WO2014014099A1 - 微細繊維セルロース層を含む多層構造体 - Google Patents
微細繊維セルロース層を含む多層構造体 Download PDFInfo
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- WO2014014099A1 WO2014014099A1 PCT/JP2013/069685 JP2013069685W WO2014014099A1 WO 2014014099 A1 WO2014014099 A1 WO 2014014099A1 JP 2013069685 W JP2013069685 W JP 2013069685W WO 2014014099 A1 WO2014014099 A1 WO 2014014099A1
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- multilayer structure
- total heat
- nonwoven fabric
- fine cellulose
- heat exchanger
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
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- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F12/00—Use of energy recovery systems in air conditioning, ventilation or screening
- F24F12/001—Use of energy recovery systems in air conditioning, ventilation or screening with heat-exchange between supplied and exhausted air
- F24F12/006—Use of energy recovery systems in air conditioning, ventilation or screening with heat-exchange between supplied and exhausted air using an air-to-air heat exchanger
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
- F28D21/0001—Recuperative heat exchangers
- F28D21/0014—Recuperative heat exchangers the heat being recuperated from waste air or from vapors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
- F28D21/0015—Heat and mass exchangers, e.g. with permeable walls
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- F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
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- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
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Definitions
- the present invention divides a multilayer structure including at least one layer of fine cellulose fiber nonwoven fabric, a sheet for a total heat exchanger composed of the multilayer structure, and the sheet for a total heat exchanger into two kinds of air currents having different temperatures, humidity, or both.
- the present invention relates to a total heat exchange element used as a partition material, and a total heat exchanger using the total heat exchange element.
- Air conditioning equipment (approximately 38%) accounts for the largest proportion of energy consumed by buildings such as general office buildings. Of these, 30-40% cannot ventilate the outside air, and reducing air-conditioning energy loss due to ventilation can be said to be an energy-saving issue in office buildings.
- sick house syndrome caused by volatile organic compounds emanating from building materials and daily necessities is becoming a problem.
- One of the causes of such problems is that the confidentiality of the buildings has increased, the air conditioning has become widespread and ventilation has become difficult, and the volatilized organic compounds have become easier to stay indoors. Under such circumstances, the revised Building Standards Act of Japan in July 2003 made it mandatory to install ventilation equipment on buildings. Attempts have also been made to add ventilation functions to home air conditioners, and this movement is not limited to Japan, and ventilation of buildings is being promoted worldwide.
- the total heat exchanger that reduces energy consumption by making it difficult to release heat or cold to the outside while performing ventilation.
- the total heat exchanger include a rotary total heat exchanger that recovers heat from exhaust to intake air by rotation of a hygroscopic rotor, and a static total heat exchanger as shown in FIG.
- the gas barrier total heat exchanger element arranged in a corrugated plate separates the external fresh supply air exchanged by ventilation and the polluted exhaust air in the room, At the same time as the sensible heat is moved, the latent heat of water is transmitted from the exhaust air to the supply air by allowing moisture to pass therethrough, thereby suppressing the release of heat or cold to the outside.
- the total heat exchanger sheet used for the element for the total heat exchanger of the stationary total heat exchanger can move sensible heat and can move latent heat by passing moisture, thus increasing the heat exchange efficiency.
- Such sheets include, for example, Japanese paper and pulp flame retardant paper, glass fiber mixed paper, inorganic powder-containing mixed paper, a microporous membrane or paper made of a synthetic polymer, a sheet for a total heat exchanger using a nonwoven fabric, and the like. It is done. However, since air also permeates through ordinary microporous membranes, paper, and nonwoven fabric, a sheet for a total heat exchanger having a surface treated with a polymer coating or the like has been reported.
- Patent Document 1 discloses a sheet for a total heat exchanger in which a porous sheet made of polytetrafluoroethylene is coated with a polyurethane-based resin containing an oxyethylene group.
- a total heat exchanger sheet made of polyester and polyethylene or polypropylene has been reported.
- a hydrophobic polymer is used as a base material, sufficient moisture permeability cannot be obtained, and as a result, sufficient thermal conductivity cannot be obtained for use as a sheet for a total heat exchanger. .
- Patent Document 3 describes a filter for a total heat exchanger in which viscose is coated on a nonwoven fabric of rayon pulp as hydrophilic fibers.
- moisture permeability 6900g / m 2 / 24hr or more air permeability 10000s / 100 ml or more sheets have been reported to be produced.
- the moisture permeability is insufficient, a material having sufficient performance for use as a total heat exchanger sheet has not been obtained.
- Patent Document 4 a non-woven fabric structure containing fine cellulose composed of fine cellulose fibers as a layer in Patent Document 4 below.
- the multilayer nonwoven fabric structure described in Patent Document 4 has high air permeability (air permeability resistance of 2000 s / 100 ml or less) and is not suitable for use as a sheet for a total heat exchanger.
- the problem to be solved by the present invention is to provide a multilayer structure having a high air permeability resistance and a high moisture permeability, and having high suitability as a sheet for a total heat exchanger.
- the inventors of the present invention pay attention to the fact that the fine cellulose fiber nonwoven fabric contained in the multilayer nonwoven fabric structure has a very fine fiber diameter, and dry it after laminating by a papermaking method from an aqueous dispersion.
- a result of studying to form a uniform dense and thin layer with a low basis weight by utilizing the property of densification due to strong drying shrinkage in the thickness direction at the time as a result of earnest examination to solve further problems, for total heat exchanger Achieved to provide a multilayer structure as a sheet material that can be widely used not only for sheets but also for application fields that require both high air resistance and high moisture permeability. It is.
- a multilayer structure including at least one layer of fine cellulose fiber nonwoven fabric composed of fine cellulose fibers, and the average fiber diameter of the fine cellulose fibers forming the fine cellulose fiber nonwoven fabric layer is 0.005 ⁇ m or more and 0.5 ⁇ m or less. And the average thickness of the multilayer structure is 10 ⁇ m or more and 200 ⁇ m or less, the density is 0.10 g / cm 3 or more and 0.90 g / cm 3 or less, and the air resistance is 2000 s / 100 ml or more. Multilayer structure.
- the average thickness of the multilayer structure is 10 ⁇ m or more and 150 ⁇ m or less, the density is 0.30 g / cm 3 or more and 0.80 g / cm 3 or less, and the air resistance is 3000 s /
- a sheet for a total heat exchanger comprising the multilayer structure according to any one of [1] to [8].
- the multilayer structure of the present invention has a high air permeability resistance and a high moisture permeability, and therefore can be suitably used for all applications where compatibility of the physical properties is required.
- a heat exchanger a household total heat exchanger, etc.
- it can be suitably used as a partition material (total heat exchange element) that partitions two types of air having different temperatures, humidity, or both.
- the total heat exchange element is thin in the closed portion that partitions the air, the total heat exchange element is more likely to transmit moisture than the conventional total heat exchanger sheet, and thus the effect of maintaining humidity is enhanced.
- the multilayer structure provided by the present invention is excellent in durability, by using this for a total heat exchanger, a heat exchanger having a very high humidity exchange efficiency and total heat exchange efficiency over a long period of time can be obtained. Can be provided.
- the multilayer structure of the present invention includes at least one or a plurality of fine cellulose fiber nonwoven fabric layers made of fine cellulose fibers. If it is not composed of fine cellulose fibers, the desired air resistance, moisture permeability, and durability cannot be achieved.
- the material of the fine cellulose fiber that constitutes the fine cellulose fiber non-woven fabric layer is cellulose softwood pulp, hardwood pulp, cotton-derived pulp, hemp (Abaca and Zaisal) etc.-derived pulp, kenaf-derived pulp, bamboo-derived pulp, bagasse-derived
- cellulose derivative fibers such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, carboxymethylcellulose, carboxyethylcellulose, nitrocellulose, and methylcellulose It is preferable that the cellulose fiber which consists of 50 to 100 weight% is contained.
- the composition of the fine cellulose fibers in the fiber material constituting the fine cellulose fiber nonwoven fabric layer is preferably 70% by weight, and higher.
- the fine cellulose fine fibers are more preferably 80% by weight or more, and most preferably 90% by weight or more. Thereby, it becomes possible to achieve a large moisture permeability at the same time as a suitably large air resistance.
- other fine fibers may be mixed as long as the content is 50% by weight or more of cellulose fiber.
- polyethylene fiber, polypropylene fiber, polyketone fiber, polyester having heat melting property It may also contain fine fibers such as fibers.
- the fine cellulose fiber constituting the fine cellulose fiber nonwoven fabric layer is preferably cellulose microfibril.
- the cellulose microfibril means a cellulose fiber having a fiber diameter of several nanometers to 200 nm or a bundle thereof called microfibril made of natural cellulose or regenerated cellulose.
- microfibrillated cellulose cellulose derived from acetic acid bacteria or bacteria, which is called bacterial cellulose, or plant-derived cellulose such as pulp or animal-derived cellulose, such as squirt cellulose, called microfibrillated cellulose is used as a high-pressure homogenizer or super It means independent microfibrils peeled off from the fiber surface or fine fibers in which they converge, which are obtained by refining with a highly shearing device such as a high-pressure homogenizer or a grinder. In the present invention, it is particularly preferable to use microfibrillated cellulose as a raw material from the viewpoint of cost and quality control.
- a cut yarn of regenerated cellulose fiber having a fine fiber diameter, a cut yarn of cellulose derivative fiber having a fine fiber diameter, a regenerated cellulose obtained by an electrospinning method, or a cut yarn of ultrafine yarn of a cellulose derivative are also fine cellulose. Can be used as fiber.
- the average fiber diameter of the fine cellulose fiber of the present invention is 0.005 ⁇ m or more and 0.5 ⁇ m or less.
- the average fiber diameter of the fine cellulose fibers means the number average fiber diameter recognized from the SEM image or TEM image on the surface, and conforms to the evaluation means described in International Publication No. WO2006 / 4012.
- a non-woven fabric composed of cellulose fibers tends to have higher thermal conductivity as the fiber diameter becomes smaller under the condition of a constant porosity.
- the network density of the fiber network occupying a certain space decreases, and the efficiency of surface conduction, which is thought to contribute to heat conduction, deteriorates, resulting in a decrease in thermal conductivity.
- the fiber diameter of the cellulose fiber By setting the fiber diameter of the cellulose fiber to 0.5 ⁇ m or less, it is possible to form a very dense layer having a high air permeability resistance as a nonwoven fabric layer with a low basis weight, and the fiber diameter of the constituent fibers is thin and the basis weight.
- the present inventors have found that a sheet having a relatively high thermal conductivity can be produced because the design can be made low.
- the fine cellulose fiber nonwoven fabric layer can be composed of a fine cellulose fiber nonwoven fabric composed of fine cellulose fibers having a degree of polymerization (DP) of 100 or more and 12,000 or less.
- the degree of polymerization is the number of glucose rings that form a cellulose molecular chain.
- the degree of polymerization of the cellulose fiber is 100 or more, the tensile strength and elastic modulus of the fiber itself are improved. As a result, the strength of the nonwoven fabric structure is improved, the handling property when the total heat exchange element is attached, and the total heat. Quality stability when using the exchanger is improved.
- the degree of polymerization of the fine cellulose fibers is preferably 150 to 8,000, more preferably 300 to 6000, from the viewpoints of handling properties and industrial implementation.
- the surface or the inside of the fine cellulose fiber constituting the fine cellulose fiber nonwoven fabric layer may be chemically modified.
- some or most of the hydroxyl groups present on the surface of fine cellulose fibers are esterified including acetate ester, nitrate ester, sulfate ester, alkyl ether typified by methyl ether, carboxymethyl
- alkyl ether typified by methyl ether
- carboxymethyl A hydroxyl group at the 6-position is oxidized by a carboxy ether represented by ether, an etherified one containing cyanoethyl ether, or a TEMPO oxidation catalyst (for example, 2,2,6,6-tetramethylpiperidinooxy radical).
- a carboxyl group including acid type and salt type).
- the basis weight of the fine cellulose fiber nonwoven fabric layer is small, and as a result, the thickness of the layer is thin.
- a thin layer having a small and small pore diameter, which is substantially composed of fine cellulose fibers, is formed. Therefore, it is possible to design with a high air resistance and a high moisture permeability. This is because the water vapor permeation path can be designed to be short because the layer is thin, and the layer is made of fine fibers.
- the moving path density per unit volume of water vapor moving through the interface can be designed to be high, and as a result, high moisture permeability can be expressed.
- the thin and dense fine cellulose fiber nonwoven fabric layer ensures the surface thermal conductivity at the fiber interface due to its thinness and the size of the density of the fine fibers constituting the unit volume (that is, the internal interface area). And the layer itself possesses high thermal conductivity.
- the basis weight of the fine cellulose fiber nonwoven fabric layer in the multilayer structure of the present invention is 1 g / m 2 or more and 15 g / m 2 or less, preferably 2 g / m 2 or more and 10 g / m 2 or less, more preferably 3 g / m 2 or more. It is in the range of 8 g / m 2 or less. Within this range, the three physical properties of air permeability resistance, moisture permeability, and thermal conductivity can be expressed with a good balance.
- sum total of fabric weight means what added the fabric weight of each layer, when this nonwoven fabric has two or more layers. For example, when a fine cellulose dispersion is applied to a nonwoven fabric by a coating dip, a three-layer structure (two fine cellulose fiber nonwoven fabric layers) having a support as a central layer is taken.
- the total thickness of the fine cellulose fiber nonwoven fabric layer is 0.5 ⁇ m or more and 15 ⁇ m or less, more preferably 1 ⁇ m or more and 12 ⁇ m or less, and most preferably 1.5 ⁇ m or more and 8 ⁇ m or less. These three physical properties can be expressed in a well-balanced manner. If the total thickness of the layers is less than 0.5 ⁇ m, it becomes difficult to keep the air resistance uniformly 2000 s / 100 ml or more, and if it exceeds 15 ⁇ m, the moisture permeability tends to decrease. Is also not preferable.
- the thickness of the fine cellulose fiber nonwoven fabric layer means that obtained by observing a cross-sectional SEM image of the split cross section of the multilayer structure of the present invention.
- the present invention it is important to design a thin layer of a fine cellulose fiber nonwoven fabric with a low basis weight, and in that case, the mechanical strength that can be handled as a sheet material is maintained only by the fine cellulose fiber nonwoven fabric layer. Therefore, in the present invention, another porous sheet is used as a support, and one or more layers are laminated to form a multilayer structure.
- the average thickness of the multilayer structure of the present invention including the support layer is from 10 ⁇ m to 200 ⁇ m, preferably from 10 ⁇ m to 150 ⁇ m, more preferably from 10 ⁇ m to 70 ⁇ m, and even more preferably from 10 ⁇ m to 30 ⁇ m.
- the multilayer structure of the present invention It is difficult to design the multilayer structure of the present invention with an average thickness of less than 10 ⁇ m and a mechanical strength that does not cause a problem in handling, and an average thickness greater than 200 ⁇ m increases the rigidity as a sheet, which is also difficult to handle in handling. It is not preferable.
- the total weight per unit area of the multilayer structure of the present invention is preferably 10 g / m 2 or more and 100 g / m 2 or less. If it is less than 10 g / m 2 , the air permeability resistance and the mechanical strength cannot be obtained.
- a non-woven fabric structure having a basis weight exceeding 100 g / m 2 is disadvantageous from the viewpoint of thermal conductivity as well as being difficult to obtain sufficient moisture permeability.
- the multilayer structure of the present invention is a nonwoven structure having a two-layer structure of a fine cellulose fiber nonwoven fabric layer and a support layer made of fine cellulose fibers having an average fiber diameter of 0.005 ⁇ m to 0.5 ⁇ m.
- the basis weight of the fine cellulose fiber nonwoven fabric layer is 2 g / m 2 to 10 g / m 2 and the basis weight of the support layer is 10 g / m 2 to 78 g / m 2 , most preferably fine.
- the basis weight of the cellulose fiber nonwoven fabric layer is 3 g / m 2 or more and 8 g / m 2 or less and the basis weight of the support layer is 11 g / m 2 or more and 57 g / m 2 or less, Performance can be achieved.
- the multilayer structure of the present invention has a density of 0.10 g / cm 3 or more and 0.90 g / cm 3 or less, more preferably 0.30 g / cm 3 or more and 0.80 g / cm 3 or less. Since the multilayer structure of the present invention has a structure in which a fine fine cellulose fiber layer is laminated on a porous support as described above, the sheet as a whole is not limited in this way despite its high air resistance. It is characterized by a low density as a material. When the density is less than 0.10 g / cm 3 , the mechanical strength as the sheet material cannot be secured, which is not preferable.
- the multilayer structure of the present invention has a gas permeability resistance (measured by JAPAN TAPPI paper pulp test method) of 2000 s / 100 ml or more.
- a gas permeability resistance measured by JAPAN TAPPI paper pulp test method
- the air resistance is preferably 3000 s / 100 ml or more, and when used as a total heat exchange sheet, it is preferably 4000 s / 100 ml or more.
- the upper limit of the air resistance is preferably as high as possible (the larger it is), but is preferably 10 million s / 100 ml or less, which is the detection limit of the measuring device.
- the proportion of fine cellulose fibers contained in the fine cellulose fiber nonwoven fabric layer is 50% by weight or more and 100% by weight or less, and preferably 70% by weight or more and 100% by weight or less.
- other materials contained in the layer include fiber materials made of materials other than cellulose, inorganic fillers, polymers, and inorganic particles, but the air resistance is uniform so as to maintain 2000s / 100 ml or more. Any material that can form a dense layer may be used. If the proportion of fine cellulose fibers in the layer is less than 50% by weight, it is difficult to design the air resistance at 2000 s / 100 ml or more, which is not preferable.
- one layer is a nonwoven fabric layer composed of any one or a plurality of combinations selected from the group consisting of regenerated cellulose fibers, natural cellulose fibers, nylon fibers, polyester fibers, and polyolefin fibers, And / or a porous membrane and / or a fabric achieves high strength as a sheet material without inhibiting the thinness and high moisture permeability of the fine cellulose fiber nonwoven fabric layer, which is an important element of the present invention. be able to.
- porous membranes include polyolefin resins such as polyethylene and polypropylene, nylon resins such as polysulfone, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polycarbonate, 6-nylon, 6,6-nylon, poly A porous film composed of acrylic resin such as methyl methacrylate, polyketone, polyetheretherketone and the like can be mentioned, but is not limited thereto.
- the fabric include, but are not limited to, cellulose fibers (including cellulose derivative fibers), nylon fibers, polyester fibers, polyurethane fibers, or fabrics composed of these mixed yarns (including unwoven fabrics). It is not a thing.
- the air resistance is 200 s / 100 ml or less, preferably When it is 100 s / 100 ml or less, high moisture permeability is easily developed.
- the multilayer structure of the present invention preferably includes a nonwoven fabric as a layer other than the fine cellulose fiber nonwoven fabric layer.
- the multilayered nonwoven fabric of the present invention is preferably a nonwoven fabric made of a material having a reactive hydroxyl group or amide group, such as cellulose and nylon, from the viewpoint of water resistance and hydrophilization treatment.
- a non-woven fabric layer and / or a non-woven fabric layer composed of natural cellulose fibers that is, a paper-based material
- Examples of the material of the nonwoven fabric layer made of the regenerated cellulose fiber used in the present invention include one or more selected from regenerated cellulose fibers such as cupra, viscose rayon and polynosic rayon, and purified cellulose by solvent spinning.
- the form of a fiber can use both a short fiber and a long fiber, Preferably it is a long fiber, More preferably, it is a continuous long fiber.
- a short fiber nonwoven fabric layer made of natural cellulose fibers may be included as one layer of the nonwoven structure.
- the material of the nonwoven fabric layer is softwood pulp, hardwood pulp, cotton-derived pulp. , Hemp (Abaca seeds, Zaisal seeds, etc.) derived pulp, kenaf derived pulp, bamboo derived pulp, bagasse derived pulp.
- a cupra ammonium method rayon stock solution is continuously spun onto the net by the falling tension spinning method, and self-adhesion of the fiber itself or necessary
- regenerated cellulose continuous long fibers obtained by entanglement of fibers by hydroentanglement to form a nonwoven fabric can be mentioned.
- Specific examples thereof include Asahi Kasei Fibers Co., Ltd. registered trademark: Benlyse (registered trademark).
- Regenerated cellulose continuous long fiber has a higher thermal conductivity and higher hygroscopicity than other regenerated cellulose fibers such as rayon, so it can be designed to have a large moisture permeability for exchanging latent heat. It is particularly preferred when used as a layer of the body. Benlyse is capable of obtaining sufficient strength as a non-woven fabric without entanglement by high-pressure water flow unlike a short-fiber non-woven fabric because many continuous long fibers are self-adhering while solidifying in a spinning bath. This is a preferable point used as a single layer of the nonwoven fabric structure.
- the fineness of the continuous long fiber can be in the range of 0.1 dtex to 3 dtex, but when used as a composite with fine cellulose fibers, it can maintain the entanglement strength with the fine cellulose fibers and the air permeability. From the viewpoint that it can be reduced, a range of 0.1 to 1.0 dtex is preferable.
- the multilayer structure of the present invention preferably has a two-layer structure of a fine cellulose fiber nonwoven fabric layer comprising fine cellulose fibers and a nonwoven fabric layer or a porous membrane as a support, Furthermore, for the reasons described above, the non-woven fabric structure having a two-layer structure of a fine cellulose fiber nonwoven fabric layer made of fine cellulose fibers and a nonwoven fabric layer made of regenerated cellulose fibers is suitable for the performance as a sheet for a total heat exchanger. It is preferable at the point which can express to. From the viewpoint of maintaining strength, the nonwoven fabric layer made of regenerated cellulose fibers is preferably a nonwoven fabric layer made of regenerated cellulose continuous long fibers.
- the tensile strength of the multilayer structure of the present invention is preferably 0.3 kg / 15 mm or more and 4.0 kg / 15 mm or less.
- the tensile strength of this nonwoven fabric structure is 4.0 kg / 15 mm at the maximum, but there is no upper limit of this tensile strength. The higher the tensile strength, the more preferable for applying the multilayer structure to various applications. More preferably, it is 0.5 kg / 15 mm or more, More preferably, it is 0.8 kg / 15 mm or more.
- the multilayer structure according to the present invention can be suitably used in applications requiring durability by performing water-resistant treatment.
- an additive for internal addition such as a sizing agent, a wet paper strength enhancer or a crosslinking agent may be added during the production of the multilayer structure, or a water-resistant treatment agent may be applied in post-processing. .
- internally added water-proofing agents include rosin soap, alkyl ketene dimer, alkenyl succinic anhydride, sizing agent such as polyvinyl alcohol, wet formability enhancer such as urea formaldehyde resin, melamine formaldehyde resin, and polyvinylamine.
- Cross-linking agents such as, but not limited to, polyamide polyamine epichlorohydrin (PAE) and block type polyfunctional isocyanate (BI) can be mentioned.
- cross-linking type water-proofing agents such as PAE and BI are particularly preferable because they exhibit a very large water-proofing effect, and considering that the surface of fine cellulose fibers has a negative zeta potential, From the viewpoint, it is preferable to use cationic BI or cationic compound PAE because the water resistance effect can be efficiently expressed.
- the crosslinking type water-resistant agent for example, when a support made of cellulose (hydroxyl group) or nylon (amide group) having a crosslinking reaction site is used, a covalent bond with a polyfunctional isocyanate generated from BI is generated. Since the adhesive strength between a support body and a micronized cellulose nonwoven fabric layer can also be made high, it is preferable.
- BI is a compound that provides stability in water by protecting the polyfunctional isocyanate with a blocking group (such as amidoxime or ⁇ -caprolactam) and is stable in the papermaking dispersion used in the papermaking process described below. It is a compound that can be dispersed in the paper, and after paper making, dried and heat-treated (usually 130 ° C. or higher), the blocking group is eliminated and isocyanate is produced, which reacts with the surrounding reaction sites (hydroxyl groups and amide groups). is there.
- a blocking group such as amidoxime or ⁇ -caprolactam
- Water resistance treatment in post-processing includes treatment with a diisocyanate-based crosslinking agent such as hexamethylene diisocyanate or 4,4′-methylenebisphenyl isocyanate in an organic solvent, melamine resin, or ethylene glycol diglycidyl.
- a treatment in an aqueous medium with a crosslinking agent such as ether can be mentioned, but is not limited thereto.
- the moisture permeability can be further improved.
- a hydrophilized treatment is preferable because the moisture permeability can be designed higher.
- a means of hydrophilization treatment a method of imparting high hydrophilicity to the surface and / or the inside of the fine cellulose fiber layer by an internal addition method, and a method of introducing a hydrophilic compound into the surface layer of the multilayer structure by post-processing, There is.
- a cationic hygroscopic hydrophilic compound is added and adsorbed in the dispersion for papermaking of fine cellulose fibers, and after that, By laminating the dispersion on paper and a support, the entire fine cellulose nonwoven fabric layer can be made more hydrophilic.
- a hydrophilic compound is internally added in combination with the crosslinking agent in the water resistance treatment described above, adsorbed and fixed on the surface of fine cellulose fibers, and then laminated on paper and support, and simultaneously by heat treatment.
- the progress of the crosslinking reaction is effective because it leads to water resistance and at the same time, immobilization of the hydrophilic compound on the surface and / or inside of the fine cellulose nonwoven fabric layer.
- the hydrophilic compound used for such a purpose is preferably a hydrophilic compound containing a site that reacts with a crosslinking agent in the molecular skeleton.
- hydrophilic compounds having a hydroxyl group, amine group, amide group, etc. reactive to isocyanate such as anionic or cationic polyvinyl alcohol (vinyl alcohol and anion) Copolymer with a functional or cationic vinyl monomer), but this is only an example and is not limited.
- Examples of the post-processing method include a method of applying or spraying a solution or dispersion of a hydrophilic compound having high hydrophilicity to the multilayer structure, and a method of drying after immersing the multilayer structure in the hydrophilic compound solution.
- Examples of hydrophilic compounds that can be used for the hydrophilization treatment include inorganic acid salts, organic acid salts, inorganic fillers, polyhydric alcohols, ureas, hygroscopic (water-absorbing) polymers (water-soluble polymers and hydrogel formation).
- aluminum hydroxide calcium carbonate, aluminum silicate, magnesium silicate, talc, clay, zeolite, diatomaceous earth, sepiolite, silica gel, activated carbon, polyhydric alcohol, glycerin, ethylene glycol, triethylene glycol, polyglycerin, ureas are Urea, hydroxylethylurea, moisture absorption (water absorption)
- polymers polyaspartic acid, polyacrylic acid, polyglutamic acid, polylysine, alginic acid, carboxymethylcellulose, carboxyethylcellulose, hydroxylalkylcellulose and their salts or cross-linked products, carrageenan, pectin, gellan gum, agar, xanthan gum, hyaluronic acid, guar
- the inorganic filler refers to inorganic minerals, inorganic salts, and the like that are used for purposes such as bulking agents and bulking agents in addition to moisture absorption purposes.
- the hygroscopic agent to prevent the moisture permeable agent from moving at high humidity, it may be effective to coexist with the water-soluble polymer including the above description and an inorganic salt or an organic salt.
- the multilayer structure of the present invention contains an optional additive as long as the moisture permeability and air permeability resistance of the multilayer structure of the present invention are not impaired, in addition to the water-resistant agent and the hydrophilic compound. May be.
- Water-proofing agents, hydrophilic compounds and other additives can be used as appropriate to improve the performance of the multilayer structure of the present invention as described above.
- the total amount is preferably suppressed to 30% by weight or less of the total weight of the total heat exchanger sheet, more preferably 20% by weight or less, and still more preferably 10% by weight or less. Within this range, it is possible to provide a high-performance multilayer structure of the present invention.
- the multilayer nonwoven fabric structure of the present invention which is a base material Since durability of a sheet
- nonwoven structure of the total heat exchanger sheet according to the present invention (measured by JIS L 1099 A-1 method) moisture permeability, 5000g / m 2 / 24hr or more, more preferably is 7000 g / m 2/24 hr or more, more preferably, it is possible to express more than 8000g / m 2 / 24hr.
- the moisture permeability is preferably as high as possible for use as a sheet for a total heat exchanger.
- the multilayer structure according to the present invention can achieve a relatively high thermal conductivity in the range of 0.0100 W / (m ⁇ K) to 0.1000 W / (m ⁇ K).
- the substantial thermal conductivity is governed by a dense fine cellulose fiber nonwoven fabric layer that serves as an air resistance layer.
- a heat conduction efficiency higher than the numerical value of the heat conductivity of the multilayer structure shown in the embodiment, that is, a sensible heat exchange rate can be expressed.
- the multilayer structure of the present invention can be applied to any application that can make use of high moisture permeability, high air resistance, and relatively high heat conductivity, in addition to the above-described total heat exchanger sheet.
- Examples of such applications include water-treated membranes such as membrane distillation that require high water vapor permeability, and materials for clothing that require low water permeability (corresponding to high air resistance) and water vapor permeability.
- water-treated membranes such as membrane distillation that require high water vapor permeability, and materials for clothing that require low water permeability (corresponding to high air resistance) and water vapor permeability.
- the multilayer structure of the present invention can contribute to a high energy exchange rate when used as a total heat exchange sheet. That is, in particular, in the structure of a total heat exchange element (stacked cartridge called an element) used in a static total heat exchanger, in FIG. 1, the multilayer structure of the present invention has a high air resistance, a high moisture permeability and Due to the relatively high thermal conductivity, it can be suitably used as a partition material for partitioning exhaust / intake.
- the sheet for the total heat exchanger of the present invention is preferably a thin sheet because of the demand for compactness of the total heat exchange element and thermal conductivity, and the overall average thickness is 10 ⁇ m to 200 ⁇ m, preferably 10 ⁇ m to 120 ⁇ m, more preferably.
- the total heat exchanger sheet of the present invention can be designed with a flame retardant treatment.
- the sheet for a total heat exchanger according to the present invention passes the flameproof class 3 in the “flammability test method for thin materials for buildings (JIS A 1322)”. It is preferable to have flame retardancy. In addition, it is more preferable if it has the flame retardance which passes the flame-proof grade 2 and the flame-proof grade 1.
- the flame retardant treatment include a method of applying a flame retardant to the nonwoven fabric structure, specifically, a method of applying or spraying a flame retardant on the surface of the nonwoven fabric structure, and a flame retardant solution. And a method of immersing the nonwoven structure in
- Examples of the flame retardant that can be used in the present invention include an inorganic flame retardant, an inorganic phosphorus compound, a nitrogen-containing compound, a chlorine compound, and a bromine compound.
- an inorganic flame retardant for example, a mixture of borax and boric acid, aluminum hydroxide , Antimony trioxide, ammonium phosphate, ammonium polyphosphate, ammonium sulfamate, guanidine sulfamate, guanidine phosphate, amide phosphate, chlorinated polyolefin, ammonium bromide, non-ether polybromo cyclic compound, etc. Flame retardants that are possible are mentioned.
- the content of the flame retardant is preferably 1% by weight or more and 15% by weight of the total heat exchanger sheet. If it is less than 1% by weight, it is difficult to exert a flame-retardant effect. Moreover, when it contains exceeding 15 weight%, a water vapor transmission rate will reduce and heat exchange efficiency will reduce. More preferably, it is 2 to 10% by weight, and further preferably 3 to 8% by weight.
- the multilayer structure including the fine cellulose fiber nonwoven fabric layer used in the present invention is obtained by first preparing an aqueous dispersion of fine cellulose fibers and forming a film by the method described below using the dispersion.
- wood pulp and non-wood pulp such as softwood pulp and hardwood pulp can be used as raw materials for producing fine cellulose fibers.
- non-wood pulp include cotton-derived pulp including cotton linter pulp, hemp-derived pulp, bagasse-derived pulp, kenaf-derived pulp, bamboo-derived pulp, and straw-derived pulp.
- Cotton-derived pulp, hemp-derived pulp, bagasse-derived pulp, kenaf-derived pulp, bamboo-derived pulp, and straw-derived pulp are respectively cotton lint, cotton linter, and hemp-based abaca (for example, many from Ecuador and the Philippines) It means a refined pulp obtained through a refining process such as delignification or bleaching process by digesting raw materials such as Zaisal, bagasse, kenaf, bamboo, and straw.
- a purified product of seaweed-derived cellulose or squirt cellulose can also be used as a raw material for fine cellulose fibers.
- a cut yarn of regenerated cellulose fiber or a cut yarn of cellulose derivative fiber can be used as the raw material, and a cut yarn of regenerated cellulose or cellulose derivative obtained by electrospinning is also used as a raw material or fine material of fine cellulose fiber. It can be used as the cellulose fiber itself.
- the cellulose fiber is refined through a pretreatment process, a beating process, and a refinement process.
- the pretreatment step it is effective to make the raw material pulp easy to be refined by autoclave treatment under water impregnation at a temperature of 100 to 150 ° C., enzyme treatment, or a combination thereof.
- These pretreatments not only reduce the load of the micronization process, but also discharge impurity components such as lignin and hemicellulose present on the surface and gaps of the microfibrils that make up the cellulose fibers to the aqueous phase, resulting in a finer process. Since there is an effect of increasing the ⁇ -cellulose purity of the formed fiber, it may be very effective for improving the heat resistance of the fine cellulose fiber nonwoven fabric.
- the raw material pulp is 0.5 wt% or more and 4 wt% or less, preferably 0.8 wt% or more and 3 wt% or less, more preferably 1.0 wt% or more and 2.5 wt% or less.
- a beating device such as a beater or disc refiner (double disc refiner).
- a disc refiner When a disc refiner is used, if the clearance between the discs is set as narrow as possible (for example, 0.1 mm or less) and processing is performed, extremely advanced beating (fibrillation) proceeds, so a high-pressure homogenizer or the like is used.
- the conditions for the miniaturization treatment can be relaxed and may be effective.
- a preferable degree of beating processing is determined as follows. In our study, as the beating process was performed, the CSF value (indicating the degree of beating of the cellulose. Evaluated by the Canadian standard freeness test method for pulp as defined in JIS P 8121) decreased over time. Then, after becoming close to zero, a tendency to increase again when the beating treatment is continued is confirmed. In order to prepare fine cellulose fibers as a raw material of the nonwoven fabric structure of the present invention, a CSF value is used as a pretreatment. Once it became close to zero, it was found that it is preferable to continue the beating process until the CSF value is increased.
- the CSF value in the process of decreasing the CSF value from unbeaten is expressed as *** ⁇
- the CSF value in a tendency to increase after becoming zero is expressed as *** ⁇ .
- the CSF value is preferably at least zero, and more preferably CSF30 ⁇ .
- slurry aqueous dispersion prepared to such a beating degree, fibrillation progresses to a high degree, and at the same time, it is possible to provide a filter medium free from coarse cellulose fibers having a maximum fiber diameter of 2500 nm.
- the filter medium which consists of the fine cellulose fiber nonwoven fabric obtained from has the tendency for a tensile strength to improve. Also, highly refined slurries with a CSF value of at least zero or a *** ⁇ value that increases thereafter increase in homogeneity and can reduce clogging caused by subsequent refinement by a high-pressure homogenizer, etc. There are the above advantages.
- the solid content concentration in the aqueous dispersion is 0.5 wt% or more and 4 wt% or less, preferably 0.8 wt% or more and 3 wt% or less, more preferably 1.0 wt. % By weight to 2.5% by weight. With such a solid content concentration, clogging does not occur, and an efficient miniaturization process can be achieved.
- high-pressure homogenizers examples include NS type high-pressure homogenizers from Niro Soabi (Italy), SMT's Lanier type (R model) pressure-type homogenizers, and Sanwa Kikai Co., Ltd. high-pressure homogenizers. Any device other than these devices may be used as long as the device performs miniaturization by a mechanism substantially similar to those of these devices.
- Ultra-high pressure homogenizers mean high-pressure collision type miniaturizers such as Mizuho Kogyo Co., Ltd. microfluidizer, Yoshida Kikai Kogyo Co., Ltd. Nanomizer, and Suginoma Machine Co., Ltd.
- any device other than these devices may be used as long as the device performs miniaturization with a substantially similar mechanism.
- the grinder-type miniaturization device include the pure fine mill of Kurita Machinery Co., Ltd. and the stone mill type milling die represented by Masuyuki Sangyo Co., Ltd. Any device other than these may be used as long as the device performs miniaturization by this mechanism.
- the micronized cellulose fibers thus obtained are usually called microfibrillated cellulose (MFC).
- the fiber diameter of the fine cellulose fiber is determined according to the conditions for refinement using a high-pressure homogenizer (selection of equipment and operating pressure and number of passes) or pre-treatment conditions (for example, autoclave treatment, enzyme treatment, beating treatment). Etc.).
- a high-pressure homogenizer selection of equipment and operating pressure and number of passes
- pre-treatment conditions for example, autoclave treatment, enzyme treatment, beating treatment. Etc.
- the 6-position hydroxyl group is oxidized by the cellulose-based fine fiber that has been subjected to the chemical treatment of the surface and the TEMPO oxidation catalyst to the MFC produced by the above-described process
- carboxyl Cellulose fine fibers that are based can also be used as the fine cellulose fibers of the present invention.
- some or most of the hydroxyl groups present on the surface of fine cellulose fibers are acetate ester, nitrate ester, sulfate ester.
- An esterified product containing benzene, an alkyl ether typified by methyl ether, a carboxy ether typified by carboxymethyl ether, and an etherified product containing cyanoethyl ether can be appropriately prepared and used.
- TEMPO a catalyst called a radical
- an oxidant such as hypochlorous acid
- a purification treatment such as water washing
- an ordinary mixer By performing the treatment, a dispersion of fine cellulose fibers can be obtained very easily.
- a carboxyl group is introduced on the surface of the fine cellulose fiber obtained by the TEMPO catalyst, and due to its high hydrophilicity, high moisture permeability can be obtained by using the fine cellulose fiber as a raw material of the present invention. May be obtained.
- film forming method it is preferable to manufacture by a papermaking method.
- film formation by a papermaking method is preferable in that it can be appropriately entangled with a support layer such as a non-woven fabric and can form a film with very few defects.
- a paper dispersion or paper coating of an aqueous dispersion of fine cellulose fibers is made on the above-mentioned various supports and laminated.
- a method for forming a nonwoven fabric layer made of fine cellulose fibers contained in a multilayer structure by a papermaking method will be described.
- it is the manufacturing method of a multilayer structure including the three processes of the drying process which evaporates and removes a part of water from this concentrated composition.
- the method for forming a fine cellulose fiber nonwoven fabric layer by a papermaking method using the above aqueous dispersion is a nonwoven fabric having the above-mentioned contents as a support on a wire or filter cloth by a papermaking method from an aqueous dispersion of a predetermined fine cellulose fiber, A wet paper is formed on a porous film or a fabric, and in some cases, the wet paper is laminated to produce a wet paper having a laminated structure. Is to dry.
- the aqueous dispersion of fine cellulose fibers used in the preparation step may be an aqueous dispersion containing 0.01% to 0.5% by weight of fine cellulose fibers and 85% to 99.99% by weight of water. preferable.
- the concentration of the fine cellulose fibers in the aqueous dispersion for papermaking is 0.01% by weight or more and 0.5% by weight or less, more preferably 0.03% by weight or more and 0.35% by weight or less. If it is within such a range, stable papermaking can be carried out.
- the solvent of the fine cellulose fiber dispersion for papermaking may be water alone, but in some cases, for example, various compounds may be added for the purpose of controlling various physical properties such as moisture permeability and air resistance. It may be.
- an organic solvent that dissolves in water or a hydrophobic organic solvent that does not dissolve is added to water as a solvent, Each may be effective as an aqueous solution of an organic solvent or an emulsion of an organic solvent.
- organic solvents that dissolve in water include cellosolves such as methanol, ethanol, iso-propanol, and methyl cellosolve
- hydrophobic organic solvents that do not dissolve include hydrocarbons such as n-decane and toluene, 1- Although long chain alcohols, such as hexanol, can be mentioned, it is not limited to these.
- the boiling point is preferably 160 ° C. or lower.
- the composition in the whole solvent of the organic solvent used for economical reasons it is preferably 10% by weight or less, more preferably 3% by weight or less. Within such a range, the multilayer structure of the present invention can be obtained at a relatively low cost.
- the above-mentioned water-proofing agent and hydrophilic compound that is, water-proofing agent: sizing agent, wet paper strength enhancer, cross-linking agent, etc., hydrophilic compound: inorganic acid salt , Organic acid salts, inorganic filler polyhydric alcohols, ureas, hygroscopic (water-absorbing) polymers (water-soluble polymers and hydrophilic polymers capable of forming hydrogels), etc., are added to the papermaking dispersion. In some cases, it is possible to impart water resistance and further hydrophilicity.
- the water-proofing agent and / or hydrophilic compound needs to be added in an effective amount, but it is preferable to add it in a range that does not impair the stability of the papermaking stock solution.
- a hygroscopic (water-absorbing) polymer when added, the moisture-absorbing (water-absorbing) polymer efficiently remains on the cellulose surface, thereby effectively acting as a reinforcing binder as well as improving moisture permeability. is there.
- Moisture absorption (water absorption) polymer is dissolved or finely dispersed in the aqueous phase in the aqueous dispersion in this papermaking method, and the water permeability is increased by incorporating the water-soluble polymer in the fine fiber nonwoven fabric layer. It becomes possible.
- the concentration of the hygroscopic (water-absorbing) polymer is 0.003% to 0.3% by weight, more preferably 0.005% to 0.08% by weight, and still more preferably 0.006% by weight.
- the amount is not less than 0.07% by weight.
- the concentration is less than 0.003% by weight, the effect of adding a hygroscopic (water-absorbing) polymer is difficult to appear, which is not preferable.
- the concentration exceeds 0.3% by weight, the amount of addition such as foaming is increased. Since the accompanying negative effect tends to appear, it is not preferable.
- the aqueous dispersion contains a surfactant in the hygroscopic (water-absorbing) polymer and the total amount of the specific water-soluble polymer in the above concentration range. It doesn't matter.
- anionic surfactants such as alkyl sulfate ester salt, polyoxyethylene alkyl sulfate ester salt, alkylbenzene sulfonate, ⁇ -olefin sulfonate, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, Cationic surfactants such as benzalkonium chloride, amphoteric surfactants such as trimethylglycine, alkyldimethylaminoacetic acid betaine, alkylamidodimethylaminoacetic acid betaine, and nonionic surfactants such as alkylpolyoxyethylene ether and fatty acid glycerol ester It can be mentioned, but is not limited to these.
- additives may be added to the aqueous dispersion according to the purpose.
- inorganic particulate compounds such as silica particles, alumina particles, titanium oxide particles, calcium carbonate particles, resin fine particles, various salts, aqueous dispersions It can be added within a range (selection of type and selection of composition) that does not adversely affect the production of the multilayer structure of the present invention, such as an organic solvent that does not inhibit the stability of the liquid.
- aqueous dispersion liquid as short fiber materials other than fine cellulose fibers, polyester fibers, nylon fibers, acrylic fibers, aramid fibers, cellulose acetate fibers, etc., titanium oxide whiskers, zinc oxide whiskers, glass A filler material such as fiber or carbon fiber may be included.
- the weight fraction of water in the aqueous dispersion is 85% to 99.99% by weight, preferably 90% to 99.98% by weight, more preferably 92% to 99.97%. It is preferable that the composition is dispersed or dissolved in water. When the composition of water in the aqueous dispersion is lower than 85% by weight, the viscosity increases in many cases, and it becomes difficult to uniformly disperse the slurry in the dispersion, and a nonwoven fabric layer composed of fine cellulose fibers having a uniform structure is obtained. This is not preferable because it is difficult to be obtained.
- the aqueous dispersion is prepared by mixing all additives into water and preparing an aqueous slurry dispersion by an appropriate dispersion method, or by preparing an aqueous dispersion containing fine additives separately in advance. What is necessary is just to mix and make an aqueous dispersion.
- the aqueous dispersion prepared in the first step is dehydrated with a paper machine, and fine cellulose fibers are filtered on the support to concentrate the aqueous dispersion.
- This is a paper making process in which the support layer and the concentrated layer are laminated or integrated.
- the papermaking process is basically an apparatus that uses a filter or filter cloth (also called a wire in the technical field of papermaking) that dehydrates water from a water-containing dispersion and keeps fine cellulose fibers on the support layer. Any apparatus may be used as long as it is present.
- a porous structure including a sheet-like fine cellulose fiber nonwoven fabric layer with few defects is preferably obtained. Can do. Whether the paper machine is a continuous type or a batch type, it may be properly used according to the purpose.
- a paper-based aqueous dispersion prepared under the above-described conditions has a yield ratio of a water-insoluble component containing cellulose or the like contained in the dispersion of 70% by weight or more, preferably 95%.
- any wire or filter cloth can be used as long as it is capable of making paper at weight% or more, more preferably 99 weight% or more.
- a non-woven fabric and / or a porous membrane and / or a fabric as a support is provided in the lower layer, and paper making is performed from above. Therefore, depending on the support, the support itself may be fine. It may have a high yield of cellulose fibers. In such a case, a metal mesh or plastic wire used for normal papermaking can also be used. However, even if the yield ratio of cellulose and the like is 70% by weight or more, if the drainage is not high, it takes time to make paper, and the production efficiency is remarkably deteriorated.
- water permeation amount preferably 0.005ml / cm 2 ⁇ s or more, more preferably used as is 0.01ml / cm 2 ⁇ s or more. If it is within this range, papermaking suitable from the viewpoint of productivity becomes possible.
- the yield ratio of the water-insoluble component is lower than 70% by weight, not only the productivity is remarkably reduced, but also the water-insoluble component such as cellulose is clogged in the wire or filter cloth to be used. The peelability of the subsequent multilayer structure is also significantly deteriorated.
- the water permeation amount of the wire or filter cloth under atmospheric pressure shall be evaluated as follows.
- a wire or filter cloth to be evaluated on a batch paper machine for example, an automatic square sheet machine manufactured by Kumagai Riki Kogyo Co., Ltd.
- the wire is used as it is, and the filter cloth is 80 to 120 mesh.
- a filter cloth is placed on a metal mesh (assuming that there is almost no drainage resistance), a sufficient amount (yml) of water is poured into a paper machine having a papermaking area of xcm 2 , and filtered under atmospheric pressure.
- Measure time The amount of water permeation when the drainage time is zs (seconds) is defined as y / (xz) (ml / cm 2 ⁇ s).
- wet paper which is a concentrate of fine cellulose fibers.
- the solid content ratio of the wet paper is controlled by the suction pressure (wet suction or dry suction) of the papermaking or the pressing process, and the solid content concentration is preferably 6 wt% or more and 60 wt% or less, more preferably the solid content.
- the concentration is adjusted to a range of 10% by weight to 50% by weight.
- a method may be used in which papermaking is performed on a filter cloth, and water in the obtained wet paper is replaced with an organic solvent in a substitution step with an organic solvent and dried.
- This method is effective when designing a high porosity to improve moisture permeability, but the resistance to air permeability is reduced compared to the case where it is not replaced. decide.
- the details follow the pamphlet of International Publication No. 2006/004012. That is, the support is placed on a paper machine on which a wire or filter cloth is set, and a part of water constituting the aqueous dispersion is dehydrated (paper making) on the support, and fine cellulose fibers are formed on the support.
- a multilayered sheet comprising a multilayer structure of at least two layers can be produced.
- a support having a multilayer structure having two or more layers may be used.
- seat of three or more layers by performing the multistage papermaking of the fine cellulose fiber nonwoven fabric of this invention of two or more layers on a support body.
- the aqueous dispersion is made on a wire at room temperature.
- the papermaking temperature is set to a temperature higher than usual of 30 ° C. or higher and 80 ° C. or lower, a multilayer structure having both high air resistance, high moisture permeability, and relatively high thermal conductivity can be manufactured more stably. You can also.
- the papermaking temperature is 40 ° C. or higher, since the degree of swelling of each fine cellulose fiber is high, the surface tension between the fibers when papermaking is increased, and the inside of the nonwoven fabric structure is tightly packed.
- the wet paper obtained in the paper making process evaporates a part of the water in the drying process by heating to form the multilayer structure of the present invention.
- the drying process is a constant-length drying type that can dry the water while keeping the width constant with the wet paper sandwiched between the dryer surface and the felt, such as a drum dryer used in the papermaking process. Is preferably used because a multilayer structure having high air resistance can be stably obtained.
- the drying temperature may be appropriately selected according to the conditions, but is preferably in the range of 80 ° C. or higher and 180 ° C. or lower, more preferably 90 ° C. or higher and 150 ° C. or lower. If it is this range, the multilayer structure of this invention can be manufactured suitably.
- the drying temperature is less than 80 ° C.
- the evaporation rate of water is slow in many cases, and it is not preferable because productivity cannot be ensured.
- the drying temperature is higher than 180 ° C.
- the hydrophilic polymer constituting the multilayer structure is heated. There are cases where denaturation occurs, and energy efficiency affecting the cost is reduced, which is not preferable.
- it is also effective to obtain a highly uniform multilayer structure by performing rough drying at low temperature drying of 100 ° C. or lower and performing multi-stage drying in which drying is performed at a temperature of 100 ° C. or higher in the next stage. Sometimes.
- a heat treatment step for advancing the reaction of the crosslinking agent is performed separately from the drying step. It is important to provide it. As a matter of course, it is preferable to set an appropriate reaction temperature for the cross-linking agent.
- the heat treatment temperature is Considering the completeness of the reaction at 100 ° C. or higher, it is 120 ° C. or higher, preferably 130 ° C. or higher.
- the multilayer structure of the present invention obtained in the above step is provided with a calendering step for post-processing as a coating treatment or chemical treatment and / or for adjusting the average thickness (usually for the purpose of thinning), if necessary.
- the post-processing step is performed in order to provide a function necessary for post-processing rather than the internal addition method.
- a predetermined moisture permeable or flame retardant coating liquid which may be aqueous or organic solvent
- the coating liquid is applied and dried in a process such as spray coating, printing, or coating.
- heat treatment is performed in the same manner as in the internal addition method to advance the reaction.
- the multilayer structure obtained in the drying step described above when provided with a calendering process for smoothing or thinning with a calendering device, it has an average thickness of 15 ⁇ m to 30 ⁇ m as a preferred embodiment of the present invention.
- a multilayer structure can be manufactured stably. That is, by including a step of subjecting the multilayer structure after drying to a smoothing process by a calender device, a thin film can be formed, and the fine cellulose of the present invention having a wide range of combinations of average thickness / air permeability / strength.
- a multilayer structure comprising a fibrous nonwoven layer can be provided.
- a multilayer structure having an average thickness of 30 ⁇ m or less (lower limit is about 3 ⁇ m) under the setting of an overall basis weight of 30 g / m 2 or less.
- the calendering process extremely fine pores of the layer made of the fine cellulose fiber of the present invention are crushed and the pore size is averaged, and the air permeability performance such as air resistance and moisture permeability is remarkably stabilized.
- the calendar device in addition to a normal calendar device using a single press roll, a super calendar device having a structure in which these are installed in a multistage manner may be used.
- Providing a multilayer structure having excellent performance as a sheet for a total heat exchanger for example, by selecting the material (material hardness) and linear pressure on each side of the roll during calendar processing according to the purpose. Can do.
- the roll material is a metal roll and a high-hardness resin roll, or a metal roll and a cotton roll, or a metal roll and an aramid roll
- a multilayer structure having the above average thickness range can be produced.
- filling the above conditions the multilayer structure containing the nonwoven fabric layer which consists of a fine cellulose fiber can be provided, and the sheet
- the total heat exchanger using the total heat exchanger element using the sheet for the total heat exchanger of the present invention as a partition material for partitioning two kinds of air having different temperatures, humidity, or both is the total heat exchange of the present invention.
- the sensible heat is used to partition the air with a nonwoven fabric structure that has a high moisture permeability and thermal conductivity, and is not covered by a thick film, has a thin film, or has only a hole embedded therein. As it is easy to conduct, it exhibits excellent heat exchange capacity. Furthermore, since the closed portion partitioning the air is thin, moisture is more easily transmitted than the conventional sheet for a total heat exchanger, so that the effect of maintaining the humidity is enhanced.
- a specific method for using the total heat exchanger element includes, for example, a total heat exchanger in which the total heat exchanger element is combined with a supply fan and an exhaust fan.
- a supply gas such as outside air is sucked into the total heat exchanger element by the supply fan and comes into contact with the total heat exchanger sheet incorporated in the total heat exchanger element.
- exhaust gas such as room air is sucked into the total heat exchanger element by the exhaust fan and similarly contacts the total heat exchanger sheet.
- the supply gas and the exhaust gas that are in contact with each other via the sheet for total heat exchanger exhibit either behavior of supply or discharge according to temperature and humidity, and perform heat exchange.
- the supply gas subjected to heat exchange is blown into a supply fan, and is taken into a room, for example.
- the exhaust gas subjected to heat exchange is blown into the exhaust fan, and is exhausted, for example, outdoors.
- the total heat exchanger element using the multilayered nonwoven fabric of the present invention as a total heat exchanger sheet is efficient. Total heat that can perform heat exchange and maintain the thermal effect of air conditioning while ventilating the interior air containing volatile organic compounds and increasing carbon dioxide while suppressing the release of heat or cold in the building The efficiency of the exchanger can be further increased.
- the main measured values of physical properties were measured by the following methods.
- (1) Average fiber diameter of fine cellulose fibers The surface of the multilayer structure composed of fine cellulose fibers is randomly observed at three locations by a scanning electron microscope (SEM) 10,000 to 100,000 times depending on the fiber diameter of the fine fibers. Perform at an appropriate magnification. With respect to the obtained SEM image, a line is drawn in the horizontal direction and the vertical direction with respect to the screen, and the fiber diameter of the fiber intersecting the line is measured from the enlarged image, and the number of intersecting fibers and the fiber diameter of each fiber are counted. In this way, the number average fiber diameter is calculated using two series of measurement results for one image. Further, the number average fiber diameter is calculated in the same manner for the other two extracted SEM images, and the results for a total of three images are averaged to obtain the average fiber diameter of the target sample.
- SEM scanning electron microscope
- Weight per unit area The weight per unit area W (g / m 2 ) of the multilayer structure is evaluated according to JIS P-8124.
- Average thickness Measure the thickness of each layered multilayer structure in an automatic micrometer manufactured by Hibridge Corporation at 10 points in the width direction under an atmosphere of room temperature 20 ° C and humidity 65% RH, and calculate the average value for the multilayer value. It was set as the average thickness of the structure.
- Density (g / cm 3 ) W / D
- Air permeability resistance (sec / ml) The 25 cm square multi-layer structure is divided into 10 equal parts, and the air resistance is measured for the 10 sections using the Oken air permeability resistance tester (Asahi Seiko Co., Ltd., model EG01). The air resistance of the sample was determined by taking an average value of 10 points.
- Tensile strength was evaluated according to a method defined in JIS P 8113, using a tabletop horizontal tensile tester (No. 2000) manufactured by Kumagaya Riki Kogyo Co., Ltd. The average value was taken as the tensile strength.
- Moisture permeability measurement method For each multi-layer structure, measurement was performed at a humidity of 90% RH in an environment where air at 40 ° C. was circulated by the A-1 method described in JIS L 1099. The moisture permeability (g / m 2 ⁇ 24h) was measured as the initial moisture permeability.
- Example 1 Cotton linter pulp is immersed in water to 10% by weight, heat-treated in an autoclave at 130 ° C. for 4 hours, and the resulting swollen pulp is washed with water many times and swollen in a state of impregnation with water Got.
- the swollen pulp is dispersed in water to a solid content of 1.5% by weight to form a water dispersion (400 L), and a SDR14 type laboratory refiner (pressure type DISK type) manufactured by Aikawa Tekko Co., Ltd. is used as the disc refiner device.
- the beating treatment was continued for 20 minutes on the 400 L aqueous dispersion with a clearance between the disks of 1 mm, and then the beating treatment was continued under the condition that the clearance was reduced to almost zero. Sampling was carried out over time, and the CSF value of the Canadian standard freeness test method (hereinafter referred to as CSF method) of pulp defined by JIS P 8121 was evaluated for the sampling slurry. Then, once it was close to zero, if the beating process continued further, a tendency to increase was confirmed. The beating treatment was further continued under the above conditions to obtain a beating slurry having a CSF value of 73 ml ⁇ .
- the obtained beating slurry was subjected to refinement treatment 5 times under an operating pressure of 100 MPa using a high-pressure homogenizer (NS015H manufactured by Niro Soabi (Italy)) as it was, and an aqueous dispersion M1 (solid content) of fine cellulose fibers. Concentration: 1.5% by weight).
- M1 was diluted with water to a solid content concentration of 0.1% by weight, and dispersed for 4 minutes at room temperature using a home mixer to prepare a papermaking dispersion.
- a cupra rayon nonwoven fabric manufactured by Asahi Kasei Fibers, trade name: Benlyse (registered trademark) TN150 basis weight: 15 g / m 2 , thickness: 50 ⁇ m, density: 0.28 g / cm 3 average single yarn fineness: 0.2 dtex
- Paper making was performed by laminating a fine cellulose fiber layer thereon.
- a plain fabric made of PET / nylon blend as a filter cloth (NT20 manufactured by Shikishima Canvas Co., Ltd., NT20) on a batch-type paper machine (manufactured by Kumagai Riki Kogyo Co., Ltd., automatic square sheet machine, paper making area: 25 cm ⁇ 25 cm, 80 mesh).
- the water permeation amount at 25 ° C. in the atmosphere: 0.03 ml / cm 2 ⁇ s) is set, and the above-described cupra rayon nonwoven fabric is laid thereon, and the formation of a fine cellulose nonwoven fabric layer having a basis weight of 10 g / m 2 is taken as a guide.
- S1 has a laminated structure of two layers, but is a sheet-like structure (weight per unit: 25 g / m 2 ) having a fully integrated tensile strength of 1.4 kg weight / 15 mm and sufficient strength. there were.
- the number average fiber diameter of the fine cellulose fibers on the surface of the fine cellulose fibers was 104 nm.
- 2 and 3 show 1000 times SEM images of the front surface (the fine fiber layer side) and the back surface (the support layer side) of S1, respectively. Both patterns are clearly different, and it can be seen that a laminated structure is formed.
- required from the SEM image of the cut surface was 7.1 micrometers.
- Example 1 except that a fine cellulose fiber layer having a basis weight of 5 g / m 2 is formed on the cupra rayon nonwoven fabric used in Example 1 using the aqueous dispersion slurry M1 of fine cellulose fibers prepared in Example 1. Papermaking and drying were performed under exactly the same conditions to obtain an integrated sheet-like structure S2 (weight per unit area: 20 g / m 2 ) (Example 2) having a two-layer laminated structure. Although S2 had a smaller basis weight of the fine cellulose fiber layer than S1, the tensile strength was 1.1 kg weight / 15 mm, which was sufficient for handling.
- the thickness of the fine cellulose nonwoven fabric layer of S2 obtained from the SEM image of the fractured surface was 3.6 ⁇ m.
- a calendar process (using a roll press manufactured by Yuri Roll Co., Ltd.) was applied to S1 and S2, and an attempt was made to reduce the film thickness.
- the upper roll is a metal roll and the lower roll is an aramid (hardness: I29) roll, and a calendering process is performed at a running speed of 2 m / min at a linear pressure of 2.0 ton / 20 cm.
- Samples S3 (Example 3) and S4, respectively. (Example 4) was obtained.
- the thicknesses of the fine cellulose nonwoven fabric layers of S3 and S4 were 6.9 ⁇ m and 3.5 ⁇ m, respectively.
- the sheets for total heat exchanger had high performance (high moisture permeability and high durability).
- the calendering resistance increases the air permeability resistance, improves the physical property variation, and further improves the thermal conductivity based on the thin film, so that it is higher as a sheet for a total heat exchanger. It became clear that it has aptitude.
- Examples 5 and 6 Abaca pulp is immersed in water to 10% by weight and heat treated in an autoclave at 130 ° C. for 4 hours. The resulting swollen pulp is washed with water many times to obtain a swollen pulp impregnated with water. It was. The swollen pulp is dispersed in water to a solid content of 1.5% by weight to obtain an aqueous dispersion (400 L). Thereafter, beating (beating until the CSF value becomes 588 ml ⁇ ) and fine as in Example 1 The aqueous cellulose dispersion M2 (solid content concentration: 1.5 weight%) of the fine cellulose fiber was obtained.
- Example 5 Thereafter, dilution with water from M2 and dispersion were performed in the same manner as in Example 1 to prepare a papermaking dispersion (solid content: 0.1% by weight), and the basis weight of the fine cellulose fiber layer on the cuprarayon substrate
- the paper S was made so as to be 5 g / m 2 , and the pressing and drying were performed in the same manner as in Example 1, and the sample had a tensile strength of 1.3 kgf / 15 mm and sufficient strength for handling (Example 5) 5) was obtained.
- Example 6 a sample S6 (Example 6) having a tensile strength of 1.4 kg weight / 15 mm and sufficient strength for handling was obtained. It was.
- the surface of the fine fiber layer side of S5 was subjected to SEM image analysis at a magnification of 10,000 times, the number average fiber diameter of the fine cellulose fibers on the surface of the fine cellulose fibers was 45 nm.
- the thicknesses of the fine cellulose nonwoven fabric layers of S5 and S6 were both 3.3 ⁇ m.
- the suitability as a sheet for total heat exchanger of S5 and S6 was examined, the multilayer structure had high performance (high moisture permeability, high durability) as a sheet for total heat exchanger as shown in Table 1 below. Met.
- Example 7 Except that the wet paper was pressed, replaced with an organic solvent with 50% water-containing isobutyl alcohol and dried, refinement, dispersion preparation, papermaking and drying, and calendering were performed in the same manner as in Example 6, and sample S7 ( Example 7) was obtained.
- the thickness of the fine cellulose nonwoven fabric layer of S7 was 5.6 ⁇ m.
- S7 had high performance (high moisture permeability, high durability) as a total heat exchanger sheet.
- Example 8 As in Example 1, refinement and preparation of a papermaking dispersion were carried out, and after stirring the dispersion for 10 minutes at 50 ° C., it was immediately poured into the batch paper machine used in Example 1 to perform papermaking.
- the multilayer structure S8 (Example 8) was obtained by performing press treatment and drying in the same manner as in Example 1.
- the thickness of the fine cellulose nonwoven fabric layer of S8 was 6.9 ⁇ m, which was a slightly thinner thickness of the fine cellulose fiber layer than S1 obtained by papermaking under the same conditions and room temperature.
- the multilayer structure could be used appropriately as a sheet for a total heat exchanger.
- S8 is a sheet produced under the same conditions as in Example 1 except for the papermaking temperature. Compared to S1 obtained in Example 1, the sheet for a total heat exchanger has higher air resistance and higher moisture permeability. In terms of suitability, it had better performance.
- Example 9 a hydroentangled nonwoven fabric having a basis weight of 20 g / m 2 was prepared by hydroentangled a semi-random card web made of rayon fibers having a fiber length of 40 mm and a fineness of 1.7 dtex as a support layer.
- This rayon short fiber nonwoven fabric had a thickness of 100 ⁇ m.
- the microfiber fiber layer was used on the rayon short fiber nonwoven fabric layer with a basis weight of 10 g / m 2 under the same conditions as in Example 1 except that the rayon short fiber nonwoven fabric was used instead of the cupra rayon nonwoven fabric.
- Example 10 Using the slurry of 73 ml ⁇ with a CSF value obtained by beating the linter pulp in Example 1, the slurry was diluted with water to a fiber concentration of 0.08% by weight, at room temperature using a household mixer. A dispersion treatment was performed for 4 minutes to obtain a papermaking dispersion. Using the papermaking dispersion, papermaking was first carried out in the manner of Example 1 with a design having a basis weight of 20 g / m 2 , press treatment, and drying were first performed to produce a short fiber nonwoven fabric made of natural cellulose fibers.
- Example 1 a short fiber nonwoven fabric made of the natural cellulose fiber was used instead of the cupra rayon nonwoven fabric, and the other components were the same as in Example 1 except that 10 g of a fine cellulose fiber layer was formed on the rayon short fiber nonwoven fabric layer.
- a multilayer structure S10 (Example 10) excellent in handleability having a tensile strength of 0.9 kg weight / 15 mm was obtained by laminating at a weight of / m 2 .
- the thickness of the fine cellulose nonwoven fabric layer of S10 was 7.1 ⁇ m. As shown in Table 1 below, the multilayer structure could be used appropriately as a sheet for a total heat exchanger.
- Examples 11 and 12 Samples coated with lithium chloride were prepared as hydrophilization treatments for the two types of multilayer structures prepared in Example 2 and Example 6, S2 and S6, respectively.
- An appropriate amount of 5% by weight lithium chloride aqueous solution is spray-applied uniformly to the surface of each of the fine cellulose fiber nonwoven fabric layers of S2 and S6 and dried in a dryer at 100 ° C. for 10 minutes while fixed to a fixed length frame. It was.
- the multilayer structure coated with lithium chloride obtained from each of S2 and S6 was designated as S11 and S12.
- the adhesion amount of lithium chloride contained in S11 and S12 calculated from the absolute dry weight change before and after the coating treatment was 5% by weight.
- S11 and S12 have a laminated structure of two layers, but the tensile strengths are 1.1 kg weight / 15 mm and 1.8 kg weight / 15 mm, respectively, and both have sufficient strength (weight per unit: 23 g) / M 2 , of which the basis weight was 3 g / m 2 minutes was lithium chloride + the weight of moisture contained in the coating layer).
- the obtained multilayer structure was suitable for use as a total heat exchanger sheet as shown in Table 1 below.
- Table 1 Table 1 below.
- the samples subjected to hydrophilic treatment showed high moisture permeability, and as a sheet for a total heat exchanger, showed higher suitability (high moisture permeability). It has been found that there is a problem in terms of durability of moisture permeability.
- Example 13 A sample was prepared by dispersing and fixing lithium chloride inside the water-soluble polymer coating film as a hydrophilization treatment for S6 produced in Example 6.
- Alcox E-60 manufactured by Meisei Chemical Co., Ltd., which is an ultra-high molecular weight polyethylene glycol as a water-soluble polymer
- an aqueous solution having a lithium chloride concentration of 10% by weight and E-60 of 1% by weight was prepared.
- the surface of S6 is fixed on a glass plate so as to be a fine cellulose fiber nonwoven fabric layer, and an appropriate amount of the aqueous solution is applied thereon using an applicator, and dried in the same manner as in Example 11 to obtain the multilayer of the present invention.
- Structure S13 was obtained.
- S13 The amounts of lithium chloride and E-60 contained in S13 calculated from the absolute dry weight change before and after the hydrophilic treatment were 5% by weight and 0.5% by weight, respectively.
- S13 has a laminated structure of two layers, but has a tensile strength of 1.2 kg weight / 15 mm and possesses sufficient strength (weight: 23 g / m 2 , weight per weight: 3 g / m 2 min. Lithium chloride + E-60 + weight of water contained in the coating layer).
- the obtained multilayer structure was suitable for use as a total heat exchanger sheet as shown in Table 1 below.
- Example 14 and 15 The aqueous dispersion M1 prepared in Example 1 was diluted with water to a fine cellulose fiber concentration of 0.1% by weight, and after dispersion at room temperature for 4 minutes with a home mixer, a water-resistant agent (crosslinking agent) As an emulsion-based aqueous dispersion of blocked polyfunctional isocyanate (BI), an appropriate amount of Meikanate WEB manufactured by Meisei Chemical Co., Ltd. was added, and the BI concentration was adjusted to 0.005% by weight. Stirring was performed for 3 minutes to prepare a papermaking dispersion A.
- BI blocked polyfunctional isocyanate
- aqueous dispersion M2 prepared in Example 5 prepare a dispersion diluted with water so that the fine cellulose fiber concentration becomes 0.1% by weight, and disperse at room temperature for 4 minutes using a home mixer. After the addition, an appropriate amount of mayanate WEB was added so that the BI concentration was 0.005% by weight, and then gently stirred for 3 minutes to prepare a papermaking dispersion B.
- Paper making was performed by laminating a fine cellulose fiber layer on a cupra rayon nonwoven fabric and TN150, and two types of dry sheets were obtained. Next, these two kinds of dry sheets were attached to a fixed length frame, and heat treatment was performed for 2 minutes in an oven set at 160 ° C., so that a crosslinking reaction with a cellulose surface hydroxyl group by isocyanate was advanced. After heat treatment, it was removed from the fixed length frame at room temperature to obtain two types of multilayer structures of the present invention.
- the multilayer structures obtained from each of the papermaking dispersion A and the papermaking dispersion B are designated as S14 (Example 14) and S15 (Example 15).
- S14 and S15 have a laminated structure of two layers, but the tensile strengths are 1.6 kg weight / 15 mm and 1.8 kg weight / 15 mm, respectively, and both have sufficient strength (both weights: 21 g / m 2 ).
- Table 1 the obtained two types of multilayer structures could be used appropriately as a sheet for a total heat exchanger.
- Examples 16 and 17 In the preparation of the dispersion A for papermaking in Example 14, after adding BI which is a water-proofing agent (crosslinking agent) and gently stirring for 3 minutes, as a hydrophilizing agent, trimethylglycine manufactured by Asahi Kasei Chemicals Co., Ltd. Amino Coat (registered trademark), 0.01% by weight, was added and further gently stirred for 3 minutes to prepare a dispersion C for papermaking. Thereafter, in the same manner as in Example 14, papermaking, drying and heat treatment were performed using the dispersion C for papermaking with the basis of formation of a fine cellulose nonwoven fabric layer having a basis weight of 5 g / m 2 , and the multilayer structure of the present invention.
- BI is a water-proofing agent (crosslinking agent)
- Amino Coat registered trademark
- Body S16 (Example 16) was obtained.
- Dispersion D for papermaking was prepared by adding 0.01% by weight of Aron Frock (registered trademark), C-508, which is a functional polymer, and further gently stirring for 3 minutes. Thereafter, in the same manner as in Example 14, papermaking, drying and heat treatment were performed using the dispersion D for papermaking, with the basis of the formation of a fine cellulose nonwoven fabric layer having a basis weight of 5 g / m 2 , and the multilayer structure of the present invention.
- Body S17 (Example 17) was obtained.
- S16 and S17 have a laminated structure of two layers, but the tensile strengths are 1.4 kg weight / 15 mm and 1.7 kg weight / 15 mm, respectively, and both have sufficient strength (weight per unit: 22 g) / M 2 (S16) and 23 g / m 2 (S17)).
- Table 1 the multilayer structure could be used appropriately as a sheet for a total heat exchanger.
- the two types of hydrophilizing agents obtained from the change in basis weight seem to be retained on the surface of the fine cellulose fibers and then fixed on the surface and inside of the fine cellulose fiber layers by subsequent papermaking.
- the water vapor transmission rate increased and also durability was favorable.
- the tensile strengths in the wet environment of S16 and S17 were 0.48 kg weight / 15 mm and 0.49 kg weight / 15 mm, respectively, and both were multilayer structures usable in a wet environment.
- Example 18 The oil agent of Tencel (registered trademark) cut yarn (3 mm length) supplied by Lenzing Fibers, Inc. was sufficiently removed by washing several times with a surfactant-added system in water, and the water-containing short state A fiber yarn was obtained.
- the short fiber yarn is dispersed in water to a solid content of 1.5% by weight to obtain an aqueous dispersion (400 L), and thereafter beating as in Example 1 (beating until the CSF value reaches 90 ml ⁇ ) And a high-pressure homogenizer were used to obtain an aqueous dispersion M3 (solid content concentration: 1.5% by weight) of fine cellulose fibers.
- both dispersions are mixed so that the weight ratio of the fine cellulose fibers contained in the dispersion M2 prepared in Example 5 and the fine cellulose fibers contained in the dispersion M3 is 50:50, respectively.
- the solid content concentration was adjusted to 0.15% by weight, and dispersion was performed for 4 minutes at room temperature using a household mixer to prepare a papermaking dispersion.
- Paper is made on a cupra rayon substrate so that the basis weight of the fine cellulose fiber layer is 5 g / m 2 , pressing and drying are performed in the same manner as in Example 1, and the tensile strength is 1.1 kg weight / 15 mm.
- Sample S18 (Example 18) having sufficient strength was obtained.
- the number average fiber diameter of the fine cellulose fibers on the surface of the fine cellulose fibers was 273 nm.
- the thickness of the fine cellulose nonwoven fabric layer of S18 was 6.2 ⁇ m.
- Example 19 and 20 In Example 14 and Example 16, the support on which the fine cellulose fiber nonwoven fabric layer is laminated is replaced with TN150 by Asahi Kasei Fibers Co., Ltd. nylon spunbond, NO5020, and the others are exactly the same, and the multilayer nonwoven fabric S19 of the present invention is used. (Example 19) and S20 (Example 20) were obtained. S19 and S20 have a laminated structure of two layers, but the tensile strengths are 2.0 kg weight / 15 mm and 1.9 kg weight / 15 mm, respectively, and both have sufficient strength (weight per unit: 21 g) / M 2 (S19) and 22 g / m 2 (S20)).
- the tensile strengths in the wet environment of S19 and S20 were 1.9 kg weight / 15 mm and 1.7 kg weight / 15 mm, respectively, and both were multilayer structures usable in a wet environment. As shown in Table 1 below, both samples were suitable for use as a total heat exchanger sheet.
- Example 21 The multilayer structure S4 obtained in Example 4 was immersed in a 20% by weight aqueous solution of a guanidine sulfamate flame retardant (manufactured by Sanwa Chemical Co., Ltd .: Apinone-101) and dried to obtain a flame retardant content. 22.9% by weight of a flame retardant treated total heat exchanger sheet was obtained. The sheet was subjected to a flame retardancy test in accordance with JIS A 1322 “Flame retardance test method for thin materials for building”, and as a result of observing carbonization length, after flame, and residual dust, it became a flameproof second grade.
- the physical properties of this flame retardant multilayer structure sample S21 (Example 21) are shown in Table 1 below. S21 could be used appropriately as a sheet for a total heat exchanger.
- Example 1 In the same manner as in Example 10, the slurry having a CSF value of 73 ml ⁇ obtained by beating the linter pulp in Example 1 was diluted with water to a fiber concentration of 0.08% by weight. Using a home mixer, dispersion was performed at room temperature for 4 minutes to obtain a papermaking dispersion. Using this papermaking dispersion, first, papermaking was performed in the manner of Example 1 with a design having a basis weight of 20 g / m 2 , press treatment, and drying, and a short fiber nonwoven fabric sample R1 made of natural cellulose fibers (Comparative Example 1). Got.
- both R1 and R2 do not include a layer made of a predetermined fine cellulose fiber, there is a problem in particular that a large air resistance cannot be expressed. Even in the increased R2, it was a value smaller than any air permeability resistance of the example. That is, both samples were clearly inferior in suitability as a total heat exchanger sheet than the samples shown in Examples 1 to 20 above.
- Example 3 Cupra rayon nonwoven fabric used as a base material in Example 1 (manufactured by Asahi Kasei Fibers, trade name: Benrise (registered trademark) TN150 basis weight: 15 g / m 2 , thickness: 50 ⁇ m, density: 0.28 g / cm 3) Average single yarn fineness: 0.2 dtex) was overlapped and calendered under the same calendering conditions as described in Example 3 to obtain Sample R3 (Comparative Example 3). When the suitability of R3 as a sheet for a total heat exchanger was evaluated, the results shown in Table 2 below were obtained.
- R3 does not include a layer made of a predetermined fine cellulose fiber, it largely deviates from a predetermined air permeation resistance, and is not suitable for use as a sheet for a total heat exchanger in terms of air intake and exhaust air blocking properties. .
- Example 4 The paper was calendered under the same calendering conditions as described in Example 3 to obtain Sample R4 (Comparative Example 4).
- R4 was subjected to a hydrophilization treatment under the same lithium chloride coating conditions as described in Example 11 to obtain sample R5 (Comparative Example 5) in which lithium chloride was uniformly coated in an amount of 1 g / m 2 . .
- R4 and R5 both had sufficient tensile strength of 1.6 kg weight / 15 mm, the suitability evaluation as a sheet for a total heat exchanger was performed, and the results shown in Table 2 below were obtained.
- R4 does not achieve both high air permeability and high moisture permeability (low air resistance), and R5, which has slightly increased air resistance due to the application of lithium chloride, has higher moisture permeability due to the effect of the hygroscopic agent.
- the moisture permeability after a high humidity history is greatly reduced, and there is a problem in terms of durability. That is, both samples were sheets inferior to those of Examples 1 to 20 as total heat exchanger sheets.
- Example 22 The total heat exchanger sheet S17 obtained in Example 17 and the step-molded glossy kraft paper (weight per unit of 65 g / m 2 manufactured by Shiroyama Paper Co., Ltd.) were bonded to produce a total heat exchanger element. A cross flow type static total heat exchanger (190 mm ⁇ 190 mm ⁇ 350 mm, 134 stages) was produced. When the heat exchange rate was measured according to JIS B 8628, the total heat exchange rate was 81%.
- the multilayer structure of the present invention Since the multilayer structure of the present invention has air permeability resistance, moisture permeability, and relatively high thermal conductivity, it is a partition material for an air conditioning total heat exchanger for offices and a total heat exchanger for home use (all It can be suitably used as a heat exchange element.
- the multilayer structure of the present invention when used as a sheet for a total heat exchanger, it not only has excellent air resistance, moisture permeability, and thermal conductivity, but also has excellent durability. By using it for an exchanger, it is possible to provide a heat exchanger that has extremely high humidity exchange efficiency and total heat exchange efficiency over a long period of time.
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Abstract
Description
かかる全熱交換器としては、吸湿性のあるローターの回転によって排気から吸気に熱回収する回転型全熱交換器や、図1に示すような静止型全熱交換器が挙げられる。この静止型全熱交換器は、波板状に配されたガスバリア性のある全熱交換器用素子が、換気により交換される外部の新鮮な供給空気と室内の汚濁した排出空気とを分けながら、顕熱を移動させると同時に、湿気を透過させることによって水が有する潜熱を排出空気から供給空気へ通過することで、外部への熱又は冷熱の放出を抑えるものである。
[1]微細セルロース繊維からなる微細セルロース繊維不織布層を少なくとも一層含む多層構造体であって、該微細セルロース繊維不織布層を形成する微細セルロース繊維の平均繊維径が0.005μm以上0.5μm以下であり、さらに該多層構造体の平均厚みが10μm以上200μm以下、密度が0.10g/cm3以上0.90g/cm3以下、かつ、透気抵抗度が2000s/100ml以上であることを特徴とする多層構造体。
不織布層上に平均繊維径が0.005μm以上0.5μm以下である微細セルロース繊維不織布層を抄紙法により積層形成させる工程、及び
得られた積層不織布を乾燥させる工程、
を含む、前記[1]~[6]のいずれかに記載の多層構造体の製造方法。
前記[1]~[6]のいずれかに記載の多層構造体の片面又は両面に親水性塗工層を塗工により形成させる工程、
を含む、前記[14]に記載の多層構造体の製造方法。
同時に、薄くて緻密な微細セルロース繊維不織布層はその薄さと共に、構成する微細繊維の単位体積当たりの存在密度の大きさ(すなわち内部界面積)のために、繊維界面の表面熱伝導性を確保でき、該層自体が高い熱伝導性を保有することになる。
密度(g/cm3)= W×(10-2)2(g/cm2)/(D×10-4)(cm) = W/D
により、求めることができる。
製造工程の効率化の観点から、本発明の多層構造体は、微細セルロース繊維からなる微細セルロース繊維不織布層と、支持体としての不織布層又は多孔質膜との2層構造であることが好ましく、さらに上述した理由により、微細セルロース繊維からなる微細セルロース繊維不織布層と、再生セルロース繊維からなる不織布層との2層構造である不織布構造体であることが、全熱交換器用シートとしての性能を好適に発現できる点で、好ましい。また、強度保持の観点からは、再生セルロース繊維からなる不織布層は、再生セルロース連続長繊維からなる不織布層であることが好ましい。
内添法に関しては、上述したセルロースのマイナスの表面ゼータ電位を利用して、微細セルロース繊維の抄紙用分散液中にカチオン性である吸湿性の親水性化合物を添加、吸着させておき、しかる後に分散液を抄紙、支持体上に積層させることにより微細セルロース不織布層全体をより親水的にすることができる。本法は上述の耐水化処理における架橋剤と併用して親水性化合物を内添させ、微細セルロース繊維の表面に吸着、固定化させた上で抄紙、支持体上に積層化させると同時に熱処理による架橋反応の進行により耐水化と同時に親水性化合物の微細セルロース不織布層の表面及び/又は内部への固定化にも繋がり有効である。このような目的で使用する親水性化合物としては架橋剤と反応する部位を分子骨格に含む親水性化合物であることが好ましい。例えば、耐水化剤としてカチオン化BIを用いる場合にはイソシアネートに反応性を有する水酸基、アミン基、アミド基等を有する親水性の化合物、例えば、アニオン性やカチオン性のポリビニルアルコール(ビニルアルコールとアニオン性またはカチオン性ビニルモノマーとの共重合体)を挙げることができるがこれは一例に過ぎず、限定されるものではない。
上記親水化処理に用いることのできる親水性化合物としては、無機酸塩、有機酸塩、無機質填材、多価アルコール、尿素類、吸湿(吸水)性高分子(水溶性高分子やハイドロゲル形成能のある親水性高分子)などがあり、例えば、無機塩としては、塩化リチウム、塩化カルシウム、塩化マグネシウム、有機塩としては、乳酸ナトリウム、乳酸カルシウム、ピロリドンカルボン酸ナトリウム、無機質填材としては、水酸化アルミニウム、炭酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、タルク、クレー、ゼオライト、珪藻土、セピオライト、シリカゲル、活性炭、多価アルコールとしては、グリセリン、エチレングリコール、トリエチレングリコール、ポリグリセリン、尿素類としては、尿素、ヒドロキシルエチル尿素、吸湿(吸水)性高分子として、ポリアスパラギン酸、ポリアクリル酸、ポリグルタミン酸、ポリリジン、アルギン酸、カルボキシルメチルセルロース、カルボキシルエチルセルロース、ヒドロキシルアルキルセルロース及びそれらの塩または架橋物、カラギーナン、ペクチン、ジェランガム、寒天、キサンタンガム、ヒアルロン酸、グアーガム、アラビアゴム、澱粉及びそれらの架橋物、ポリエチレングリコール、ポリプロピレングリコール、コラーゲン、アクリルニトリル系重合ケン化物、澱粉/アクリルニトリルグラフト共重合体、アクリル酸塩/アクリルアミド共重合体、ポリビニルアルコール/無水マレイン酸共重合体、多糖類、/アクリル酸塩グラフト自己架橋体等の吸湿剤が挙げられ、目的とする吸湿度に応じて種類や付着量を選んで用いられる。尚、前記無機質填量とは、無機鉱物や無機塩などであって、吸湿目的の他に増量剤、嵩高剤などの目的で使用するものをいう。該吸湿剤を固定化させる(高湿度で透湿剤が移動しないようにする)目的で、上記記載を含む水溶性高分子と無機塩類や有機塩類と共存させると有効である場合もある。
耐水化剤、親水性化合物その他添加剤(例えば、全熱交換器用シートにおける難燃剤)は上述したように本発明の多層構造体の性能を向上させるために適宜使用することができるが、その含有量としては、総和として全熱交換器用シートの全重量の30重量%以下に抑えられることが好ましく、より好ましくは20重量%以下、さらに好ましくは10重量%以下である。この範囲にあると、高性能の本発明の多層構造体を提供することが可能となる。これら添加剤類は各々の目的で効果を発揮する代わりに化学物質としての活性も高いものが多いため、含有量の総和が30重量%を超えると、基材である本発明の多層不織布構造体シートの耐久性が著しく損なわれるため、好ましくない。
この結果、本発明の多層構造体は前述の全熱交換器用シート以外にも高い透湿度と高い透気抵抗度及び比較的高い熱伝導性を活かせるあらゆる用途に適用可能である。このような用途として、高い水蒸気透過性が問われる膜蒸留のような水処理膜、低い透水性(高い透気抵抗度に相当)と水蒸気透過性が問われる衣料用素材等を挙げることができるがこれらに限定されるものではない。
本発明の全熱交換器用シートは、全熱交換素子のコンパクト化や熱伝導率の要求から薄いものを用いる方が好ましく、全体平均厚みは10μm以上200μm以下、好ましくは10μm以上120μm以下、より好ましくは10μm以上70μm以下、さらに好ましくは10μm以上30μm以下である。該平均厚みが10μm未満のシートは技術的に製造が困難であり、また120μmよりも大きな平均厚みのものでは熱伝導率が著しく低くなるため好ましくない。
上記難燃剤の含有量としては、全熱交換器用シートの1重量%以上15重量%であると好適である。1重量%未満であると、難燃効果を発揮し難い。また15重量%を超えて含有すると、透湿度が減少し、熱交換効率が減少する。より好ましくは2量%以上10重量%以下で、さらに好ましくは3重量%以上8重量%以下である。
本発明で使用する微細セルロース繊維不織布層を含む多層構造体は、まず、微細セルロース繊維の水分散液を調製し、該分散液を用いて以下に記載する方法により製膜して得る。
微細セルロース繊維を製造する際の原料としては、針葉樹パルプや広葉樹パルプ等のいわゆる木材パルプと非木材パルプを使用することができる。非木材パルプとしては、コットンリンターパルプを含むコットン由来パルプ、麻由来パルプ,バガス由来パルプ,ケナフ由来パルプ,竹由来パルプ,ワラ由来パルプを挙げることができる。コットン由来パルプ,麻由来パルプ,バガス由来パルプ,ケナフ由来パルプ,竹由来パルプ、ワラ由来パルプは、各々、コットンリントやコットンリンター、麻系のアバカ(例えば、エクアドル産やフィリピン産のものが多い)、ザイサルや、バガス、ケナフ、竹、ワラ等の原料を蒸解処理による脱リグニン等の精製工程や漂白工程を経て得られる精製パルプを意味する。この他、海藻由来のセルロースやホヤセルロースの精製物も微細セルロース繊維の原料として使用することができる。さらに、再生セルロース繊維のカット糸やセルロース誘導体繊維のカット糸もその原料として使用でき、また、エレクトロスピニング法により得られた再生セルロース又はセルロース誘導体の極細糸のカット糸も微細セルロース繊維の原料や微細セルロース繊維そのものとして使用することができる。
セルロース繊維の微細化は、前処理工程、叩解処理工程及び微細化工程を経ることが好ましい。
前処理工程においては、100~150℃の温度での水中含浸下でのオートクレーブ処理、酵素処理等、又はこれらの組み合わせによって、原料パルプを微細化し易い状態にしておくことは有効である。これらの前処理は、微細化処理の負荷を軽減するだけでなく、セルロース繊維を構成するミクロフィブリルの表面や間隙に存在するリグニンやヘミセルロースなどの不純物成分を水相へ排出し、その結果、微細化された繊維のα-セルロース純度を高める効果もあるため、微細セルロース繊維不織布の耐熱性の向上に大変有効であることもある。
我々の検討において、叩解処理を行うにつれCSF値(セルロースの叩解の程度を示す。JIS P 8121で定義されるパルプのカナダ標準ろ水度試験方法で評価)が経時的に減少していき、一旦、ゼロ近くとなった後、さらに叩解処理を続けると再び増大していく傾向が確認され、本発明の不織布構造体の原料である微細セルロース繊維を調製するためには、前処理として、CSF値が一旦、ゼロ近くとなった後、さらに叩解処理を続けCSF値が増加している状態まで叩解することが好ましいことが分かった。本発明では、未叩解からCSF値が減少する過程でのCSF値を***↓、ゼロとなった後に増大する傾向におけるCSF値を***↑と表現する。該叩解処理においては、CSF値は少なくともゼロが好ましく、より好ましくはCSF30↑である。このような叩解度に調製した水分散体(以下「スラリー」ともいう。)ではフィブリル化が高度に進行し、最大繊維径2500nmを越える粗大セルロース繊維を含まない濾材を提供できると同時に、当該スラリーから得られた微細セルロース繊維不織布からなる濾材は、セルロースミクロフィブリル同士の接着点の増加からか、引張強度が向上する傾向がある。また、CSF値が少なくともゼロ又はその後増大する***↑の値をもつ高度に叩解されたスラリーは均一性が増大し、その後の高圧ホモジナイザー等による微細化処理での詰まりを軽減できるという製造効率上の利点がある。
さらに、本発明に使用できる微細セルロース繊維として、上述した工程により製造されたMFCに対し、表面の化学処理を加えたセルロース系の微細繊維、及びTEMPO酸化触媒によって6位の水酸基が酸化され、カルボキシル基(酸型、塩型を含む)となったセルロース系の微細繊維を本発明の微細セルロース繊維として使用することもできる。前者の場合は、目的に応じて種々の表面化学処理を施すことにより、例えば、微細セルロース繊維(セルロースミクロフィブリル)の表面に存在する一部又は大部分の水酸基が酢酸エステル、硝酸エステル、硫酸エステルを含むエステル化されたもの、メチルエーテルを代表とするアルキルエーテル、カルボキシメチルエーテルを代表とするカルボキシエーテル、シアノエチルエーテルを含むエーテル化されたものを、適宜調製して使用することができる。また、後者、すなわち、TEMPO酸化触媒によって6位の水酸基が酸化された微細セルロースの調製においては、必ずしも高圧ホモジナイザーのような高エネルギーを要する微細化装置を使用することは必要なく、微細セルロースの分散体を得ることができる。例えば、文献(A.Isogai et al.,Biomacromolecules,7,1687-1691(2006))に記載されるように、天然セルロースの水分散体に2,2,6,6-テトラメチルピペリジノオキシラジカルのようなTEMPOと呼ばれる触媒とハロゲン化アルキルを共存させ、これに次亜塩素酸のような酸化剤を添加し、一定時間反応を進行させることにより、水洗等の精製処理後に、通常のミキサー処理を施すことにより極めて容易に微細セルロース繊維の分散体を得ることができる。TEMPO触媒により得られた微細セルロース繊維の表面には、カルボキシル基が導入されることが知られており、その高い親水性により、該微細セルロース繊維を本発明の原料として使用することにより高い透湿度が得られることもある。
製膜方法としては、抄紙法により製造することが好ましい。塗布法による形成も可能ではあるが、不織布等の支持体層に適度に絡み合い、欠陥が極めて少なく製膜できるという点で、抄紙法による製膜の方が好ましい。いずれの場合も上述した各種支持体の上から微細セルロース繊維の水分散体を抄紙又は塗布し、積層化させる。
(1)微細セルロース繊維0.05重量%以上0.5重量%以下、水85重量%以上99.5重量%以下を含む水系分散液を調製する調製工程、(2)水系分散液を構成する水の一部を抄紙機にセットした支持体上で脱水することによって、微細セルロース繊維の濃度を該水系分散液より増加させた濃縮組成物を得る抄紙工程、(3)濃縮組成物を加熱することによって、該濃縮組成物から水の一部を蒸発させて除去する乾燥工程、の3つの工程を含む多層構造体の製造方法である。この中の(2)で、抄紙法を採用することで、好適に本発明の多層構造体を製造することができる。
上記の水系分散液を用いた抄紙法による微細セルロース繊維不織布層の形成方法は、所定の微細セルロース繊維の水系分散液から抄紙法によりワイヤーや濾布上で支持体としての上述した内容の不織布、多孔質膜、または布帛の上に湿紙を製膜し、場合によってはこれを積層させて積層構造の湿紙を製造し、該湿紙(積層体の場合には積層体の湿紙全体)を乾燥させるというものである。
調製工程で使用する微細セルロース繊維の水系分散液は、微細セルロース繊維0.01重量%以上0.5重量%以下、水85重量%以上99.99重量%以下を含む水系分散液であることが好ましい。
抄紙用の水系分散液中の微細セルロース繊維の濃度は、0.01重量%以上0.5重量%以下、より好ましくは0.03重量%以上0.35重量%以下である。かかる範囲にあると、安定な抄紙を実施することができる。該水系分散液中の微細セルロース繊維濃度が0.01重量%よりも低いと濾水時間が非常に長くなり生産性が著しく低くなると同時に膜質均一性も著しく悪くなるため好ましくない。また、微細セルロース繊維濃度が0.5重量%よりも高いと、分散液の粘度が上がり過ぎてしまうため、均一に製膜することが困難になり、やはり好ましくない。
微細セルロース繊維の抄紙用分散液の溶媒は水のみであっても構わないが場合によっては、例えば、透湿度や透気抵抗度等の諸物性をコントロールする目的で各種化合物を添加しても有効であることがある。
該水系分散液の調製は、一切の添加物を水中へ混入し、適当な分散方法により水系スラリー分散液とするか、又は予め添加物を含む水溶液を別途調製した微細セルロース繊維の水分散体と混合して水系分散液とすればよい。その際、混合、分散する手法としては、ブレンダー(家庭用ミキサー)やディスパータイプの羽根をもつ分散機での低速又は高速で攪拌するか、又は高圧ホモジナイザーを適宜条件制御した条件で使用することが好ましい。
抄紙機としては、傾斜ワイヤー式抄紙機、長網式抄紙機、円網式抄紙機のような装置を用いると好適に欠陥の少ないシート状の微細セルロース繊維不織布層を含む多孔構造体を得ることができる。抄紙機は連続式であってもバッチ式であっても目的に応じて使い分ければよい。
但し、セルロース等の歩留まり割合が70重量%以上であっても濾水性が高くないと抄紙に時間がかかり、著しく生産効率が悪くなるため、大気圧下25℃でのワイヤー又は濾布としては、水透過量が好ましくは0.005ml/cm2・s以上、より好ましくは0.01ml/cm2・s以上であるものを用いる。この範囲にあると、生産性の観点から好適な抄紙が可能となる。上記水不溶成分の歩留まり割合が70重量%よりも低くなると、生産性が著しく低減するばかりか、用いるワイヤーや濾布内にセルロース等の水不溶性成分が目詰まりしていることになり、製膜後の多層構造体の剥離性も著しく悪くなる。
バッチ式抄紙機(例えば、熊谷理機工業社製の自動角型シートマシーン)に評価対象となるワイヤー又は濾布を設置するにおいて、ワイヤーの場合はそのまま、濾布の場合は、80~120メッシュの金属メッシュ(濾水抵抗がほとんど無いものとして)上に濾布を設置し、抄紙面積がxcm2の抄紙機内に十分な量(ymlとする)の水を注入し、大気圧下で濾水時間を測定する。濾水時間がzs(秒)であった場合の水透過量を、y/(xz)(ml/cm2・s)と定義する。
すなわち、ワイヤー又は濾布をセットした抄紙機に当該支持体をのせて、水系分散液を構成する水の一部を該支持体上で脱水(抄紙)を行い、該支持体上に微細セルロース繊維から成る微細セルロース繊維不織布の湿紙を積層化させ、一体化させることにより、少なくとも2層以上の多層構造体からなる多層化シートを製造することができる。3層以上の多層化シートを製造するためには、2層以上の多層構造を有する支持体を使用すればよい。また、支持体上で2層以上の本発明の微細セルロース繊維不織布の多段抄紙を行って3層以上の多層シートとしてもよい。抄紙により本発明の多層構造体を製造後、別の支持体(不織布、多孔質膜あるいは布帛)あるいは別途製造した本発明の多層化不織布と加熱プレス処理等により貼り合せ、一体化させてもよい。
後加工の工程は、内添法でなく後加工で必要な機能を設けるために行う。例えば、全熱交換器用シートを製造する場合には、前述した内容の所定の透湿剤又は難燃剤の塗工液(水系であっても有機溶媒系であっても構わない)を調製し、該塗工液をスプレー塗布又は印刷法、塗工法などの工程で塗布、乾燥させる。化学処理の場合には、乾燥工程の後に、内添法と同様に熱処理させ、反応を進行させる。
以上の条件を満たすことにより、微細セルロース繊維から成る不織布層を含む多層構造体を提供でき、また、該多層構造体からなる全熱交換器用シートを提供することができる。
全熱交換器用シートを介して接触した供給気体と排出気体とは、温度及び湿度に応じて、供給及び排出のいずれかの挙動を示して熱交換を行う。熱交換された供給気体は、供給ファンに吹き込んで、例えば、室内に取り込まれたりする。一方で、熱交換された排出気体は、排出ファンに吹き込んで、例えば、屋外に排出されたりする。
本発明の多層化不織布を全熱交換器用シートとして使用した全熱交換素子である全熱交換器用素子を、単数又は複数備えた全熱交換器を用いて全熱交換を行うと、効率的な熱交換が行え、建築物内の熱又は冷熱の放出を抑制しつつ、揮散性の有機化合物を含み二酸化炭素が増加した内部の空気を排出する換気を行いつつ冷暖房による熱効果を維持する全熱交換器の効率をより高められる。
尚、物性の主な測定値は以下の方法で測定した。
(1)微細セルロース繊維の平均繊維径
微細セルロース繊維からなる多層構造体の表面に関して、無作為に3箇所、走査型電子顕微鏡(SEM)による観察を微細繊維の繊維径に応じて10000~100000倍相当の倍率で行う。得られたSEM画像に対し、画面に対し水平方向と垂直方向にラインを引き、ラインに交差する繊維の繊維径を拡大画像から実測し、交差する繊維の個数と各繊維の繊維径を数える。こうして一つの画像につき縦横2系列の測定結果を用いて数平均繊維径を算出する。さらに抽出した他の2つのSEM画像についても同じように数平均繊維径を算出し、合計3画像分の結果を平均化し、対象とする試料の平均繊維径とする。
多層構造体の目付W(g/m2)の評価は、JIS P-8124に準じて算出する。
室温20℃、湿度65%RHの雰囲気下で、調湿した多層構造体をハイブリッジ製作所製のオートマティックマイクロメーターにて、それぞれのシートについて幅方向10点で厚みを測定し、その平均値を多層構造体の平均厚みとした。
多層構造体の密度は、前記目付Wと平均厚みDとから、次式に従って算出した:
密度(g/cm3)=W/D
25cm角の多層構造体を10等分にエリア分けし、当該10区画について王研式透気抵抗試験機(旭精工(株)製、型式EG01)を用いて、透気抵抗度を測定し、10点の平均値をとることにより試料の透気抵抗度とした。
引張強度の評価は、JIS P 8113にて定義される方法に従い、熊谷理機工業(株)の卓上型横型引張試験機(No.2000)を用い、幅15mmのサンプル10点について測定し、その平均値を引張強度とした。
各多層構造体について、JIS L 1099に記載のA-1法により、40℃の空気を循環させた環境で、湿度90%RHに設定して測定した24時間あたりの透湿度(g/m2・24h)を、初期の透湿度として測定した。
室温20℃、湿度65%RHの雰囲気下で、100mm×100mmの大きさに切り出したそれぞれの不織布構造体を上部29.9℃、下部22.3℃の試験板(50mm×50mm)に挟み、60秒間の熱流をカトーテック社製の精密迅速熱物性測定装置KES-F7 THERMO LABOIIを用いて測定し、その値から熱伝導率を算出した。
多層構造体の透湿度測定を実施後、25℃,50%RHにて1時間保持後、該多層構造体を定長枠にセットし、多層構造体を一定面積に温度30℃,湿度99%以上に設定したデシケータ内に48時間保存した。その後に定長枠ごと25℃,50%RHにて1時間保持後、多層構造体を定長枠から取り外し、(7)と同じ要領で透湿度測定を行い、高湿履歴後の透湿度として全熱交換器用シートの透湿耐久性能の尺度とした。
コットンリンターパルプを10重量%となるように水に浸液させてオートクレーブ内で130℃,4時間の熱処理を行い、得られた膨潤パルプを何度も水洗し、水を含浸した状態の膨潤パルプを得た。
該膨潤パルプを固形分1.5重量%となるように水中に分散させて水分散体(400L)とし、ディスクリファイナー装置として相川鉄工(株)製SDR14型ラボリファイナー(加圧型DISK式)を用い、ディスク間のクリアランスを1mmとして400Lの該水分散体に対して、20分間叩解処理を進めた後、引き続いてクリアランスをほとんどゼロに近いレベルにまで低減させた条件下で叩解処理を続けた。経時的にサンプリングを行い、サンプリングスラリーに対して、JIS P 8121で定義されるパルプのカナダ標準ろ水度試験方法(以下、CSF法)のCSF値を評価したところ、CSF値は経時的に減少していき、一旦、ゼロ近くとなった後、さらに叩解処理を続けると、増大していく傾向が確認された。上記条件でさらに叩解処理を続け、CSF値で73ml↑の叩解スラリーを得た。得られた叩解スラリーを、そのまま高圧ホモジナイザー(ニロ・ソアビ社(伊)製NS015H)を用いて操作圧力100MPa下で5回の微細化処理を実施し、微細セルロース繊維の水系分散液M1(固形分濃度:1.5重量%)を得た。次に、M1を水で希釈し、固形分濃度を0.1重量%とし、家庭用ミキサーで、室温で4分間分散を行い、抄紙用分散液を調製した。
実施例1において調製した微細セルロース繊維の水分散スラリーM1を用い、実施例1で使用したキュプラレーヨン不織布上に目付が5g/m2相当の微細セルロース繊維層を形成させる点以外は実施例1と全く同等の条件で抄紙および乾燥を行い、2層の積層構造をもつ一体化したシート状構造体、S2(目付:20g/m2)(実施例2)を得た。S2はS1に比べ微細セルロース繊維層の目付が小さいものの引張強度は1.1kg重/15mmと取扱いに十分な強度を保有していた。割断面のSEM画像から求めたS2の微細セルロース不織布層の厚みは、3.6μmであった。
次に、S1とS2に対して、カレンダー処理(由利ロール社製ロールプレス装置を使用)を施し、薄膜化を試みた。上部ロールを金属ロールとし、下部ロールをアラミド(硬度:I29)ロールとして線圧2.0トン/20cmで2m/minの走行速度でカレンダー処理を施し、それぞれ、サンプルS3(実施例3)とS4(実施例4)を得た。S3とS4の微細セルロース不織布層の厚みは、それぞれ、6.9μmおよび3.5μmであった。S2~S4の全熱交換器用シートとしての適性を調べたところ、以下の表1に示すとおり、全熱交換器用シートとして高い性能(高透湿度,高耐久性)を有するものであった。特に、S3とS4では、カレンダー処理により、透気抵抗度が増大し、物性ばらつきも改善され、さらに薄膜化に基づく熱伝導性の向上も付与されることから、全熱交換器用シートとしてより高い適性を有することが明らかになった。
アバカパルプを10重量%となるように水に浸液させてオートクレーブ内で130℃,4時間の熱処理を行い、得られた膨潤パルプを何度も水洗し、水を含浸した状態の膨潤パルプを得た。
該膨潤パルプを固形分1.5重量%となるように水中に分散させて水分散体(400L)とし、以降、実施例1と同様に叩解(CSF値として588ml↑になるまで叩解)と微細化処理を行い、微細セルロース繊維の水系分散液M2(固形分濃度:1.5重量%)を得た。以降、実施例1と同じ要領でM2からの水による希釈と分散を施し抄紙用分散液(固形分率:0.1重量%)を調製し、キュプラレーヨン基材上に微細セルロース繊維層の目付が5g/m2となるように抄紙を行い、プレス、乾燥も実施例1と同等の内容で行い、引張強度が1.3kg重/15mmと取扱いに十分な強度を保有するサンプルS5(実施例5)を得た。
さらに、S5に対して、実施例3と実施例4と同等の条件でカレンダー処理を行い引張強度が1.4kg重/15mmと取扱いに十分な強度を保有するサンプルS6(実施例6)を得た。
S5の微細繊維層側の表面を10000倍の倍率でSEM画像解析を行ったところ、微細セルロース繊維の表面における微細セルロース繊維の数平均繊維径は45nmであった。S5とS6の微細セルロース不織布層の厚みは、共に、3.3μmであった。S5とS6の全熱交換器用シートとしての適性を調べたところ、多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして高い性能(高透湿度,高耐久性)を有するものであった。
湿紙をプレス処理後、50%含水のイソブチルアルコールで有機溶媒置換して乾燥する以外は、実施例6と同様に微細化、分散液調製、抄紙及び乾燥、さらにカレンダー処理を行い、サンプルS7(実施例7)を得た。S7の微細セルロース不織布層の厚みは、5.6μmであった。S7は、以下の表1に示すとおり、全熱交換器用シートとして高い性能(高透湿度,高耐久性)を有するものであった。
実施例1と同様に微細化、及び抄紙用分散液の調製を行い、分散液を50℃として10分間攪拌を続けた後、直ちに実施例1で用いたバッチ式抄紙機に注ぎ、抄紙を行い、プレス処理及び乾燥を、同じく実施例1の要領で行うことにより、多層構造体S8(実施例8)を得た。S8の微細セルロース不織布層の厚みは、6.9μmであり、同一条件、室温で抄紙を実施して得たS1に比べ若干薄い微細セルロース繊維層の厚みであった。多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。S8は、実施例1と抄紙温度以外は変わらない条件で作製したシートであるが、実施例1で得られたS1に比べ、透気抵抗度が高くかつ透湿度の高い、全熱交換器用シートとしての適性において、より優れた性能を有していた。
まず、支持体層として、繊維長が40mm、繊度が1.7dtexのレーヨン繊維からなるセミランダムカードウエッブを水流交絡処理して目付が20g/m2の水流交絡不織布を作製した。このレーヨン短繊維不織布は、厚み100μmであった。実施例1でキュプラレーヨン不織布の代わりに該レーヨン短繊維不織布を用いて、その他は実施例1と全く同じ条件で該レーヨン短繊維不織布層の上に微細セルロース繊維層を10g/m2の目付で積層させ、引張強度が1.2kg重/15mmである取扱い性に優れた多層構造体S9(実施例9)を得た。S9の微細セルロース不織布層の厚みは、7.2μmであった。多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。
実施例1でリンターパルプを叩解して得られた、CSF値で73ml↑のスラリーを用いて、該スラリーを水で希釈し、繊維濃度を0.08重量%とし、家庭用ミキサーで、室温で4分間分散処理を行い、抄紙用分散液とした。該抄紙用分散液を用い、実施例1の要領でまず目付が20g/m2の設計で抄紙を行い、プレス処理、乾燥を行って天然セルロース繊維からなる短繊維不織布をまず作製した。さらに、実施例1でキュプラレーヨン不織布の代わりに該天然セルロース繊維からなる短繊維不織布を用いて、その他は実施例1と全く同じ条件で該レーヨン短繊維不織布層の上に微細セルロース繊維層を10g/m2の目付で積層させ、引張強度が0.9kg重/15mmである取扱い性に優れた多層構造体S10(実施例10)を得た。S10の微細セルロース不織布層の厚みは、7.1μmであった。多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。
実施例2と実施例6で作製した2種類の多層構造体、S2とS6のそれぞれに対して親水化処理として、塩化リチウム塗布したサンプルを作製した。S2とS6のそれぞれの微細セルロース繊維不織布層の表面に対して5重量%の塩化リチウム水溶液を適量、均一にスプレー塗布し、定長枠に固定した状態で100℃の乾燥機内で10分間乾燥させた。S2とS6のそれぞれから得られた塩化リチウム塗布した多層構造体をS11とS12とした。塗布処理前後の絶乾重量変化から算出したS11とS12に含まれる塩化リチウムの付着量は、共に5重量%であった。S11とS12は2層の積層構造をもつが、引張強度が、それぞれ、1.1kg重/15mmと1.8kg重/15mmであり、共に十分な強度を保有したシート状構造体(目付:23g/m2,うち目付:3g/m2分は塗布層に含まれる塩化リチウム+水分の重量)であった。得られた多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。特に、親水化処理を施していないS2とS6に比べ、親水化処理されたサンプルはいずれも高い透湿度を示し、全熱交換器用シートとして、より高い適性(高い透湿度)を示したが、透湿性能の耐久性という観点では課題もあることが判明した。
実施例6で作製したS6に対して、親水化処理として、塩化リチウムを水溶性高分子塗膜内部に分散固定化したサンプルを作製した。まず、水溶性高分子として超高分子量ポリエチレングリコールである、明成化学(株)製のアルコックスE-60を用い、塩化リチウム濃度が10重量%、E-60が1重量%の水溶液を作製し、ガラス板上にS6の表面を微細セルロース繊維不織布層となるように固定化し、その上からアプリケータを用いて該水溶液を適量塗布し、実施例11と同じ要領で乾燥させて本発明の多層構造体S13を得た。親水化処理前後の絶乾重量変化から算出されたS13に含まれる塩化リチウムとE-60の量は、それぞれ、5重量%と0.5重量%であった。S13は2層の積層構造をもつが、引張強度が1.2kg重/15mmであり、十分な強度を保有したシート状構造体(目付:23g/m2,うち目付:3g/m2分は塗布層に含まれる塩化リチウム+E-60+水分の重量)であった。得られた多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。特に、親水化処理を施していないS6に比べ、親水化処理されたサンプルはいずれも高い透湿度を示し、本発明の全熱交換器用シートとして、より高い適性を示した。透湿性能の耐久性という観点でも、S13は塩化リチウムのみを塗布したS12よりも透湿度の低下率は改善(低減)されており、S12と比較するとより全熱交換器用シートとしての適性に優れたシートであることが判明した。
実施例1で調製した水系分散液M1を水で希釈し、微細セルロース繊維濃度が0.1重量%として、家庭用ミキサーで、室温で4分間分散を行った後に、耐水化剤(架橋剤)として、ブロックド多官能性イソシアネート(BI)のエマルジョン系水分散体である、明成化学(株)製のメイカネートWEBを適量加え、BI濃度が0.005重量%となるように調製した後に、緩やかな撹拌を3分間行い、抄紙用分散液Aを調製した。同じく、実施例5で調製した水系分散液M2についても、微細セルロース繊維濃度が0.1重量%となるように水で希釈した分散液を調製し、家庭用ミキサーで、室温で4分間分散を行った後に、BI濃度が0.005重量%となるようにメイカネートWEBを適量加えた後に、緩やかな撹拌を3分間行い、抄紙用分散液Bを調製した。抄紙用分散液Aと抄紙用分散液Bのそれぞれに対し、実施例2で示したのと同じ要領で、目付5g/m2の微細セルロース不織布層の形成を目安にした抄紙と乾燥を行い、キュプラレーヨン不織布、TN150上に微細セルロース繊維層を積層させる抄紙をそれぞれ行い、2種類の乾燥シートを得た。次に、これら2種類の乾燥シートを定長枠に取り付け、160℃に設定されたオーブン内で2分間熱処理を行い、イソシアネートによるセルロース表面水酸基との間の架橋反応を進行させた。熱処理後、室温で定長枠から取り外し、2種類の本発明の多層構造体を得た。抄紙用分散液Aと抄紙用分散液Bのそれぞれから得られた多層構造体を、S14(実施例14)とS15(実施例15)とする。S14とS15は2層の積層構造をもつが、引張強度が、それぞれ、1.6kg重/15mmと1.8kg重/15mmであり、共に十分な強度を保有したシート状構造体(共に目付:21g/m2)であった。得られた2種類の多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。また、S14とS15の耐水処理されていないサンプルに該当する、それぞれ、S2とS6では水中では容易に構造が崩壊してしまいウェット強度を評価することさえできない耐水性のないシートであったのに対し、S14とS15のウェット強度を、濡れたサンプルに対する引張強度測定((6)に準ずる)により評価したところ、それぞれ、0.52kg重/15mmと0.59kg重/15mmであり、ウェット環境でも使用可能な本発明の多層構造体となっていた。
実施例14における抄紙用分散液Aの調製において、耐水化剤(架橋剤)であるBIを加え、緩やかな撹拌を3分間行った後に、親水化剤として、旭化成ケミカルズ(株)製、トリメチルグリシンであるアミノコート(登録商標)を0.01重量%加え、さらに緩やかな撹拌を3分間行って抄紙用分散液Cを調製した。それ以降は、実施例14と全く同じ要領で、抄紙用分散液Cを用いて目付5g/m2の微細セルロース不織布層の形成を目安にした抄紙、乾燥及び熱処理を行い、本発明の多層構造体S16(実施例16)を得た。
同様に、実施例14における抄紙用分散液Aの調製において、耐水化剤であるBIを加え、緩やかな撹拌を3分間行った後に、親水化剤としてMTアクアポリマー(株)製、カチオン性水溶性ポリマーであるであるアロンフロック(登録商標)、C-508を0.01重量%加え、さらに緩やかな撹拌を3分間行って抄紙用分散液Dを調製した。それ以降は、実施例14と全く同じ要領で、抄紙用分散液Dを用いて目付5g/m2の微細セルロース不織布層の形成を目安にした抄紙、乾燥及び熱処理を行い、本発明の多層構造体S17(実施例17)を得た。S16とS17は2層の積層構造をもつが、引張強度が、それぞれ、1.4kg重/15mmと1.7kg重/15mmであり、共に十分な強度を保有したシート状構造体(目付:22g/m2(S16)と23g/m2(S17))であった。多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして適性に使用できるものであった。特に、目付の変化からも得られた2種類の親水化剤は微細セルロース繊維表面に歩留り、その後の抄紙によって微細セルロース繊維層の表層及び内部に固定化していると思われ、単純に耐水化処理のみを行ったS14と比較して透湿度が増大しており、しかも耐久性も良好であった。さらには、S16とS17のウェット環境下での引張強度は、それぞれ、0.48kg重/15mmと0.49kg重/15mmであり、共にウェット環境でも使用可能な多層構造体となっていた。
レンチング・ファイバーズ社より供給されたテンセル(登録商標)カット糸(3mm長)の油剤を水中、界面活性剤添加系での数回の洗浄により十分に落とした上、水を含んだ状態の短繊維原糸を得た。
該短繊維原糸を固形分1.5重量%となるように水中に分散させて水分散体(400L)とし、以降、実施例1と同様に叩解(CSF値として90ml↑になるまで叩解)と高圧ホモジナイザーによる微細化処理を行い、微細セルロース繊維の水系分散体M3(固形分濃度:1.5重量%)を得た。次に、実施例5で調製した分散体M2に含まれる微細セルロース繊維と、分散体M3に含まれる微細セルロース繊維の重量比率が、それぞれ、50:50になるように両分散体を混合し、さらに水で希釈することにより、固形分濃度が0.15重量%とし、家庭用ミキサーで、室温で4分間分散を行い、抄紙用分散液を調製した。
キュプラレーヨン基材上に微細セルロース繊維層の目付が5g/m2となるように抄紙を行い、プレス、乾燥も実施例1と同等の内容で行い、引張強度が1.1kg重/15mmと取扱いに十分な強度を保有するサンプルS18(実施例18)を得た。
S18の微細繊維層側の表面を10000倍の倍率でSEM画像解析を行ったところ、微細セルロース繊維の表面における微細セルロース繊維の数平均繊維径は273nmであった。S18の微細セルロース不織布層の厚みは、6.2μmであった。S18の全熱交換器用シートとしての適性を調べたところ、多層構造体は、以下の表1に示すとおり、全熱交換器用シートとして高い性能(高透湿度,高耐久性)を有するものであった。
実施例14と実施例16において微細セルロース繊維不織布層を積層させる支持体を、TN150から、旭化成せんい(株)ナイロンスパンボンド、NO5020に置き換え、その他は全く同じ要領で、それぞれ本発明の多層不織布S19(実施例19)とS20(実施例20)を得た。S19とS20は2層の積層構造をもつが、引張強度が、それぞれ、2.0kg重/15mmと1.9kg重/15mmであり、共に十分な強度を保有したシート状構造体(目付:21g/m2(S19)と22g/m2(S20))であった。また、S19とS20のウェット環境下での引張強度は、それぞれ、1.9kg重/15mmと1.7kg重/15mmであり、共にウェット環境でも使用可能な多層構造体となっていた。以下の表1に示すとおり、両サンプル共、全熱交換器用シートとして適性に使用できるものであった。
実施例4で得た多層構造体S4を、スルファミン酸グアニジン系難燃剤((株)三和ケミカル社製:アピノン-101)の20重量%水溶液に浸漬し、乾燥することで、難燃剤含有量が22.9重量%の難燃処理した全熱交換器用シートを得た。そのシートについて、JIS A 1322の「建築用薄物材料の難燃性試験方法」に従って難燃性試験を行い、炭化長、残炎、残じんを観測した結果、防炎2級となった。尚、この難燃処理した多層構造体サンプルS21(実施例21)の物性を、以下の表1に示す。S21は、全熱交換器用シートとして適性に使用できるものであった。
実施例10と同様に、実施例1でリンターパルプを叩解して得られた、CSF値で73ml↑のスラリーを用いて、該スラリーを水で希釈し、繊維濃度を0.08重量%とし、家庭用ミキサーで、室温で4分間分散処理を行い、抄紙用分散液とした。該抄紙用分散液を用い、実施例1の要領でまず目付が20g/m2の設計で抄紙を行い、プレス処理、乾燥を行って天然セルロース繊維からなる短繊維不織布サンプルR1(比較例1)を得た。
次に、R1に対し、実施例3に記載したのと同じカレンダー処理条件でカレンダー処理を行い、サンプルR2(比較例2)を得た。R1の表面のSEM画像を観察したところ、数μmから10μm以上の繊維径の繊維と200nm以下の繊維が混在しており、平均繊維径は画像毎に大きく異なる数値となり、定量的に算出することは困難であった。また、R1とR2は、それぞれ、0.9kg重/15mmと1.1kg重/15mmと取扱可能な引張強度を保有していたものの、いずれも地合いと呼ばれるシートの均一性が良くなく、品質安定性の面で課題のあるシートであった。全熱交換器用シートとしての適性評価を行ったところ、以下の表2に示す結果を得た。R1とR2は共に、所定の微細セルロース繊維からなる層を含んでいないため、特に、大きな透気抵抗度を発現できていない点で問題があり、カレンダー処理による高密度化で透気抵抗度を高めたR2においても、実施例のいずれの透気抵抗度よりも小さな値であった。すなわち、両サンプルは共に上記実施例1~20に示す各サンプルよりも全熱交換器用シートとしての適性において明らかに劣っていた。
実施例1で基材として用いたキュプラレーヨン不織布(旭化成せんい製、商品名:ベンリーゼ(登録商標)TN150目付:15g/m2、厚み:50μm、密度:0.28g/cm3 平均単糸繊度:0.2dtex)を3枚重ねにして、実施例3に記載したのと同じカレンダー処理条件でカレンダー処理を行い、サンプルR3(比較例3)を得た。R3の全熱交換器用シートとしての適性評価を行ったところ、以下の表2に示す結果を得た。R3は、所定の微細セルロース繊維からなる層を含んでいないため、所定の透気抵抗度から大きくはずれ、吸気と排気の遮断性の面において全熱交換器用シートとして適性に使用できるものではなかった。
針葉樹クラフトパルプ(NBKP)を濃度2.5重量%となるように水中に分散させて水分散体(400L)とし、ディスクリファイナー装置として実施例1と同じSDR14型ラボリファイナー(加圧型DISK式)を用い、ディスク間のクリアランスを0.8mmとして400Lの該水分散体に対して、約40分間叩解処理を進め、CSF値で90ml↓の叩解スラリーを得た。実施例1の要領でまず目付が40g/m2の設計で抄紙を行い、プレス処理、乾燥を行って天然セルロース繊維からなる紙サンプルを得た。該紙に実施例3に記載したのと同じカレンダー処理条件でカレンダー処理を行い、サンプルR4(比較例4)を得た。R4に対し、実施例11に記載したのと同じ塩化リチウム塗布の条件で親水化処理を行い、塩化リチウムが1g/m2の量だけ均一に塗布されたサンプルR5(比較例5)を得た。R4とR5は、共に1.6kg重/15mmと十分な引張強度を保有していたものの、全熱交換器用シートとしての適性評価を行ったところ、以下の表2に示す結果を得た。R4は高い透気抵抗度と高透湿度を両立できておらず(低い透気抵抗度)、また、塩化リチウム塗布により若干透気抵抗が大きくなったR5は吸湿剤による効果でより高い透湿度を発現できているものの、高湿履歴後の透湿度は大幅に低減しており、耐久性の面でも問題があった。すなわち両サンプルは共に、全熱交換器用シートとしては実施例1~20のものよりも劣ったシートであった。
実施例17で得られた全熱交換器用シートS17と、段成形した型艶クラフト紙((株)城山製紙社製 目付け65g/m2)とを貼り合わせ全熱交換器用素子を作製し、次に直交流型の静止型全熱交換器(190mm×190mm×350mm、134段)を作製した。JIS B 8628に準拠し、熱交換率を測定したところ、全熱交換率は81%であった。
Claims (18)
- 微細セルロース繊維からなる微細セルロース繊維不織布層を少なくとも一層含む多層構造体であって、該微細セルロース繊維不織布層を形成する微細セルロース繊維の平均繊維径が0.005μm以上0.5μm以下であり、さらに該多層構造体の平均厚みが10μm以上200μm以下、密度が0.10g/cm3以上0.90g/cm3以下、かつ、透気抵抗度が2000s/100ml以上であることを特徴とする多層構造体。
- 2層構造であり、かつ、該多層構造体の平均厚みが10μm以上150μm以下、密度が0.30g/cm3以上0.80g/cm3以下、かつ、透気抵抗度が3000s/100ml以上である、請求項1に記載の多層構造体。
- 前記微細セルロース繊維不織布層に含まれる微細セルロース繊維の割合が50重量%以上100重量%以下である、請求項1又は2に記載の多層構造体。
- 前記微細セルロース繊維不織布層の目付の総和が1g/m2以上15g/m2以下、かつ、厚みの総和が0.5μm以上15μm以下である、請求項1~3のいずれか1項に記載の多層構造体。
- 前記多層構造体の一層が、再生セルロース繊維、天然セルロース繊維、ナイロン繊維、ポリエステル繊維、及びポリオレフィン繊維からなる群から選ばれるいずれか一つ又は複数の組合せから構成される不織布層、及び/又は多孔質膜、及び/又は布帛である、請求項1~4のいずれか1項に記載の多層構造体。
- 前記多層構造体の一層が、再生セルロース連続長繊維からなる不織布層である、請求項1~4のいずれか1項に記載の多層構造体。
- 前記多層構造体は耐水処理されたものである、請求項1~6のいずれか1項に記載の多層構造体。
- 前記多層構造体は親水化処理されたものである、請求項1~7のいずれか1項に記載の多層構造体。
- 請求項1~8いずれか1項に記載の多層構造体からなる全熱交換器用シート。
- 前記多層構造体の平均厚みが10μm以上70μm以下である、請求項9に記載の全熱交換器用シート。
- 前記多層構造体の平均厚みが10μm以上30μm以下である、請求項10に記載の全熱交換器用シート。
- 前記多層構造体は難燃処理されたものである、請求項9~11のいずれか1項に記載の全熱交換器用シート。
- 前記多層構造体を構成する素材に占めるセルロース繊維の割合が90重量%以上である、請求項9~12のいずれか1項に記載の全熱交換器用シート。
- 以下の工程:
不織布層上に平均繊維径が0.005μm以上0.5μm以下である微細セルロース繊維不織布層を抄紙法により積層形成させる工程、及び
得られた積層不織布を乾燥させる工程、
を含む、請求項1~6のいずれか1項に記載の多層構造体の製造方法。 - 前記乾燥工程の後に、熱処理する工程をさらに含む、請求項14に記載の方法。
- 以下の工程:
請求項1~8のいずれか1項に記載の多層構造体の片面又は両面に親水性塗工層を塗工により形成させる工程、
を含む、請求項14に記載の多層構造体の製造方法。 - 請求項9~13のいずれか1項に記載の全熱交換器用シートを、温度、湿度又はその両方が異なる二種類の気流を仕切る仕切り材として用いた全熱交換素子。
- 請求項17に記載の全熱交換素子を用いた全熱交換器。
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Also Published As
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US20160194832A1 (en) | 2016-07-07 |
JP6189842B2 (ja) | 2017-08-30 |
CA2879447A1 (en) | 2014-01-23 |
BR112015000927B1 (pt) | 2021-01-12 |
JPWO2014014099A1 (ja) | 2016-07-07 |
EP2875950A1 (en) | 2015-05-27 |
EP2875950A4 (en) | 2015-07-15 |
US9580873B2 (en) | 2017-02-28 |
CA2879447C (en) | 2018-02-06 |
BR112015000927A2 (pt) | 2017-06-27 |
CN104470720B (zh) | 2016-08-24 |
CN104470720A (zh) | 2015-03-25 |
US9670622B2 (en) | 2017-06-06 |
US20150167249A1 (en) | 2015-06-18 |
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