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WO2015111610A1 - Particules polymères hygroscopiques, ainsi que feuille, élément, et échangeur thermique total ayant lesdites particules - Google Patents

Particules polymères hygroscopiques, ainsi que feuille, élément, et échangeur thermique total ayant lesdites particules Download PDF

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WO2015111610A1
WO2015111610A1 PCT/JP2015/051496 JP2015051496W WO2015111610A1 WO 2015111610 A1 WO2015111610 A1 WO 2015111610A1 JP 2015051496 W JP2015051496 W JP 2015051496W WO 2015111610 A1 WO2015111610 A1 WO 2015111610A1
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hygroscopic
weight
polymer particles
sheet
parts
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Japanese (ja)
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竹下悠史
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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Priority to KR1020167014725A priority Critical patent/KR102234761B1/ko
Priority to CN201580004107.6A priority patent/CN105916569B/zh
Priority to JP2015559087A priority patent/JP6528687B2/ja
Publication of WO2015111610A1 publication Critical patent/WO2015111610A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • B01J20/3282—Crosslinked polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • 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
    • F28D21/0015—Heat and mass exchangers, e.g. with permeable walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/34—Specific shapes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic

Definitions

  • the present invention relates to hygroscopic polymer particles having excellent film-forming properties, and a sheet, element and total heat exchanger having the particles.
  • inorganic hygroscopic agents such as calcium chloride, lithium chloride and phosphorus pentoxide
  • inorganic hygroscopic agents such as silica gel, zeolite, activated alumina and activated carbon
  • hygroscopic substances such as silica gel, zeolite, activated alumina and activated carbon
  • An organic polymer type hygroscopic agent is also known, and this hygroscopic agent adsorbs water by a salt-type carboxyl group contained in the structure.
  • it since it has a flexible structure that swells and contracts due to moisture absorption / release due to its internal cross-linking structure, it can adsorb a large amount of water without deliquescent.
  • hygroscopic agents may be used alone as air drying agents, or may be carried on a substrate and used as processed products.
  • An example of a processed product in which a moisture absorbent is supported on a substrate sheet such as paper is a total heat exchange element.
  • the total heat exchange element is the main component of the total heat exchanger, and in order to reduce the air conditioning load that occurs during ventilation, the sensible heat and latent heat between the air taken in from the outside and the air exhausted from the room to the outside Is to replace.
  • the block-type total heat exchange element has a structure in which each flow path for air supply and exhaust is separated by a partition plate, making it difficult for dirty air to be exhausted and fresh air to be supplied to hardly cross have.
  • the sheet used for the partition plate that separates the flow paths includes heat transfer for improving sensible heat exchange efficiency and moisture permeability for latent heat exchange, as well as air supply and exhaust through the sheet. Air barrier properties that do not cross are required.
  • Patent Document 1 In order to improve the latent heat exchange efficiency of the block-type total heat exchange element described above, a sheet containing a hygroscopic agent has been proposed.
  • Patent Document 2 An alkali metal salt is added as a hygroscopic agent, and Patent Document 2 describes the use of calcium chloride.
  • Patent Document 3 a hygroscopic agent in which silica gel and aluminum hydroxide are blended instead of an inorganic salt having deliquescence such as alkali metal or calcium chloride is used.
  • Inorganic salt hygroscopic agents such as alkali metal salts and calcium chloride have the feature of high moisture absorption, but since deliquescent occurs due to moisture absorption, the hygroscopic agent elutes in areas with a lot of moisture, and the shape of the element It becomes difficult to maintain. Further, there is a problem that the sheet is blocked during processing.
  • hygroscopic agents with a porous structure such as silica gel and zeolite have problems such as the accumulation of malodorous components in the pores and the deterioration of moisture absorption performance due to the destruction of the porous structure by repeated moisture absorption and desorption. There is.
  • the organic polymer-based hygroscopic agent described in Patent Document 4 does not have a problem like an inorganic hygroscopic agent and exhibits high hygroscopic performance, and thus is considered to be an effective material for the hygroscopic sheet.
  • organic polymer-based hygroscopic agents have low film-forming properties, and on the other hand, have the property of swelling and shrinking. Therefore, the hygroscopic coating film composed of the hygroscopic agent is prone to cracking, making it a perfect heat exchanger element. This is a problem in achieving the required air barrier properties.
  • the present invention has been made in view of the current state of the prior art, and the object thereof is an organic polymer-based hygroscopic agent having a film-forming property, a sheet and an element having the hygroscopic agent, and such an element. It is in providing the total heat exchanger using this.
  • the present inventors have determined that the hygroscopic polymer particles having a carboxyl group have a structure having different crosslink densities in the central portion and the surface layer portion of the particles, thereby achieving excellent hygroscopic properties.
  • the present inventors have found that a water-absorbing polymer particle can be obtained, and furthermore, by using such a water-absorbing polymer particle, it is possible to obtain a hygroscopic coating film that does not crack even at a high content.
  • the present invention is achieved by the following means.
  • the moisture absorption according to [1], wherein the particle size when dispersed in water is 4 times or more the particle size when dispersed in water after all the carboxyl groups in the particles are made H-shaped Polymer particles.
  • the hygroscopic sheet according to [6] wherein a cross-linking agent that cross-links between the hygroscopic polymer particles is contained as a constituent component of the hygroscopic coating film.
  • the substrate sheet is porous, the moisture absorption rate of the hygroscopic coating film is 20% by weight or more at 20 ° C. and 65% RH, and the air permeability of the hygroscopic sheet is 2 ⁇ m / (Pa ⁇ s).
  • the hygroscopic sheet according to [6] or [7] which is as follows.
  • a moisture absorbing / releasing element comprising the moisture absorbing sheet according to any one of [6] to [8] as a constituent material.
  • a total heat exchange element comprising the hygroscopic sheet according to any one of [6] to [8] as a constituent material.
  • a total heat exchanger having the total heat exchange element according to [10].
  • hygroscopic polymer particles of the present invention By using the hygroscopic polymer particles of the present invention, it is possible to form a hygroscopic coating film having high hygroscopic performance without causing cracks. Thereby, a hygroscopic coating film can be uniformly supported on the base sheet, and the resulting hygroscopic sheet has both moisture permeability and air barrier properties.
  • the hygroscopic element obtained by processing such a hygroscopic sheet can be suitably used for a desiccant air conditioner or a total heat exchanger.
  • Hygroscopic polymer particles The hygroscopic polymer particles employed in the present invention have a carboxyl group and a crosslinked structure.
  • the carboxyl group present in the hygroscopic polymer particles has a characteristic of chemically adsorbing moisture in the air.
  • the carboxyl group is preferably a salt type (hereinafter also referred to as a salt type carboxyl group), and the cation forming a pair is not particularly limited.
  • an alkali metal such as Li, Na, K, Rb, or Cs
  • Be Alkaline earth metals such as Mg, Ca, Sr and Ba
  • other metals such as Cu, Zn, Al, Mn, Ag, Fe, Co and Ni
  • organic cations such as NH 4 and amine, etc. I can do it.
  • alkali metal and alkaline earth metal cations are preferred from the viewpoint of moisture absorption / release rate.
  • the amount of carboxyl groups contained in the hygroscopic polymer particles is preferably 3 to 10 mmol / g, more preferably 5 to 10 mmol / g.
  • the amount of carboxyl groups is less than 3 mmol / g, sufficient moisture absorption / release performance may not be obtained.
  • the amount exceeds 10 mmol / g swelling of the coating film formed using hygroscopic polymer particles with respect to water becomes larger and the durability becomes insufficient.
  • the amount of carboxyl groups represents the mol amount of carboxyl groups relative to the weight of hygroscopic polymer particles when all the carboxyl groups of the hygroscopic polymer particles are H-type (hereinafter also referred to as H-type carboxyl groups). It is.
  • the crosslinked structure of the hygroscopic polymer particles is mainly formed at the center of the particles, and is formed by polymerizing a monomer group including a crosslinking monomer having a double bond in the molecule.
  • the hygroscopic polymer particles of the present invention can maintain the particle state without being dissolved even after hydrolysis due to such a crosslinked structure, and can contribute to water resistance.
  • the film-forming property in the present invention means that a film can be formed when the coating liquid containing hygroscopic polymer particles is dried, and it is judged that the film-forming property is good if the film can be formed without causing cracks. Is done.
  • the hygroscopic polymer particles have a structure having almost no cross-linking structure in the particle surface layer portion.
  • the polymer chain in the particle surface layer portion is greatly expanded due to electrical repulsion of carboxylate ions when the carboxyl group is dissociated in water or the like, and the particle diameter is also increased. That is, it becomes possible that the polymer chain can be expanded in three dimensions, so that the entanglement of the polymer chain between the hygroscopic polymer particles is strengthened, and therefore, good film-forming property is easily exhibited.
  • the particle diameter of the hygroscopic polymer particles measured by the method described below is preferably 4 times or more compared to the particle diameter in a state where all the carboxyl groups of the particles are H-type carboxyl groups. More preferably, if it is 5 times or more, it can be judged that the polymer chain of the particle surface layer portion is sufficiently spread and has a good film forming property.
  • the particle diameter of the hygroscopic polymer particles of the present invention is preferably less than 5 ⁇ m, more preferably less than 2 ⁇ m, and even more preferably less than 1 ⁇ m.
  • the viscosity of the aqueous dispersion is lower than that of hygroscopic polymer particles having a crosslinked structure in the particle surface layer. It is considered that the lower the viscosity, the more easily the polymer chains in the particle surface layer part are entangled between the hygroscopic polymer particles when forming a coating film, which will be described later, and it becomes easier to obtain excellent film forming properties.
  • the viscosity when the hygroscopic polymer particles are dispersed in water by 10% by weight is preferably 500 mPa ⁇ s or less, and more preferably 300 mPa ⁇ s or less.
  • the following method can be exemplified.
  • the ratio of the first monomer group including the crosslinking monomer in the methods (1) and (2) is preferably 1 to 70% by weight with respect to the total amount of monomers used, and is 5 to 70% by weight. It is more preferable.
  • the ratio of the first monomer group is low, the hydrophilicity of the polymer obtained by hydrolysis becomes too strong, and as a result, a water-soluble polymer may be obtained.
  • the ratio of the crosslinking monomer in the first monomer group is preferably 20% by weight or more from the viewpoint of water resistance.
  • examples of the monomer having a functional group that can be converted to a carboxyl group by hydrolysis include monomers having a nitrile group such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, malein Examples include anhydrides, ester derivatives, and amide derivatives of monomers having a carboxylic acid group such as acid, itaconic acid, and vinylpropionic acid.
  • the functional group of these monomers is converted into a carboxyl group by undergoing hydrolysis.
  • the crosslinking monomer in the methods (1) and (2) is not particularly limited as long as it is a monomer having two or more double bonds in the molecule.
  • glycidyl methacrylate, triallyl isocyanurate, triallyl cyanurate examples thereof include crosslinkable vinyl compounds such as divinylbenzene, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and methylenebisacrylamide.
  • the crosslinking monomer which forms the crosslinked structure which does not hydrolyze such as triallyl isocyanurate, triallyl cyanurate, divinylbenzene, can be used conveniently.
  • examples of the crosslinking monomer that forms a hydrolyzable crosslinked structure include glycidyl methacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
  • the crosslinked structure formed at the time of polymerization using these is destroyed by being subjected to hydrolysis, and the crosslinked structure of the surface layer portion of the particles can be changed.
  • monomers other than the above-described monomers may be included in each monomer group for polymerization.
  • any monomer can be used as long as it can be copolymerized with the monomer as described above.
  • the precursor particles obtained by polymerization are heated in a basic aqueous solution such as alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or sodium carbonate or ammonia.
  • a basic aqueous solution such as alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or sodium carbonate or ammonia.
  • generated by hydrolysis forms a cation and a salt corresponding to the chemical
  • the hygroscopic coating film in the present invention is a coating film containing the hygroscopic polymer particles of the present invention as a constituent component of the coating film.
  • the hygroscopic polymer particles of the present invention can form a hygroscopic coating film alone when applied as an aqueous dispersion or the like, but as a constituent component other than the hygroscopic polymer particles, the hygroscopic polymer particles are formed between the hygroscopic polymer particles.
  • a crosslinking agent that crosslinks By adding a crosslinking agent that crosslinks, a hygroscopic coating film having better water resistance can be obtained.
  • Examples of such a crosslinking agent include compounds having a functional group capable of reacting with a carboxyl group.
  • compounds having an epoxy group such as ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, Epocross
  • compounds having an oxazoline group such as (made by Nippon Shokubai Co., Ltd.), compounds having an aziridine group such as chemitite (made by Nippon Shokubai Co., Ltd.), and compounds having a carbodiimide group such as carbodilite (made by Nisshinbo Chemical Co., Ltd.).
  • the crosslinking agent by a metal ion is mentioned.
  • the addition amount of the crosslinking agent is preferably 1 to 50 parts by weight, particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the hygroscopic polymer particles.
  • the addition amount of the crosslinking agent is small, the moisture-absorbing polymer particles may not be sufficiently crosslinked and the effect of improving water resistance may not be obtained.
  • the amount added is too large, most of the carboxyl groups, which are hygroscopic sites in the hygroscopic polymer particles, are consumed in the reaction with the crosslinking agent, and sufficient hygroscopicity may not be obtained.
  • resin-based emulsions urethane, acrylic, vinyl acetate, ethylene, etc.
  • polyvinyl alcohol and poly-1-methylvinyl are used as necessary to change the physical properties such as hardness and strength of hygroscopic coatings.
  • Polymers having hydroxyl groups such as alcohol, polyallyl alcohol, ethylene-vinyl alcohol copolymer, poly (hydroxyalkyl acrylate), poly (hydroxyalkyl methacrylate), and water-soluble polysaccharides may be added.
  • an antibacterial / antifungal agent or a flame retardant can be added depending on the purpose.
  • the hygroscopic sheet of the present invention comprises the above-mentioned hygroscopic coating film supported on a base sheet.
  • the base sheet include paper bases containing organic fibers and inorganic fibers, and metal plates such as aluminum plates, iron plates, stainless steel plates, and copper plates.
  • a method of supporting the hygroscopic coating film on the base sheet a method of preparing a coating liquid containing hygroscopic polymer particles and impregnating the base sheet with the coating liquid, and applying the coating liquid to a bar coder and a blade And the like, and a method of spraying the coating liquid on the base sheet.
  • the amount of the hygroscopic coating film supported on the base sheet is not particularly limited, it is preferably 10 g / m 2 or more and more preferably 30 g / m 2 or more for forming the coating film.
  • the hygroscopic sheet of the present invention can be processed three-dimensionally and used for a hygroscopic element.
  • the hygroscopic element of the present invention has a structure that can have a gas penetrating passage and can make the area of the sheet in contact with the passing air as wide as possible in order to efficiently use the hygroscopic polymer particles supported on the sheet. It is preferable.
  • a honeycomb structure examples thereof include a hexagonal type, an OX type, a flex type, a bisecting type, and a feather type (hereinafter referred to as a corrugated type).
  • a corrugated type that is easy to process, has a high processing speed, and is advantageous in terms of cost is preferable.
  • characteristics such as the size and length of the gas penetration path can be appropriately selected according to required performance such as pressure loss (air resistance).
  • the external shape of the hygroscopic element can be freely set according to the application. Applications include desiccant air conditioners and total heat exchangers.
  • the hygroscopic sheet of the present invention can be suitably used as a constituent material of the total heat exchange element.
  • the total heat exchange element of the present invention has two types of flow paths separated by using the above-described hygroscopic sheet as a partition plate, and has a structure that allows two types of air in different states to pass through without crossing each other.
  • the shape is not particularly limited.
  • the total heat exchange element which has the structure which laminated
  • two types of independent flow paths are secured, and the temperature and humidity can be exchanged through the partitioned hygroscopic sheet without the air passing through each flow path intersecting.
  • the moisture absorption rate of the hygroscopic coating film supported on the hygroscopic sheet is preferably 20% by weight or more, more preferably 30% by weight or more at 20 ° C. and 65% RH.
  • the content of the hygroscopic polymer particles in the hygroscopic coating film is preferably 40% by weight or more, and more preferably 50% by weight or more.
  • the upper limit of the moisture absorption rate of the hygroscopic coating film is not particularly limited, but when it exceeds 60% by weight in an atmosphere of 20 ° C. and 65% RH, attention should be paid to deformation due to moisture absorption and a decrease in water resistance. is required.
  • the hygroscopic polymer particles of the present invention are excellent in film-forming properties, the hygroscopic coating film formed on the base sheet does not crack and the air permeability of the obtained hygroscopic sheet is increased. It can be set to a low level of 2 ⁇ m / (Pa ⁇ s) or less, preferably 1 ⁇ m / (Pa ⁇ s) or less, and air barrier properties are exhibited.
  • the hygroscopic sheet of the present invention can achieve both excellent moisture permeability and air blocking properties, and sensible heat exchange and latent heat exchange can be performed without interchanging air between two separated flow paths. It is effective as a material for a total heat exchanger that only performs.
  • Average particle size The result of measurement using water as a dispersion medium using the particle size measurement system “ELSZ-2” manufactured by Otsuka Electronics Co., Ltd. is represented by the scattered light intensity distribution, and the median diameter is defined as the average particle diameter.
  • the air permeability in the hygroscopic sheet is measured as follows. Porous Materials, Inc. Using an “Envelop Surface Area Analyzer” manufactured by Nikon, nitrogen gas was passed through the hygroscopic sheet, and the pressure difference before and after passing through the hygroscopic sheet was measured. At this time, the air permeability ( ⁇ m / (Pa ⁇ s)) is obtained from the average value of the gas flow rate (mL / s) passing through the sheet in the pressure difference range of 1000 to 3000 Pa. The lower the value, the lower the air permeability of the sheet, and it can be determined that the total heat exchange element using the sheet has less air crossing between the two flow paths.
  • Example 1 A reactor was charged with 440 parts by weight of water, 4 parts by weight of Eleminol MON-7 (manufactured by Sanyo Chemical Industries), 3 parts by weight of methyl methacrylate and 15 parts by weight of divinylbenzene, and the temperature was raised to 60 ° C. . Next, 196 parts by weight of methyl acrylate, 2 parts by weight of methacrylic acid, monomer group 2 and 70 parts by weight of 1.3% by weight aqueous sodium pyrosulfite solution and 70% by weight of 1.5% by weight aqueous ammonium persulfate solution were added to the reaction vessel.
  • Eleminol MON-7 manufactured by Sanyo Chemical Industries
  • the obtained hygroscopic polymer particles A had an average particle size of 930 nm, and those having all the carboxyl groups in the H-type were 120 nm, and the particle swelling ratio was a large value of 7.8.
  • the viscosity in a 10% by weight aqueous dispersion was as low as 200 mPa ⁇ s, and the film forming property was also good.
  • Example 2 To 100 parts by weight of the solid content of the precursor emulsion obtained in Example 1, 27 parts by weight of sodium hydroxide and 720 parts by weight of water were added and heated at 90 ° C. for 16 hours to carry out the hydrolysis reaction and absorb moisture. An aqueous dispersion of polymer particles B was obtained. As shown in Table 1, the film forming property of the obtained hygroscopic polymer particles B was good.
  • Example 3 435 parts by weight of water and 9 parts by weight of Eleminol MON-7 (manufactured by Sanyo Chemical Industries) were added to the reaction vessel, and the temperature was raised to 60 ° C. Next, monomer group 1 consisting of 6 parts by weight of methyl methacrylate, 30 parts by weight of divinylbenzene and 102 parts by weight of methyl acrylate, 45 parts by weight of 1.3% by weight aqueous sodium pyrosulfite solution, and 1.5% by weight ammonium persulfate Polymerization was carried out while adding 45 parts by weight of an aqueous solution over 1.5 hours.
  • Eleminol MON-7 manufactured by Sanyo Chemical Industries
  • monomer group 2 consisting of 76 parts by weight of methyl acrylate and 2 parts by weight of methacrylic acid, 25 parts by weight of 1.3% by weight aqueous sodium pyrosulfite and 1.5% by weight ammonium persulfate were further added to the reaction vessel.
  • Polymerization was performed while adding 25 parts by weight of an aqueous solution over 1 hour to obtain a precursor emulsion of hygroscopic polymer particles C having an average particle size of 160 nm.
  • 38 parts by weight of potassium hydroxide and 782 parts by weight of water are added, heated at 90 ° C.
  • a monomer group consisting of 3 parts by weight of methyl methacrylate, 15 parts by weight of divinylbenzene, 196 parts by weight of methyl acrylate, 2 parts by weight of methacrylic acid, 70 parts by weight of a 1.3% by weight sodium pyrosulfite aqueous solution, and 1.5 parts by weight 70 parts by weight of an aqueous ammonium persulfate solution was added over 2 hours, followed by polymerization to obtain a precursor emulsion before hydrolysis.
  • the solid content of the obtained precursor emulsion is 100 parts by weight, 38 parts by weight of potassium hydroxide and 782 parts by weight of water are added and heated at 90 ° C. for 16 hours to carry out the hydrolysis reaction. It became a water-soluble polymer. For this reason, some evaluations were not performed.
  • a monomer group 2 consisting of 60 parts by weight of methyl acrylate and 2 parts by weight of methacrylic acid, 20 parts by weight of a 1.3% by weight aqueous sodium pyrosulfite solution and 1.5% by weight of ammonium persulfate were further added to the reaction vessel.
  • Polymerization was carried out while adding 20 parts by weight of an aqueous solution over 1 hour to obtain a precursor emulsion of hygroscopic polymer particles D.
  • 38 parts by weight of potassium hydroxide and 782 parts by weight of water are added, heated at 90 ° C.
  • hygroscopic polymer particles D For 16 hours, and subjected to a hydrolysis reaction to form hygroscopic polymer particles D.
  • An aqueous dispersion was obtained.
  • the obtained hygroscopic polymer particles D have a slightly higher proportion of the monomer group 1 than the hygroscopic polymer particles C of Example 3, and the particle increase ratio is smaller than that of the hygroscopic polymer particles C.
  • the viscosity of the 10% by weight aqueous dispersion was 20 times higher. It was suggested that the hygroscopic polymer particles D were in a gel state in which water was collected in the particle surface layer portion, and the film forming property could not be obtained.
  • the particle increase rate of the hygroscopic polymer particles E was 4.9 similar to the hygroscopic polymer particles C of Example 3, but the viscosity in the 10 wt% aqueous dispersion was 10,000 mPa. -It became very high with more than s, and the film-forming property was not obtained.
  • hygroscopic polymer particles F To 100 parts by weight of the solid content of the obtained precursor emulsion, 50 parts by weight of potassium hydroxide and 850 parts by weight of water are added and heated at 90 ° C. for 16 hours to perform a hydrolysis reaction, and then an ion exchange resin is used. After removing the remaining potassium hydroxide, an aqueous dispersion of hygroscopic polymer particles F was obtained. As shown in Table 1, the particle increase rate of the hygroscopic polymer particles F is low, and the viscosity of the 10% by weight aqueous dispersion is also as low as 20 mPa ⁇ s. Although the structure is presumed to be built, the film-forming property of the hygroscopic polymer particles was not obtained.
  • Example 4 A 15% by weight aqueous dispersion of the hygroscopic polymer particles A obtained in Example 1 was impregnated onto a porous sheet mainly composed of glass fibers having a basis weight of 25 g / m 2 and an air permeability of 5720 ⁇ m / (Pa ⁇ s). Thus, a hygroscopic sheet having a hygroscopic coating film carrying amount of 60 g / m 2 was obtained. As shown in Table 2, the obtained hygroscopic sheet exhibited high moisture permeability although the air permeability was low.
  • Example 5 7.5 parts by weight of ethylene glycol diglycidyl ether was mixed with 1000 parts by weight of the 15% by weight aqueous dispersion of the hygroscopic polymer particles A obtained in Example 1 to prepare a coating solution.
  • a hygroscopic sheet having a hygroscopic coating film carrying amount of 60 g / m 2 was prepared in the same manner as in Example 4 except that the obtained coating solution was used.
  • the obtained hygroscopic sheet had the same level of air permeability and moisture permeability as the hygroscopic sheet of Example 4.
  • the stickiness of the hygroscopic coating film was not felt even under high humidity conditions, and an improvement in water resistance was confirmed by adding a crosslinking agent.
  • Example 6 317 parts by weight of Superflex 500M (Daiichi Kogyo Seiyaku Co., Ltd.), which is a 45% by weight aqueous dispersion of a urethane resin, was added to 1000 parts by weight of the 15% by weight aqueous dispersion of the hygroscopic polymer particles A obtained in Example 1. 7.5 parts by weight of ethylene glycol diglycidyl ether was mixed to prepare a coating solution. A hygroscopic sheet having a hygroscopic coating film loading of 60 g / m 2 was prepared in the same manner as in Example 4 except that the obtained coating solution was used.
  • the obtained hygroscopic sheet had a moisture absorption rate of 20% by weight or more although the hygroscopicity of the hygroscopic coating film decreased according to the addition of the urethane resin, and the moisture permeability was maintained.
  • Example 5 Using the urethane resin used in Example 6 and the same porous sheet as in Example 4 without using hygroscopic polymer particles, a sheet having a coating amount of 60 g / m 2 was prepared. As shown in Table 2, the sheet containing no hygroscopic polymer particles has low moisture permeability, and it was confirmed that the presence of hygroscopic polymer particles contributed to the expression of moisture permeability.
  • the moisture absorption rate of the hygroscopic coating film is low due to the low content of the hygroscopic polymer particles, and the moisture permeability is significantly higher than that of the hygroscopic sheets of Examples 4 to 6. It was confirmed that it decreased.
  • the obtained hygroscopic sheet had a substantially reduced moisture permeability although the moisture absorption rate of the hygroscopic coating film was similar to that of the hygroscopic sheet of Example 6.
  • the polymer chain having a carboxyl group as a hygroscopic site spreads in the particle surface layer portion, so that the hygroscopic polymer particles in the hygroscopic coating film While the hydrophilic network is built up in the entire coating film to be formed and the moisture permeability can be maintained even when the content ratio of water is about 50%, the hygroscopic polymer particle F has a cross-linked structure throughout the particle.
  • the hygroscopic polymer particles F have a strong cross-linked structure, it is considered that the affinity at the interface with the urethane resin is low and the air permeability is also high.

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Abstract

Le problème décrit par l'invention porte sur les revêtements classiques ayant un absorbant polymère organique d'humidité présentant un problème en ce que la teneur en pourcentage de l'absorbant polymère organique d'humidité est réduite et que la performance hygroscopique du revêtement absorbant d'humidité obtenu en résultat est réduite lorsqu'il est tenté de fabriquer un revêtement dépourvu de fissures par gonflement et rétrécissement. La présente invention a été envisagée au vu de l'état actuel de l'état de la technique, et l'un de ses buts est d'utiliser un absorbant polymère organique d'humidité ayant un revêtement autoformant, une feuille et un élément comportant ledit absorbant d'humidité, et un échange thermique total utilisant l'élément. La solution selon l'invention porte sur la découverte que dans les particules hygroscopiques de polymère ayant un groupe carboxyle, des particules hygroscopiques de polymère ayant une aptitude excellente à la formation du revêtement peuvent être obtenues en utilisant une structure dans laquelle la densité de réticulation diffère dans la partie centrale et la partie formant couche de surface des particules, et en outre un revêtement hygroscopique qui ne se fissure pas même avec une teneur élevée en pourcentage peut être obtenu en utilisant les particules hygroscopiques de polymère.
PCT/JP2015/051496 2014-01-27 2015-01-21 Particules polymères hygroscopiques, ainsi que feuille, élément, et échangeur thermique total ayant lesdites particules Ceased WO2015111610A1 (fr)

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JP2020118059A (ja) * 2019-01-22 2020-08-06 アイシン精機株式会社 送風装置
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CN114080241A (zh) * 2019-06-28 2022-02-22 尤妮佳股份有限公司 吸收体和吸收性物品
WO2022071166A1 (fr) * 2020-09-30 2022-04-07 ダイキン工業株式会社 Organe de séparation pour éléments d'échange de chaleur totale, élément d'échange de chaleur totale et appareil de ventilation
JP2022161246A (ja) * 2021-04-08 2022-10-21 日本エクスラン工業株式会社 耐水性吸放湿シート、耐水性吸放湿シートの製造方法および該耐水性吸放湿シートを構成材料とする吸放湿用または潜熱交換用の素子

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CN114182570B (zh) * 2020-08-25 2023-07-07 中国制浆造纸研究院有限公司 一种基于聚磷酰胺螯合物的无水加湿器件及其制备方法和应用
CN114086423A (zh) * 2020-08-25 2022-02-25 中国制浆造纸研究院有限公司 一种磺化改性无水加湿器件及其制备方法和应用
CN114134756A (zh) * 2020-09-04 2022-03-04 中国制浆造纸研究院有限公司 一种聚多巴胺型无水加湿器件及其制备方法和应用
KR102320604B1 (ko) 2021-06-18 2021-11-02 주식회사 와이디산업 열회수용 환기장치
KR102795508B1 (ko) * 2022-05-20 2025-04-17 한국철도기술연구원 철도차량용 공조시스템 내장형 전열교환장치

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JP6833121B1 (ja) * 2020-01-06 2021-02-24 三菱電機株式会社 除湿素子、この除湿素子を備えた除湿装置および除湿素子の製造方法
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JP2022161246A (ja) * 2021-04-08 2022-10-21 日本エクスラン工業株式会社 耐水性吸放湿シート、耐水性吸放湿シートの製造方法および該耐水性吸放湿シートを構成材料とする吸放湿用または潜熱交換用の素子
JP7644410B2 (ja) 2021-04-08 2025-03-12 日本エクスラン工業株式会社 耐水性吸放湿シート、耐水性吸放湿シートの製造方法および該耐水性吸放湿シートを構成材料とする吸放湿用または潜熱交換用の素子

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