2017-02-28|Asahi Kasei Fibers Corporation|Multilayered structure comprising fine fiber cellulose layer|

---

FI127526B|2012-11-03|2018-08-15|Upm Kymmene Corp|Method for producing nanofibrillar cellulose|

---

CN105074062B|2013-02-26|2017-09-29|三菱化学株式会社|Spinning-nozzle, the manufacture method of fiber assembly, fiber assembly and paper|

---

KR20160020524A|2013-07-19|2016-02-23|아사히 가세이 셍이 가부시키가이샤|Fine cellulose fiber sheet|

---

JP6364618B2|2013-09-17|2018-08-01|パナソニックＩｐマネジメント株式会社|Partition member for total heat exchange element, total heat exchange element and total heat exchange type ventilator using the same|

---

PL3077734T3|2013-12-02|2020-02-28|Zehnder Group International Ag|System and process for fixing a heating or cooling body|

---

US9780334B2|2014-03-12|2017-10-03|Panasonic Corporation|Organic EL device having a hygroscopic layer|

---

JP6387514B2|2014-03-19|2018-09-12|パナソニックＩｐマネジメント株式会社|Partition member for total heat exchange element, total heat exchange element and total heat exchange type ventilator using the same|

---

JP6323950B2|2014-06-30|2018-05-16|ヤンマー株式会社|Exhaust purification device|

---

JP6259729B2|2014-06-30|2018-01-10|ヤンマー株式会社|Exhaust purification device|

---

KR20190039340A|2014-09-26|2019-04-10|아사히 가세이 가부시키가이샤|Thin-film sheet including cellulose fine-fiber layer|

---

JP6402005B2|2014-11-04|2018-10-10|太陽ホールディングス株式会社|Resin-containing sheet, and structure and wiring board using the same|

---

CZ2014956A3|2014-12-23|2016-05-18|2Vv S.R.O.|Enthalpic heat-exchange apparatus|

---

CA2974468A1|2015-01-23|2016-07-28|Zehnder Group International Ag|Enthalpy exchanger element, enthalpy exchanger comprising such elements and method for their production|

---

FR3035611B1|2015-04-28|2019-08-09|Centre Technique Du Papier|METHOD AND DEVICE FOR MANUFACTURING LAMINATED MATERIAL COMPRISING A FIBRILED CELLULOSE LAYER|

---

JP6783078B2|2015-06-16|2020-11-11|大王製紙株式会社|Cellulose nanofiber manufacturing method and cellulose nanofiber manufacturing equipment|

---

JP6947033B2|2015-10-27|2021-10-13|王子ホールディングス株式会社|Laminated sheet and laminated body|

---

SE539751C2|2015-11-09|2017-11-14|Stora Enso Oyj|Active moisture control material for packaging and a method for production thereof|

---

JP6639203B2|2015-11-26|2020-02-05|旭化成株式会社|Sheet containing cellulose fiber layer|

---

JP2017101185A|2015-12-03|2017-06-08|株式会社ミマキエンジニアリング|Coating agent, manufacturing method of printed matter, printed matter|

---

JP6916425B2|2015-12-04|2021-08-11|国立大学法人愛媛大学|Manufacturing method of ultra-small cellulose|

---

WO2018003492A1|2016-06-28|2018-01-04|日本製紙株式会社|Paper for energy recovery ventilation element|

---

US20180001244A1|2016-07-01|2018-01-04|Hollingsworth & Vose Company|Multi-layered electret-containing filtration media|

---

FI127590B|2016-07-04|2018-09-28|Teknologian Tutkimuskeskus Vtt Oy|Cellulose based film structure and method for producing the same|

---

KR101795293B1|2016-08-03|2017-11-08|김진규|Functional cellulose composite|

---

JP6905318B2|2016-09-20|2021-07-21|大王製紙株式会社|Cellulose nanofiber manufacturing equipment and cellulose nanofiber manufacturing method|

---

CN106568343A|2016-11-15|2017-04-19|武汉理工大学|Efficient plate-fin air-to-air total heat exchanger suitable for trains|

---

US20180162092A1|2016-12-09|2018-06-14|The Boeing Company|Fiber-modified interlayer for a composite structure and method of manufacture|

---

US10287366B2|2017-02-15|2019-05-14|Cp Kelco Aps|Methods of producing activated pectin-containing biomass compositions|

---

US10913022B2|2017-03-29|2021-02-09|Knowlton Technologies, Llc|Process for utilizing a high efficiency synthetic filter media|

---

JP2018171730A|2017-03-31|2018-11-08|王子ホールディングス株式会社|Laminated sheet|

---

EP3385426A1|2017-04-03|2018-10-10|Lenzing Aktiengesellschaft|Nonwoven cellulose fiber fabric with increased water holding capability and low basis weight|

---

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-12-15| B09A| Decision: intention to grant|

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2021-01-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012160877|2012-07-19|

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JP2012-160877|2012-07-19|

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PCT/JP2013/069685|WO2014014099A1|2012-07-19|2013-07-19|Multilayered structure comprising fine fiber cellulose layer|

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