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WO2018105617A1 - Composition pour former une couche de stockage thermique - Google Patents

Composition pour former une couche de stockage thermique Download PDF

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Publication number
WO2018105617A1
WO2018105617A1 PCT/JP2017/043676 JP2017043676W WO2018105617A1 WO 2018105617 A1 WO2018105617 A1 WO 2018105617A1 JP 2017043676 W JP2017043676 W JP 2017043676W WO 2018105617 A1 WO2018105617 A1 WO 2018105617A1
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Prior art keywords
heat storage
storage layer
composition
cellulose
heat
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PCT/JP2017/043676
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English (en)
Japanese (ja)
Inventor
宅磨 長▲濱▼
忠之 伊左治
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日産化学工業株式会社
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Priority to JP2018555020A priority Critical patent/JPWO2018105617A1/ja
Publication of WO2018105617A1 publication Critical patent/WO2018105617A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a composition for forming a heat storage layer.
  • a heat storage material has a property capable of temporarily storing heat, and generally refers to a substance that can control the flow of heat using a phase change or chemical reaction of a substance or a material containing the substance. .
  • a heat storage material is filled in a predetermined space (container) of various apparatuses and devices according to the usage, and is widely used as a heat storage system in various heat exchangers such as ships, vehicles, and air conditioners (for example, Patent Documents). 1, Patent Document 2).
  • the heat storage material is roughly classified into a sensible heat storage material using the heat capacity (temperature change) of the material, a latent heat storage material using the phase change of the substance, and a chemical heat storage material using the chemical reaction heat.
  • Patent Document 2 in order to improve the heat exchange efficiency of the heat exchange type reactor, a coating liquid in which calcium oxide particles are dispersed is applied to the heat exchange surface to form a heat exchange structure including a chemical heat storage material. Techniques to do this are disclosed.
  • Patent Document 3 proposes a composition for forming a chemical heat storage material that can be molded into an arbitrary shape. For example, by baking the composition after it is applied to a metal substrate, the distortion of the shape caused by the increase or decrease in its own volume. It has been reported that a porous chemical heat storage material that can absorb water can be obtained.
  • Patent Document 4 As a proposal for a porous functional material (hygroscopic material) in the form of a sheet using an organic binder (Patent Document 4), as a binder for an electrode active material and a conductive aid for a lithium secondary battery, There is a proposal (Patent Document 5) that uses a refined cellulose fiber.
  • the heat storage material is not only used by filling a conventional predetermined space (container) but also used in an arbitrary shape (molded product) such as a sheet-like material obtained by application to a base material. Is being considered. In this case, it is required to maintain a desired shape in the obtained molded product of the heat storage material.
  • the volume of the heat storage material that can be generated by the chemical reaction of the chemical heat storage material that is, the reversible reaction between the chemical heat storage material and water vapor. No increase or decrease is considered.
  • Patent Document 3 although a chemical heat storage material is provided with a porous shape to absorb distortion of the shape due to volume increase / decrease, firing at a high temperature (680 ° C. or higher) is necessary for that purpose. And the usable base material is limited. Further, Patent Document 4 and Patent Document 5 do not discuss the use of the organic binder or cellulose fiber described therein as a binder for a heat storage material.
  • a film can be formed by a simple method of coating, and a uniform heat storage layer can be obtained by drying the film at a relatively gentle temperature around 100 ° C. It is an object to provide a composition for use. Another object of the present invention is to provide a composition for forming a heat storage layer that can exhibit the same performance without greatly degrading the heat storage performance of the used heat storage material in the obtained film-shaped heat storage layer.
  • the present inventor has applied a composition containing a heat storage material, refined cellulose fiber, and a water-soluble polymer, and this is applied and dried.
  • the present invention was completed by finding that a uniform film-like layer, that is, a heat storage layer can be obtained, and that the heat storage layer can obtain almost the same heat storage performance as that of the heat storage material as a raw material. It was.
  • the present invention provides the first aspect as follows: (A) Heat storage material 100 parts by mass, The present invention relates to a composition for forming a heat storage layer, comprising (B) 0.01 to 100 parts by mass of refined cellulose fiber and (C) 0.01 to 100 parts by mass of a water-soluble polymer.
  • the refined cellulose fiber (B) has a particle diameter at a cumulative volume of 50% representing a fiber median dimension measured using water as a dispersion medium using a laser diffraction / scattering particle size distribution meter.
  • the composition for forming a heat storage layer according to the first aspect characterized by being 0.01 to 40 ⁇ m.
  • the present invention relates to the composition for forming a heat storage layer according to the first aspect or the second aspect, wherein the heat storage material (A) is a compound in the form of a powder having an average particle diameter of 10 nm to 100 ⁇ m.
  • the said (A) heat storage material is related with the composition for thermal storage layer formation as described in any one of the 1st viewpoint thru
  • the (A) heat storage material is an inorganic salt hydrate, hydrocarbon (paraffin), fatty acid, fatty acid ester, aliphatic ketone, aliphatic alcohol, aliphatic ether, clathrate hydrate, and strong correlation.
  • the present invention relates to the composition for forming a heat storage layer according to the fourth aspect, which is selected from the group consisting of electronic materials.
  • the present invention relates to the composition for forming a heat storage layer according to any one of the first aspect to the third aspect, in which the (A) heat storage material is a chemical heat storage material.
  • the (A) heat storage material is selected from the group consisting of an aluminosilicate, a phenylphosphonic acid compound metal salt, and an aromatic carboxylic acid compound metal salt, wherein the heat storage layer is formed according to the sixth aspect.
  • the present invention relates to a composition for use.
  • the water-soluble polymer (C) is polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, partially neutralized polyacrylate, cationized cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, ( At least from the group consisting of carboxymethyl) (ethyl) cellulose, hydroxyethyl cellulose, (hydroxyethyl) (methyl) cellulose, (ethyl) (hydroxyethyl) cellulose, hydroxypropyl cellulose, (hydroxypropyl) (methyl) cellulose, cationized starch It is related with the composition for thermal storage layer formation as described in any one among the 1st viewpoint thru
  • the present invention relates to the composition for forming a heat storage layer according to the eighth aspect, in which the water-soluble polymer (C) is polyvinyl alcohol.
  • the thermal storage layer produced from the composition for thermal storage layer formation as described in any one of a 1st viewpoint thru
  • the heat storage material relates to a heat storage layer in which they are captured by the cellulose fiber and the water-soluble polymer to form a film shape.
  • the thermally conductive substrate is a partition wall of a flow path through which a heat medium flows, and the heat storage layer is formed on a surface of the partition opposite to the side through which the heat medium flows.
  • the heat exchanger according to the twelfth aspect As a fourteenth aspect, the present invention relates to the heat exchanger according to the thirteenth aspect, in which the heat medium is cooling water for a prime mover.
  • the heat exchanger As a 15th viewpoint, it is related with the heat exchanger as described in a 13th viewpoint or a 14th viewpoint mounted in a vehicle.
  • composition for forming a heat storage layer of the present invention can be applied and dried to obtain a uniform film-shaped heat storage layer without causing cracks such as holes and cracks.
  • a heat storage layer excellent in adhesion and fixed to the base material can be obtained.
  • FIG. 1 is a diagram showing a TG-DTA chart of a sample obtained from the heat storage layer forming composition of Example 1.
  • FIG. 2 is a diagram showing a TG-DTA chart of a sample obtained from the heat storage layer forming composition of Example 2.
  • FIG. 3 is a diagram showing a TG-DTA chart of a sample obtained from the heat storage layer forming composition of Comparative Example 1.
  • 4 is a diagram showing a TG-DTA chart of a sample obtained from the composition for forming a heat storage layer of Comparative Example 3.
  • FIG. 1 is a diagram showing a TG-DTA chart of a sample obtained from the heat storage layer forming composition of Example 1.
  • FIG. 2 is a diagram showing a TG-DTA chart of a sample obtained from the heat storage layer forming composition of Example 2.
  • FIG. 3 is a diagram showing a TG-DTA chart of a sample obtained from the heat storage layer forming composition of Comparative Example 1.
  • the present inventors have examined the use of a material that contributes to maintaining the shape of the layer structure and does not impair the heat storage performance. Specifically, a material that can absorb and relieve the shape change and volume change caused by the phase transition and chemical reaction of the heat storage material during the formation of the heat storage layer, and the binding properties between the heat storage materials and between the heat storage materials and the base material.
  • a material that does not hinder the working fluid from reaching the chemical heat storage material is studied. Proceeded.
  • the present inventors pay attention to the fact that when water is removed from the finely divided aqueous dispersion of cellulose fibers, the cellulose fibers form a nonwoven fabric-like or network-like structure.
  • the present inventors have completed the present invention by examining whether it is possible to suppress the change and improve the binding property between the heat storage materials, and whether the structure obstructs the contact between the working fluid and the heat storage material.
  • the present invention will be described in further detail.
  • (A) Heat storage material It does not specifically limit as a heat storage material which can be used for this invention, The various heat storage materials which can be used as a sensible heat storage material, a latent heat storage material, and a chemical heat storage material mentioned above are mentioned.
  • the sensible heat storage material examples include non-metallic materials such as soil, sand, rocks, concrete slabs, and bricks; metallic materials such as steel, magnesium, molten salt, and ceramic bricks.
  • the sensible heat storage material since the sensible heat storage material is used as a heat storage layer, it is preferable that the sensible heat storage material is in the form of powder.
  • the latent heat storage material is not particularly limited as long as it is a compound that can generate heat and endotherm in accordance with a phase change.
  • inorganic salt hydrate hydrocarbon (paraffin), fatty acid, fatty acid ester, aliphatic ketone
  • examples include aliphatic alcohols, aliphatic ethers, clathrate hydrates, strongly correlated electron substances, and the like.
  • the melting point of these compounds measured by differential scanning calorimetry (DSC method) is preferably in the range of 10 to 250 ° C., and in the range of 20 to 200 ° C. It is more preferable.
  • the inorganic salt hydrate examples include sodium carbonate decahydrate, potassium carbonate hexahydrate, lithium nitrate trihydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, aluminum nitrate 9 water.
  • Examples include hexahydrate, strontium hydroxide octahydrate, and barium hydroxide octahydrate.
  • hydrocarbons having 8 to 60 carbon atoms can be used. Specific examples include tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, Hexacosan, heptacosan, octacosan, nonacosan, triacontane, hentriacontan, dotriacontan, tritriacontan and the like.
  • the fatty acid examples include octanoic acid, nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosane.
  • examples include acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid and the like.
  • linear saturated fatty acids having 10 to 18 carbon atoms are preferable from the viewpoint of availability.
  • fatty acid ester a long chain fatty acid ester having 8 to 30 carbon atoms can be used. Specific examples thereof include propyl palmitate, isopropyl palmitate, vinyl stearate, isopropyl stearate, butyl stearate, and sebacic acid. Examples include dimethyl and the like. From the viewpoint of availability, methyl esters, ethyl esters, propyl esters, and butyl esters of linear saturated fatty acids having 10 to 18 carbon atoms are preferably used.
  • an aliphatic ketone having 8 to 30 carbon atoms can be used. Specific examples include 2-nonanone, tridecanal, 2-pentadecanone, 8-pentadecanone, 3-hexadecanone, 4,4 -Bicyclohexanone and the like. Among these, an aliphatic ketone having 1 oxygen atom is preferably used from the viewpoint of having a latent heat amount suitable for industrial use and being easily synthesized.
  • an aliphatic alcohol having 4 to 60 carbon atoms can be used, and even a monoalcohol having one hydroxy group in one molecule can have two or more hydroxy groups in one molecule. It may be a polyhydric alcohol having a group.
  • other than alcoholic hydroxy groups such as carboxy group, sulfo group, carboxylic anhydride group, alkoxycarbonyl group, haloformyl group, carbamoyl group, cyano group, formyl group, mercapto group, amino group, imino group in the same molecule It may have a functional group of
  • aliphatic alcohol examples include 2-dodecanol, 1-tetradecanol, 7-tetradecanol, 1-octadecanol, 1-eicosanol, 1,10-decanediol, neopentyl glycol, trimethylolethane. And pentaerythritol.
  • 1,1,1-trimethylol-2-aminoethane and the like showing solid phase-solid phase transition can be mentioned.
  • the compound represented by the formula [1] which has a hydrocarbon straight chain structure and one hydroxy group per carbon atom, has a high latent heat (that is, heat of fusion), and is used as a heat storage material.
  • These polyhydric alcohols can also be used from the viewpoint of improving the performance.
  • polyhydric alcohols include alditols such as erythritol, threitol, ribitol, arabinitol, xylitol, lyxitol, allitol, tallitol, altitol, glucitol, mannitol, iditol, galactitol, and glycitol.
  • an alcohol (primary alcohol) in which at least one hydroxy group is present at the molecular end is preferably used.
  • an aliphatic ether having 14 to 60 carbon atoms can be used, and specific examples include heptyl ether, octyl ether, tetradecyl ether, hexadecyl ether and the like.
  • ethers having a symmetric structure with 1 oxygen atom are preferably used from the viewpoint of high latent heat and easy synthesis.
  • clathrate hydrate examples include tetrabutylammonium fluoride hydrate, tetrabutylammonium bromide hydrate, trimethylolethane hydrate, cyclopentane hydrate, HCHC-141b hydrate, HFC-134a hydrate, carbon dioxide hydrate and the like can be mentioned.
  • the strongly correlated electron substance examples include V (1-X) W X O 2 (0 ⁇ X ⁇ 0.0650), V (1-X) Ta X O 2 (0 ⁇ X ⁇ 0.117). ), V (1-X) Nb X O 2 (0 ⁇ X ⁇ 0.115), V (1-X) Ru X O 2 (0 ⁇ X ⁇ 0.150), V (1-X) Mo X O 2 (0 ⁇ X ⁇ 0.161), V (1-X) Re X O 2 (0 ⁇ X ⁇ 0.0964), LiMn 2 O 4 , LiVS 2 , LiVO 2 , NaNiO 2 , LiRh 2 O 4 , V 2 O 3 , V 4 O 7 , V 6 O 11 , Ti 4 O 7 , SmBaFe 2 O 5 , EuBaFe 2 O 5 , GdBaFe 2 O 5 , TbBaFe 2 O 5 , DyBaFe 2 O 5 , HoBaFe 2 O 5
  • the chemical heat storage material is not particularly limited as long as it is a compound that can generate heat and endotherm in association with a reversible chemical reaction.
  • absorption of gas such as water vapor (water), ammonia, hydrogen, carbon dioxide ( Examples of the metal salt compound exhibiting exotherm or endotherm by occlusion or release.
  • Examples of the metal in the metal salt compound include metals in Group 1 elements, Group 2 elements and transition elements, and aluminum. Specifically, lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron And at least one metal selected from the group consisting of cobalt, nickel, copper, zinc, silver, tin and aluminum.
  • Examples of the metal salt compounds include the above-mentioned metal carbonates, nitrates, sulfates, silicates, phosphonates, carboxylates, halides, oxides and hydroxides, metal composite oxides, and metal salt-added metals. Oxides as well as their hydrates are mentioned.
  • metal salt compounds include magnesium hydroxide (magnesium oxide), calcium sulfate (hydrate), calcium chloride (hydrate), calcium hydroxide (calcium oxide), aluminosilicate (zeolite). Etc.
  • a heat storage material disclosed in JP-A-2015-215155 that is, a metal salt of a phenylphosphonic acid compound such as magnesium phenylphosphonate or manganese phenylphosphonate; magnesium 2,5-dihydroxyterephthalate, terephthalate And metal salts of aromatic carboxylic acid compounds such as manganese acid.
  • aluminosilicates, metal salts of phenylphosphonic acid compounds, and metal salts of aromatic carboxylic acid compounds are preferably used.
  • the average particle diameter in the heat storage material used by this invention means the 50% volume diameter (median diameter) obtained by measuring with the laser diffraction and the scattering method based on Mie theory. Moreover, you may use these heat storage materials individually by 1 type or in combination of 2 or more types.
  • the composition for forming a heat storage layer of the present invention contains (B) a refined cellulose fiber.
  • the refined cellulose fiber is actually used in the form of a cellulose fiber dispersion described later.
  • the cellulose fibers overlap or entangle with each other, and (C) a water-soluble polymer, which will be described later, captures the heat storage materials and binds them, so-called heat storage. This contributes to the formation of a film containing a material (that is, a layer structure).
  • a thermal storage layer on a base material it can also play the role as a useful binder for binding a thermal storage layer on this base material.
  • a raw material used in the production of a conventional cellulose fiber can be widely used.
  • cellulose derived from plants such as wood, bamboo, hemp, jute, kenaf, agricultural products / food residues, or cellulose produced by microorganisms or animals such as bacterial cellulose and squirt cellulose can be used as raw materials.
  • These celluloses may be used alone or in combination of two or more. Among them, it is preferable to use plant-derived cellulose or bacterial cellulose as a raw material.
  • the method for pulverizing the cellulose is not limited, but a medium agitating mill such as a high-pressure homogenizer, a grinder (stone mill), or a bead mill is used to reduce the size (length) of the fiber to meet the object of the present invention.
  • a method capable of obtaining a strong shearing force is preferred.
  • a wet pulverization method as disclosed in JP-A-2005-270891 that is, an aqueous dispersion in which cellulose is dispersed is used as a pair of nozzles.
  • the cellulose is pulverized by being injected and collided with each other at a high pressure, and can be carried out by using, for example, a starburst system (wet atomizer manufactured by Sugino Machine Co., Ltd.).
  • the degree of refinement and homogenization depends on the pressure fed to the ultra-high pressure chamber of the high-pressure homogenizer, the number of passes through the ultra-high pressure chamber (number of treatments), and water. It will depend on the cellulose concentration in the dispersion.
  • the pumping pressure (treatment pressure) is usually 50 to 250 MPa, preferably 100 to 245 MPa. When the pumping pressure is less than 50 MPa, the cellulose fiber is not sufficiently refined, and the effect expected by the refinement cannot be obtained.
  • the cellulose concentration in the aqueous dispersion during the micronization treatment is 0.1 to 30% by mass, preferably 1 to 10% by mass.
  • the productivity is remarkably low, and when the concentration is higher than 30% by mass, the pulverization efficiency is low and the desired finely divided cellulose fiber cannot be obtained.
  • the number of refining treatments depends on the cellulose concentration in the aqueous dispersion, but when the cellulose concentration is 0.1 to 1% by mass, the refining treatment can be sufficiently refined in about 10 to 50 passes. About 1 to 10% by mass, about 50 to 200 passes are required. On the other hand, when the concentration is higher than 30% by mass, several hundred or more treatments are required, which is unrealistic from an industrial viewpoint.
  • the refined cellulose fiber (C) used in the present invention can be evaluated for the degree of refinement by using, for example, a laser diffraction / scattering particle size distribution meter.
  • the particle diameter (median diameter) at 50% cumulative volume representing the fiber median dimension is 0.01. It is preferable to use cellulose fibers having a size of ⁇ 40 ⁇ m, particularly preferably 0.05 to 10 ⁇ m.
  • the fiber median dimension measured as the particle diameter is less than 0.01 ⁇ m, the effect of addition cannot be obtained because the cellulose fiber is made too short, that is, the heat storage layer is obtained from the composition for forming the heat storage layer subsequently obtained. Even if it is going to form the film, the uniformity of the film is insufficient and the film is inferior in film formability such as holes and cracks, and the binding property of the film to the substrate may not be sufficiently obtained. is there.
  • the fiber median size is larger than 40 ⁇ m, the cellulose fiber is not sufficiently refined, and even in this case, the expected effect is obtained because the uniformity of the film of the heat storage layer to be formed is insufficient ( There is a possibility that the film forming property and the binding property to the substrate cannot be obtained, and further, the contact of the fluid (gas) to the heat storage material is lowered, and the performance of the heat storage material is greatly impaired. Moreover, by setting it as the said range, a cellulose fiber forms a mesh-like network structure in the formed thermal storage layer, and the volume change accompanying the phase change and chemical reaction of a thermal storage material can be relieved.
  • the finely divided cellulose fiber used in the present invention is not particularly limited with respect to the fiber diameter, but is, for example, 0.001 to 10 ⁇ m, preferably 0.01 to 1 ⁇ m. Further, the aspect ratio (L / D) is not particularly limited, but is, for example, 10 to 100,000, and preferably 100 to 10,000.
  • the refined cellulose fiber used in the present invention can be used for the preparation of a heat storage layer forming composition in the form of an aqueous dispersion of cellulose fiber obtained by the wet pulverization method described above.
  • the blending amount of the (B) refined cellulose fiber is 0.01 to 100 parts by weight, preferably 0, with respect to 100 parts by weight of the (A) heat storage material. 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. If the blended amount of the refined cellulose fiber exceeds the above numerical range, the fluid (gas) contact with the heat storage material may be reduced, and the heat storage performance of the heat storage material may be impaired. If the value is less than the above numerical range, the desired film formability and binding property to the substrate may not be sufficiently obtained.
  • the composition for forming a heat storage layer of the present invention contains a water-soluble polymer as a binder component for the purpose of improving film formability.
  • the water-soluble polymer can contribute to the binding between the heat storage materials or between the heat storage material and the base material together with the above-described (B) refined cellulose fiber.
  • the water-soluble polymer is not particularly limited.
  • polyvinyl alcohol modified polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, partially neutralized polyacrylate, cationized cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, (carboxy At least one selected from the group consisting of (methyl) (ethyl) cellulose, hydroxyethylcellulose, (hydroxyethyl) (methyl) cellulose, (ethyl) (hydroxyethyl) cellulose, hydroxypropylcellulose, (hydroxypropyl) (methyl) cellulose, and cationized starch Selected.
  • polyvinyl alcohol is preferably used.
  • the weight average molecular weight Mw measured in terms of polystyrene by GPC of the water-soluble polymer is not particularly limited, but is, for example, 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably. Is 100,000 to 300,000.
  • the amount of the (C) water-soluble polymer is 0.01 to 100 parts by weight, preferably 0.01 to 100 parts by weight of the (A) heat storage material. -10 parts by mass, more preferably 0.1-5 parts by mass, particularly preferably 0.5-1 part by mass. If the amount of the water-soluble polymer exceeds the above numerical range, the contact of the fluid (gas) to the heat storage material may be reduced, and the heat storage performance of the heat storage material may be impaired. The volume change accompanying a chemical reaction cannot be relieved, and there exists a possibility that the formed thermal storage layer may be damaged. If the blending amount is less than the above numerical range, the desired film formability and binding property to the substrate may not be sufficiently obtained.
  • composition for forming a heat storage layer of the present invention may contain other components as necessary as long as the effects of the present invention are not impaired.
  • Other ingredients include additives such as organic binders, adhesion aids such as silane coupling agents, thickeners, solvents, dispersants, leveling agents, rheology modifiers, fluidity improvers, antifoaming agents, etc. Can do.
  • composition for forming a heat storage layer of the present invention (A) a heat storage material, (B) a refined cellulose fiber, (C) a water-soluble polymer, and optionally other additives are uniformly contained in the composition. It is preferably in a dispersed and dissolved state.
  • the preparation method is not particularly limited.
  • the components (A), (B) and (C) are mixed at a predetermined ratio, and other additives are further added as desired.
  • a method for obtaining a uniform solution, among these components for example, a part of the component (A) and the component (B) are mixed to obtain a uniform solution, and then the remaining component (C) is added.
  • Examples include a method in which an additive is further added and mixed to obtain a uniform solution, or a method in which a conventional solvent (such as water) is used in addition to these components.
  • a conventional solvent such as water
  • (B) refined cellulose fibers are prepared in the form of an aqueous dispersion by the wet pulverization method described above, and the (A) component and the (C) component (and other additives are added if desired) A method of mixing the agent).
  • the ratio of the solid content in the composition for forming a heat storage layer is not particularly limited as long as each component is uniformly dispersed and dissolved in the solvent. Yes, or 1-30% by mass, or 1-25% by mass.
  • the solid content is obtained by removing a solvent component (such as water) from all the components of the heat storage layer forming composition.
  • the present invention is also directed to a heat storage material, a heat storage layer containing finely divided cellulose fibers and a water-soluble polymer, wherein the heat storage materials are captured by the cellulose fiber and the water-soluble polymer, A film shape is formed.
  • the heat storage layer can be produced from the composition for forming a heat storage layer of the present invention by a method of applying the composition for forming a heat storage layer of the present invention on a suitable substrate and drying the obtained coating film, and thus the present invention.
  • the heat storage layer produced from the composition for forming a heat storage layer is also an object of the present invention.
  • the base material may be appropriately selected according to the application to which the heat storage layer is applied, and examples thereof include metal materials such as aluminum, copper, steel, and stainless steel; ceramics such as glass and alumina.
  • the method for applying the composition for forming a heat storage layer onto a substrate is not particularly limited. For example, spray coating, spin coating, flow coating, roll coating, slit coating, spin coating following slit, inkjet coating, casting Commonly used techniques such as coating and printing can be employed.
  • the means for drying the coating film formed on the surface of the substrate after coating is not particularly limited, and conventionally known techniques such as heat drying, air drying, and reduced pressure drying can be employed.
  • the drying conditions (drying time, drying temperature, etc.) of the coating film are 1 to 40 ° C., for example, depending on the coating amount of the heat storage layer forming composition and the water volatilization rate from the heat storage layer forming composition. It is appropriately selected from the range of up to 24 hours.
  • the thickness of the heat storage layer thus obtained is generally 0.1 to 5,000 ⁇ m, preferably 1 to 2,000 ⁇ m.
  • the present invention is also directed to a heat exchanger provided with the heat storage layer, specifically, a heat exchanger in which the heat storage layer is formed on the surface of a heat conductive substrate.
  • the heat conductive base material constitutes a partition wall of a flow path (heat medium flow path) through which a heat medium flows, and the heat storage layer is formed on a surface of the partition opposite to the side through which the heat medium flows.
  • the heat medium can be, for example, cooling water for a prime mover.
  • the heat exchanger targeted by the present invention can be used as a heat exchanger mounted on a vehicle, for example.
  • Example 1 To 1.35 g of the finely divided cellulose fiber aqueous dispersion obtained in Production Example 1 (solid content: 0.01 g), 0.50 g (solid content: 0.01 g) of a 2% by weight aqueous polyvinyl alcohol solution prepared in advance and water 2 .15 g was added. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer (solid content: 20% by mass).
  • Example 2 Fine cellulose aqueous dispersion 0.10 g [manufactured by Chuetsu Pulp & Paper Co., Ltd., trade name BB-CNF-A-10, pulp raw material: bamboo bleached pulp, solid content concentration: 10% by mass, particle diameter by measurement above (fiber median Dimension): 18 ⁇ m] (solid content: 0.01 g) was added with 0.50 g (solid content: 0.01 g) of a 2% by weight aqueous polyvinyl alcohol solution prepared in advance and 3.40 g of water. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer (solid content: 20% by mass).
  • Comparative Example 1 1.00 g of zeolite was added to 4.00 g of water and stirred for about 15 minutes to obtain a composition for forming a heat storage layer (solid content: 20% by mass) of Comparative Example.
  • Table 1 shows the composition of the heat storage layer forming compositions of Examples and Comparative Examples.
  • “part” represents “part by mass”.
  • the composition for forming a heat storage layer prepared in Example 1 and Example 2 had a uniform film-like zeolite-containing heat storage layer without cracks formed on a glass substrate, and the heat storage layer Even when the glass substrate on which the slab was formed was tilted to be perpendicular to the horizontal plane of the substrate, the heat storage layer was not observed to be lifted or detached from the glass substrate, and was closely adhered to the glass substrate and fixed. It was confirmed.
  • Test procedure About 50 ⁇ L of the heat storage layer forming composition prepared in Example 1, Example 2, or Comparative Example 3 was taken in an aluminum pan for TG-DTA ( ⁇ 5 mm) so that the solid content was 10 mg. This was dried on a hot plate at 110 ° C., and a heat storage layer was formed in an aluminum pan to prepare a sample. Separately, 10 mg of zeolite powder was weighed into an aluminum pan and used as a sample of Comparative Example 1. A bubbler (23 ° C.) was installed between the TG-DTA apparatus main body and the gas flow rate regulator to enable introduction of high-humidity air (water vapor-containing air: Air / H 2 O) into the apparatus main body.
  • high-humidity air water vapor-containing air: Air / H 2 O
  • the air / H 2 O flow (No. 3, No. 7) in the TG-DTA apparatus corresponds to the process of adsorbing water vapor to the heat storage layer (zeolite). While the flow rate of gas (Air / H 2 O, N 2 ) is zero (No. 4, No. 8 (No. 10)), it corresponds to the heat storage layer (zeolite) dehydration step. Further, while N 2 gas is allowed to flow (No. 1-2, No. 5-6, No. 9), it corresponds to the step of removing water vapor in the system.
  • the sample obtained from the composition for forming a heat storage layer prepared in Example 1 and Example 2 exhibited the same water vapor adsorption behavior and dehydration behavior as the heat storage material itself (zeolite, Comparative Example 1). That is, it was confirmed that a good layer maintaining the heat storage performance was formed.
  • the sample obtained from the composition for forming a heat storage layer prepared in Comparative Example 3 is significantly inferior in water vapor adsorption rate / mass increase rate compared to the heat storage material (zeolite, Comparative Example 1), and has a peak in DTA. It was not observed, and it was confirmed that water vapor was hardly adsorbed and dehydrated, that is, the layer was formed but the heat storage performance was greatly deteriorated.

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Abstract

Le problème décrit par la présente invention concerne une composition pour former une couche de stockage thermique, qui permet d'obtenir, par un procédé simple et à température modérée, une couche de stockage thermique de type film uniforme présentant une excellente adhérence à un matériau de base et qui permet, à la couche de stockage thermique, de présenter des performances de stockage thermique équivalentes à celles d'un matériau de stockage thermique utilisé comme matière première. La solution porte sur une composition pour former une couche de stockage thermique et une couche de stockage thermique produite à partir de celle-ci, caractérisées en ce qu'elles contiennent (A) 100 parties en masse d'un matériau de stockage thermique, (B) 0,01-100 parties en masse de fibre de cellulose raffinée et (C) 0,01-100 parties en masse d'un polymère soluble dans l'eau.
PCT/JP2017/043676 2016-12-05 2017-12-05 Composition pour former une couche de stockage thermique WO2018105617A1 (fr)

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WO2020130066A1 (fr) * 2018-12-20 2020-06-25 三菱日立パワーシステムズ株式会社 Objet en forme de plaque de stockage chimique de chaleur
JP2020203978A (ja) * 2019-06-17 2020-12-24 大村塗料株式会社 蓄熱塗料およびこれを用いた蓄熱性塗膜
JP2021008972A (ja) * 2019-06-28 2021-01-28 リンテック株式会社 蓄熱構造体及び蓄熱構造体の製造方法

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WO2021106881A1 (fr) * 2019-11-29 2021-06-03 タテホ化学工業株式会社 Matériau de stockage de chaleur chimique et son procédé de production, et pompe à chaleur chimique
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JP2021008972A (ja) * 2019-06-28 2021-01-28 リンテック株式会社 蓄熱構造体及び蓄熱構造体の製造方法
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