WO2007135978A1 - Carbon with adherent microcapsule, process for producing the same, and canister - Google Patents

Carbon with adherent microcapsule, process for producing the same, and canister Download PDF

Info

Publication number
WO2007135978A1
WO2007135978A1 PCT/JP2007/060207 JP2007060207W WO2007135978A1 WO 2007135978 A1 WO2007135978 A1 WO 2007135978A1 JP 2007060207 W JP2007060207 W JP 2007060207W WO 2007135978 A1 WO2007135978 A1 WO 2007135978A1
Authority
WO
WIPO (PCT)
Prior art keywords
microcapsule
impregnated
weight
activated carbon
solid content
Prior art date
Application number
PCT/JP2007/060207
Other languages
French (fr)
Japanese (ja)
Inventor
Susumu Abe
Tetsuya Hanamoto
Mitsuru Kato
Original Assignee
Kuraray Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Chemical Co., Ltd. filed Critical Kuraray Chemical Co., Ltd.
Publication of WO2007135978A1 publication Critical patent/WO2007135978A1/en

Links

Classifications

    • 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
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • 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
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
    • F02M25/0854—Details of the absorption canister
    • 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
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
    • F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • Microcapsule-impregnated charcoal its manufacturing method, and canister technology
  • the present invention relates to a microcapsule-impregnated carbon, a method for producing the same, and a canister. More specifically, in a microcapsule-impregnated carbon in which a microcapsule encapsulating a substance that absorbs and releases heat due to a phase change is attached to activated carbon, after water is evaporated, it forms a film and exhibits adhesiveness.
  • Aqueous emulsion (A) and crosslinkable liquid resin (B) Microcapsule-added charcoal using an aqueous composition obtained by diluting liquid-mixed resinous resin with water as a binder, its production method, and microcapsule-added charcoal It relates to canisters using.
  • the microcapsule is abbreviated as MC.
  • a vaporized fuel gas is adsorbed using a porous adsorbent such as activated carbon to prevent the vaporized fuel gas from being released into the atmosphere. in use.
  • a porous adsorbent such as activated charcoal
  • the adsorption performance tends to decrease.
  • the desorption performance tends to decrease. This is because when activated carbon adsorbs the vaporized fuel gas, it generates heat, while when desorbed, it absorbs heat, so the adsorption performance of activated carbon improves as the temperature decreases, and the desorption performance increases as the temperature increases. This is due to the contradictory nature.
  • Patent Document 1 Japanese Utility Model Publication No. 63-057351
  • Patent Document 2 International Publication WO 03/106833 A1 Publication
  • Patent Document 2 uses a phase change material that absorbs and releases latent heat according to temperature as a heat storage material, and therefore, a small amount of heat storage material is mixed. Therefore, it is expected that the latent heat storage type adsorbent will be effective in adsorbing and desorbing evaporated fuel.
  • Patent Document 2 also proposes a method of compressing and molding MC encapsulating a powdered heat storage material and an adsorbent, and according to this method, the heat storage material and the adsorbent are brought into close contact with each other. Perspective of heat transfer efficiency It seems to be effective.
  • the MC may be destroyed during the compression molding, and the accumulated components may leak out. Therefore, in order to mold the MC so as not to break down, the molding pressure is required. It needs to be lowered. If molding is performed at a reduced molding pressure, the amount of activated carbon per unit volume cannot be increased, and there is a problem that the amount of adsorption does not increase.
  • Patent Document 2 discloses a latent heat storage type adsorbent for canisters in which a heat storage material is attached and Z or attached to the surface of the adsorbent, and the heat storage material is attached to the surface of the adsorbent. It is known that the adsorption / desorption performance is improved.
  • the adhesion and Z or adhesion disclosed herein are the force that is simply mixed and dried with the liquid in which MC is dispersed and the adsorbent or the liquid in which MC is dispersed and methylcellulose, Carboxyl methyl A solution containing cellulose such as cellulose (hereinafter referred to as CMC), phenol resin, polybulal alcohol, and acetic acid butter is sprayed and dried.
  • CMC Carboxyl methyl
  • the adsorption performance decreases, or the MC that encloses the heat storage material due to vibration or the like is separated from the adsorbent, and the original heat absorption / heat generation capability cannot be displayed or the dropped MC becomes a dust filter in the canister.
  • There are practical problems such as clogging and increasing ventilation resistance.
  • an object of the present invention is to prevent temperature rise and temperature drop accompanying adsorption / desorption of the vaporized fuel gas, and to stably maintain excellent adsorption / desorption performance.
  • MC and adsorbent It is an object of the present invention to provide MC-impregnated coal that is difficult to separate and a method for producing the same, and a caster using the same.
  • the present inventors have used the above-mentioned object by using an aqueous composition obtained by diluting a liquid-mixed type of resin with water.
  • the present invention has been found. That is, the present invention relates to a microcapsule-added carbon in which a microcapsule encapsulating a substance that absorbs and releases heat due to a phase change is impregnated with activated carbon.
  • a microcapsule-impregnated charcoal characterized in that an aqueous composition obtained by diluting a liquid-mixed resin consisting of emulsion (A) and crosslinkable liquid resin (B) is used as a binder.
  • the aqueous emulsion (A) that forms a film after water is evaporated and develops an adhesive property may be simply referred to as an aqueous emulsion (A) t.
  • Another invention of the present invention is a method for producing MC-impregnated coal in which activated carbon is added to a mixture obtained by adding an aqueous composition to MC and mixed, and the mixture is stirred until substantially free of moisture and then dried.
  • Still another invention of the present invention is a caster using such MC-impregnated coal as a transpiration fuel gas adsorbent.
  • MC in which a substance that absorbs and releases heat due to phase change is encapsulated is mixed with a liquid mixed type resin composed of aqueous emulsion (A) and crosslinkable liquid resin (B) with water. Diluted It is possible to provide MC-added coal adsorbed on activated carbon using an aqueous composition as a binder, a method for producing the same, and a canister using MC-added coal.
  • the MC-impregnated coal of the present invention When used as a transpiration fuel gas adsorbent, the heat generation and heat absorption that accompanies the absorption and desorption of the transpiration fuel gas can be managed efficiently, so the performance as a transpiration fuel gas adsorbent
  • the MC-impregnated coal of the present invention is excellent in durability because MC and activated carbon are difficult to separate, and canister, ORVR (Onboard Refueling Vapor Recovery: gasoline discharged during refueling) It is preferably used for applications such as steam recovery equipment.
  • the raw material of activated carbon that becomes a carrier for attaching MC is not particularly limited, and any carbonaceous material that can be activated to form activated carbon may be used.
  • Such carbonaceous materials can be widely selected from plant-based, mineral-based, natural and synthetic materials.
  • fruit shells such as wood, charcoal, and coconut shells
  • mineral-based carbonaceous materials as coal, petroleum-based and Z or coal-based pitch
  • coatas and natural materials as cotton Natural fibers such as hemp, regenerated fibers such as rayon and viscose rayon, semi-synthetic fibers such as acetate and triacetate
  • polyamides such as nylon
  • polybulal alcohols such as vinylon
  • polyacrylonitrile such as acrylic And polyolefins
  • charcoal is preferred because it is easy to attach MC.
  • the shape of the carbonaceous material and the activated carbon obtained by activating the carbonaceous material is not particularly limited, and various shapes such as granular, powdery, fibrous, and sheet-like can be used.
  • the fibrous or sheet-like carbonaceous material natural cellulose fibers such as cotton, regenerated cellulose fibers such as viscose rayon and polynosic rayon, synthetic fibers such as pulp fibers, polybutanol alcohol fibers, ethylene butanol alcohol fibers and phenol fibers. Examples thereof include woven or non-woven fabrics such as fibers, films, felts, and sheet-like materials.
  • the carbonaceous material is carbonized and activated to become activated carbon. Conditions such as processing at 300 ° C or higher while flowing a small amount of inert gas through the rotary kiln can be adopted.
  • the activation method any activation method such as gas activation or drug activation may be used. Examples of the gas used in the gas activation method include water vapor, carbon dioxide gas, oxygen, LPG combustion exhaust gas, or a mixed gas thereof. These activation temperatures are usually carried out by raising the temperature to 300 ° C to 1200 ° C, preferably 900 ° C.
  • Drugs used in the method of drug activation include acids such as sulfuric acid, phosphoric acid, nitric acid, sodium hydroxide, potassium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, magnesium hydroxide Examples thereof include metal hydroxides such as salts of metal hydroxides such as salts of calcium and salts of zinc. These activation temperatures are usually in the range of 300 ° C. to 800 ° C., although depending on the drug used.
  • the same type of activated carbon may be used alone, or different types of activated carbon may be mixed and used.
  • MC on which the latent heat storage material is sealed is attached to the surface of the activated carbon with a water-based composition obtained by diluting a liquid-mixed resin consisting of an aqueous emulsion (A) and a crosslinkable liquid resin (B) with water.
  • A aqueous emulsion
  • B crosslinkable liquid resin
  • the average particle size of the activated carbon is preferably 0.5-5 mm! /.
  • molded activated carbon In order to uniformly attach MC to activated carbon, it is preferable to use molded activated carbon.
  • a known method can be employed. For example, 100 parts by weight of powdered activated carbon is mixed with 30 to 35 parts by weight of a binder such as pitch and coal tar, and a mixture is mixed with a pelleter. For example, it may be extruded into a cylindrical shape having a diameter of about 2.5 to 4 mm and a length of about 5 to 8 mm.
  • trade name 3 GX manufactured by Kuraray Chemical Co., Ltd. is suitable.
  • a known MC may be used as the MC for enclosing the latent heat storage body, but it should be understood that a MC that does not easily leak when the latent heat storage body reaches the melting temperature should be used.
  • MC obtained by the method disclosed in Patent Document 2 or MC sold by Miki Riken Kogyo Co., Ltd. can be used as the MC in which the latent heat storage body is enclosed. It is also possible to use a material made of MC with a polymer film material, or a heat storage capsule in which an organic latent heat storage material is absorbed in polyolefin or the like and the surface is coated with a resin.
  • MC The average particle size is preferably from 0.1 to 500 m.
  • MC encloses a substance that absorbs and releases heat due to phase change (hereinafter sometimes referred to as a latent heat storage body), and the latent heat storage body has a temperature of 10 ° C to 100 ° C. More preferably, from the viewpoint of energy efficiency, it is preferable to use an organic compound that undergoes a phase change at 20 ° C to 70 ° C.
  • organic compounds examples include hydrocarbon compounds such as decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, eicosane, and norafine, lauryla norconole, myristinolenolenole, cetinoleanorenorenole, stearinorenoleolecole.
  • hydrocarbon compounds such as decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, eicosane, and norafine, lauryla norconole, myristinolenolenole, cetinoleanorenorenole, stearinorenoleolecole.
  • higher alcohols such as eicosanol and seryl alcohol, higher fatty acids such as lauric acid, myristic acid, stearic acid, oleic acid and behenic acid, glycerides, amides such as propionamide, PEG400, PEG600, PEG1000, PEG2000, PEG4000 Polyethylene glycols such as PEG6000, phenols such as phenol, and mixtures thereof can be displayed.
  • the heat storage body may contain a compound having a melting point higher than that of the heat storage body!
  • the content of such a high melting point compound is preferably 0.5 to 30% by weight, more preferably 1 to 15% by weight with respect to the heat storage body.
  • the high melting point compound include aliphatic hydrocarbon compounds, aromatic compounds, esters, carboxylic acids, alcohols, amides and the like.
  • the combination of the latent heat storage body and the high melting point compound are shown.
  • the high melting point compound is cetyl alcohol, stearyl alcohol, eicosanol, myristic acid, behen. Acid and stearamide may be included. Two or more of these high melting point compounds may be used in combination.
  • inorganic compounds such as talc, silica, titanium dioxide, calcium silicate, and antimony trioxide are used. And fine particles of organic acid salts such as magnesium stearate and sodium benzoate.
  • organic acid salts such as magnesium stearate and sodium benzoate.
  • the latent heat of MC enclosing a latent heat accumulator is preferably 50 mjZmg or more, more preferably lOOmiZmg or more.
  • the latent heat here refers to the apparent latent heat of the entire MC enclosing the latent heat accumulator, and can be easily measured with a differential scanning calorimeter.
  • a binder used in MC-added carbon for use in a caster it is important that a strong adhesive effect can be exhibited in a small amount without blocking fine pores of activated carbon.
  • the biggest feature is that the aqueous activated carbon (A) that forms a film after water is evaporated and develops adhesive properties to support MC on the activated carbon surface (B) and a liquid that can also be crosslinked (B)
  • An aqueous composition obtained by diluting mixed type rosin with water is used as a binder.
  • MC can be firmly attached to the activated carbon surface by using, as a binder, an aqueous composition obtained by diluting a liquid-mixed type of resin usually used as an adhesive with water. Even when used as a transpiration fuel gas adsorbent in a canister, MC does not fall off from activated charcoal due to vibration, and it is quite surprising and surprising that a transpiration fuel gas adsorbent with excellent durability can be obtained. It is an effect.
  • the aqueous emulsion (A) which forms a film after water is evaporated and exhibits adhesiveness, may be referred to as the main agent, and the crosslinkable liquid resin (B) may be referred to as the auxiliary agent.
  • the liquid-mixed type of resin used in the present invention comprises such a main agent (A) and an auxiliary agent (B), and it is preferable to use acrylic or polyurethane-based resin as the main agent. . Use a mixture of these.
  • the auxiliary agent (B) it is preferable to use a resin containing a crosslinking agent having a reactive functional group that functions as an adhesion improver.
  • the reactive functional group is selected from the group consisting of an isocyanate group, a block isocyanate group, an epoxy group, an oxazoline group, a carbodiimide group, an aziridine group, a carbonyl group, and a hydrazide group. Of these, an isocyanate group or an epoxy group is preferred, although at least one selected functional group is preferred. These may be used in a mixture.
  • the liquid-mixed coagulant it is preferable to use the liquid-mixed coagulant at a solid content ratio of 70 to 95% by weight of the main agent and 5 to 30% by weight of the auxiliary agent, but it is recommended that these amounts be kept as small as possible.
  • the solid content ratio here refers to the percentage by weight with the solid content of the main agent or auxiliary agent as the numerator when the total solid content of the main agent and auxiliary agent is used as the denominator. It is the ratio of the main agent or auxiliary agent represented.
  • the apparent latent heat of MC-added coal is preferably 7mjZmg or more, and 15mj / mg or more is preferred. More preferred is 30 miZmg or more.
  • MC is put into a dispersion medium and dispersed by stirring (mixed solution 1).
  • the dispersion medium hydrocarbons such as water, alcohol, and acetone are used, but water is preferable from the viewpoint of handleability and safety. If the dispersion medium is too much, it takes time to remove the dispersion medium, and if it is too small, the dispersibility is not good. Therefore, it is preferable to use about 50 to 65 parts by weight of the dispersion medium with respect to 100 parts by weight of the activated carbon.
  • an aqueous composition obtained by diluting the liquid mixture type resin consisting of the main agent (A) and the auxiliary agent (B) with water is added to the mixed solution 1 and stirred so that MC does not aggregate.
  • the MC-added coal of the present invention can be produced by adding activated carbon to the mixed solution 2 or mixing and mixing the mixed solution 2 with the activated carbon, stirring sufficiently until water is substantially not observed, and drying.
  • the mixing ratio of the mixed liquid 2 with respect to the activated carbon is preferably 5 to 70 parts by weight based on 100 parts by weight of the activated carbon with the MC coconut water-based composition added as a solid content.
  • the drying conditions are not particularly limited, but are usually carried out at a temperature of 80 to 120 ° C for about 12 to 24 hours.
  • the MC-impregnated coal of the present invention it is possible to efficiently manage the heat generation and heat absorption caused by the adsorption and desorption of the vaporized fuel gas, so that the performance as the vaporized fuel gas adsorbent is highly maintained. It becomes possible.
  • MC and activated carbon are difficult to separate, it is preferably used in applications such as canisters as a vaporized fuel gas adsorbent with excellent durability.
  • the melting point, melting heat, temperature drop crystallization temperature, and crystallization heat of the latent heat accumulator are the differential scanning calorimeter (EXSTAR6000 RDC manufactured by Seiko Instruments Inc.). In 220U), the temperature increase rate and temperature decrease rate were measured at 5 ° CZ minutes.
  • the latent heat was expressed as the average value of heat of fusion and heat of crystallization.
  • Example 1 of International Publication WO 03/106833 A1 37 g of formaldehyde aqueous solution 6.5 g and 10 g of water were added to 5 g of melamine powder, pH was adjusted to 8, and the mixture was heated to about 70 ° C. A formaldehyde precondensate aqueous solution was obtained. A solution prepared by dissolving 70 g of n-octadecane as a compound with phase change in 100 g of a sodium salt aqueous solution of styrene anhydride copolymer adjusted to pH 4.5 was added to the above aqueous solution with vigorous stirring, and the particle size was reduced. Emulsification was carried out to about 1.3 m.
  • the whole amount of the above melamine formaldehyde aqueous solution was added to the obtained emulsion and stirred at 70 ° C. for 2 hours, and then the pH was adjusted to 9 to effect encapsulation. After completion of the reaction, the capsule was suction filtered and dried to obtain MC having a particle size of about 2 m.
  • the latent heat of MC obtained at this time was 195mjZmg.
  • MC41g above is dispersed in 118g of water, and Nippon Carnoid Industry Co., Ltd., Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 4.7g, and secondary agent 1 solid content 10% 4.7g of Polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water and Epoxy compound Denacor EX-614 manufactured by Nagase ChemteX Corporation diluted with water to a solid content of 10% as secondary agent 2. 2.4 g was added and stirred well. At this time, the ratio of the solid content of the main agent: secondary agent was 76.8: 23.2 by weight, and the solid content ratio of the mixed resin to 100 parts by weight of MC was 7.5 parts by weight.
  • Figure 2 shows the caster used to see the performance of MC-impregnated coal.
  • 3 is a canister
  • 4 is a purge air port
  • 5 is a dispersion plate such as a wire mesh
  • 6 is MC-added charcoal
  • 7 is an n-butane supply port
  • 8 is a thermometer
  • 9 is a heat insulating material.
  • a 63mm sq., 300mm high (effective filling height 252mm), polychlorinated bule caster with a filling volume of 100 OmL as shown in Fig. 2 is filled with 360 g equivalent of the obtained MC-impregnated coal lOOOOmL. Then, 99% of n-butane was supplied at 25 ° C in an up-flow of 1 liter (L) Z, adsorbed on MC-impregnated coal, and stopped when the outlet n-butane concentration reached 3000 ppm. .
  • n-butane was desorbed by flowing air at room temperature at a flow rate of 15 LZ for 20 minutes. This adsorption / desorption operation was repeated 10 times, and the maximum temperature and the minimum temperature in the tenth caster were measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 12.5 ° C. Similarly, 350g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was filled with only 350g equivalent of lOOOOmL, and the maximum temperature was 64 ° C and the minimum temperature was 6 ° C. It is clear that the change is suppressed.
  • MC was prepared in the same manner as in Example 1, and 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) 4. 9 g of polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent 1 and 10% solid content as an auxiliary agent 2 0.5 g of epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 94.4: 5.6 in weight ratio, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 7.1 parts by weight.
  • Example 1 The amount of fine powder falling off was determined in the same manner as in Example 1, and found to be 1.9 mgZg. As in Example 1, 355 g of lOOOOmL equivalent was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 13 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
  • PMDC 32SP particle size 10 m, MC latent heat 50 miZmg 35. 3 g is dispersed in 118 g of water.
  • Emargillon-Rikizor FX— 672 solid content 50%
  • 4.7 g of the epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water so as to have a solid content of 10% as an adjunct 2 was added and stirred well.
  • the solid content ratio of the main agent: secondary agent was 76.9: 23.18 by weight
  • the solid content ratio of the mixed type resin to 100 parts by weight of MC was 17.3 parts by weight.
  • Example 1 When the amount of fine powder falling off was determined in the same manner as in Example 1, it was 1.3 mgZg. As in Example 1, 353 g of lOOOOmL was charged into a canister and the temperature in the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 8 ° C, and the temperature change in the canister was suppressed. Obviously.
  • the solid content ratio of the main agent to the auxiliary agent was 84.2: 15.8 in weight ratio.
  • the solid content ratio of the mixed type resin to 100 parts by weight of MC was 12.9 parts by weight.
  • Example 1 The amount of fine powder fallen off as determined in Example 1 was 1.9 mgZg. As in Example 1, 35 lg equivalent to lOOOOmL was filled into a canister, and the temperature in the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 8 ° C. It is clear that it has been suppressed.
  • MC was prepared in the same manner as in Example 1, 33.5 g of MC3 was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid (50% min.) 2.4 g and 2.4 g of block isocyanate elastolone BN-4 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. diluted with water to a solid content of 10% as an adjunct were added and stirred well. At this time, the solid content ratio of the main agent: the secondary agent was 83.3: 16.7 in weight ratio, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 4.1 parts by weight.
  • Example 1 The amount of fine powder falling off was determined in the same manner as in Example 1, and found to be 1.8 mgZg.
  • 356 g of lOOOOmL equivalent was filled into a canister, and the temperature in the canister was measured. The maximum temperature was 58 ° C and the minimum temperature was 13 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
  • MC was prepared in the same manner as in Example 1, 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) 2. 2.4 g of oxazoline group-containing water-soluble polymer Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 83.3: 16.7 in weight ratio, and the solid content ratio of the mixed resin to MCIOO weight part was 4.1 parts by weight.
  • the latent heat of the MC impregnated coal obtained at this time is 29mJ
  • the maximum temperature was 59 ° C and the minimum temperature was 11 ° C, and the temperature change in the canister was suppressed. Is clear.
  • MC was prepared in the same manner as in Example 1, and 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 4 7 g and 4.8 g of Carposimide Imabsorb Calpolite V-04 manufactured by Nisshinbo Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent were added and stirred well. At this time, the ratio of the solid content of the main agent to the auxiliary agent was 83:17 in terms of weight ratio, and the solid content of the mixed resin with respect to 100 parts by weight of MC was 8 parts by weight.
  • Example 1 The amount of fine powder falling off was determined in the same manner as in Example 1, and it was 2. OmgZg. As in Example 1, 358 g of lOOOmL equivalent was filled into a canister and the temperature in the canister was measured. The maximum temperature was 58 ° C and the minimum temperature was 11 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
  • Example 2 The amount of fine powder falling off was determined in the same manner as in Example 1, and found to be 1.8 mgZg. Similar to Example 1, 352 g equivalent of lOOOOmL was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 8 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
  • MC was prepared in the same manner as in Example 1, and 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 4 7.4 g of Nippon Polyvinyl acetate 'Poval Co., Ltd.' D-Polymer DF-17, which has a carboxylic group diluted with water so that the solid content is 10% as secondary agent 1 and 10% as secondary agent 2 0.5 g of adipic acid dihydrazide having a hydrazide group diluted to% was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 70.4: 29.6 in weight ratio, and the solid content ratio of the mixed type resin to 1.00 parts by weight of MC was 9.5 parts by weight.
  • Example 2 The amount of fine powder falling off was determined in the same manner as in Example 1, and it was 1.9 mgZg. Similar to Example 1, 357 g equivalent of lOOOOmL was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 11 ° C, and the temperature change in the canister was suppressed. The It is clear that
  • MC was prepared in the same manner as in Example 1, 130 g of MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) was 13.3 g. , 13.3 g of polyisocyanate AQ210 manufactured by Nippon Polyuretan Kogyo Co., Ltd. diluted with water to a solid content of 10% as side agent 1 and diluted with water to a solid content of 10% as side agent 2 6.7 g of Epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 76.9: 23.1 by weight, and the solid content ratio of the mixed resin to 100 parts by weight of MC was 6.5 parts by weight.
  • Example 2 The amount of fine powder falling off was determined in the same manner as in Example 1. The result was 2. lmgZg. Similar to Example 1, 375 g equivalent of lOOOOmL was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 56 ° C and the minimum temperature was 14 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
  • MC was prepared in the same manner as in Example 1, and 10.4 g of the MC was dispersed in 118 g of water.
  • Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 2 lg and polyisocyanate AQ210 manufactured by Nippon Polyuretan Kogyo Co., Ltd. diluted with water to a solid content of 10% as adjunct 1 2.
  • Water to a solid content of 10% as lg and adjunct 2 1.
  • Example 1 When the amount of fine powder falling off was determined in the same manner as in Example 1, it was 0.9 mgZg. As in Example 1, 35 lg equivalent to lOOOOmL was filled into a canister and the temperature in the canister was measured. The maximum temperature was 61 ° C and the minimum temperature was 8 ° C. The temperature change in the canister was It is clear that it has been suppressed.
  • MC was prepared in the same manner as in Example 1, 41 g of MC was dispersed in 118 g of water, and 2.4 g of Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strengsol sol FX-672 (solid content 50%) was used as the main agent 1. And Kuraray Co., Ltd., polyurethane emulsion KMN-N Oc (solid content 40%) as the main agent 2 and polyisolated from Nippon Polytane Kogyo Co., Ltd. diluted with water to a solid content of 10% as the auxiliary agent 1.
  • coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 171.5 g of the obtained mixed liquid, and vigorously stirred until no surface moisture was observed, and the resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal.
  • the latent heat of the MC impregnated coal obtained at this time is 32mJ
  • the maximum temperature was 58 ° C and the minimum temperature was 12.5 ° C, and the temperature change inside the canister was suppressed. Obviously.
  • MC was prepared in the same manner as in Example 1, and 6 g of the MC was dispersed in 118 g of water.
  • 1 lg of Epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 76.6: 23.4 in weight ratio, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 22.8 parts by weight.
  • the amount of fine powder falling off was determined in the same manner as in Example 1.
  • the amount was 0.8 mgZg.
  • 350 g equivalent to lOOOOmL was charged into the caster, and the temperature in the caster was adjusted.
  • the maximum temperature was 64 ° C and the minimum temperature was 6 ° C, and the temperature change in the canister was not suppressed.
  • MC was prepared in the same manner as in Example 1 except that the main agent and the auxiliary agent were not used, and 35.3 g of the MC was dispersed in 118 g of water and stirred well.
  • the above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal.
  • the latent heat of the MC-impregnated coal obtained at this time was 29. lmiZmg.
  • Example 1 In the same manner as in Example 1, 345 g equivalent of lOOOOmL was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 12 ° C. Although the change in the degree was suppressed, the amount of fine powder falling off was determined in the same manner as in Example 1, and it was large at 122.7 mgZg.
  • MC was produced in the same manner as in Example 1, 33.5 g of MC3 was dispersed in 118 g of water, no secondary agent was used, and CMC diluted to 50% with water as the main agent, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 4.7 g of Serogen WS-A was added and stirred well. At this time, the ratio of the solid content of the mixed resin to 100 parts by weight of MC was 6.7 parts by weight.
  • Example 2 Similarly to Example 1, 348 g of lOOOOmL equivalent was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 12 ° C. However, when the amount of fine powder falling off was determined in the same manner as in Example 1, it was 14.6 mg Zg.
  • Example 2 In the same manner as in Example 1, 351 g of lOOOOmL equivalent was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 61 ° C and the minimum temperature was 9 ° C. However, when the amount of fine powder falling off was determined in the same manner as in Example 1, it was 11. lmg Zg.
  • Example 2 Similar to Example 1, 356 g of lOOOOmL equivalent was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 10 ° C. However, when the amount of fine powder falling off was determined in the same manner as in Example 1, it was 12.8 mg Zg.
  • Comparative Example 5 MC was prepared in the same manner as in Example 1 except that the main agent was not used, and 33.5 g of the MC was dispersed in 118 g of water and diluted with water to a solid content of 10%.
  • Example 1 As in Example 1, 375 g of lOOOOmL was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 56 ° C and the minimum temperature was 14 ° C. Although the change was suppressed, the amount of fine powder falling off was determined in the same manner as in Example 1, and it was as large as 12. lmgZg.
  • FIG. 1 is a 200 ⁇ micrograph of an MC-added carbon cross section obtained in Example 1.
  • FIG. 2 is a schematic cross-sectional view of a caster used to see the performance of MC-added coal of the present invention.

Abstract

A carbon having adherent MCs which is prevented from increasing or decreasing in temperature with the adsorption/desorption of a fuel gas evaporated, has excellent adsorption/desorption performances, can stably maintain the adsorption/desorption performances, and is less apt to separate into the MCs and the adsorbent; a process for producing the carbon; and a canister employing the carbon. The carbon having adherent microcapsules comprises activated carbon and, adherend thereto, microcapsules each having, enclosed therein, a substance which absorbs and emits heat with phase changes. The carbon having such microcapsules adherent thereto is obtained using as a binder an aqueous composition obtained by diluting with water a liquid mixture resin comprising an aqueous emulsion (A) which forms a film upon water evaporation to have adhesive properties and a crosslinking liquid resin (B).

Description

明 細 書  Specification
マイクロカプセル添着炭及びその製造方法、並びにキヤニスター 技術分野  Microcapsule-impregnated charcoal, its manufacturing method, and canister technology
[0001] 本発明はマイクロカプセル添着炭及びその製造方法、並びにキヤニスターに関す る。さらに詳しくは、相変化により熱の吸収及び放出を生じる物質を封入したマイクロ カプセルを活性炭に添着したマイクロカプセル添着炭にお ヽて、水を蒸発させた後 に皮膜状になって接着性を発現する水性ェマルジヨン (A)と架橋性の液状榭脂 (B) 力もなる液混合型榭脂を水で希釈した水性組成物を結合剤とするマイクロカプセル 添着炭及びその製造方法、並びにマイクロカプセル添着炭を用いたキヤニスターに 関する。以下、マイクロカプセルを MCと略記する。  [0001] The present invention relates to a microcapsule-impregnated carbon, a method for producing the same, and a canister. More specifically, in a microcapsule-impregnated carbon in which a microcapsule encapsulating a substance that absorbs and releases heat due to a phase change is attached to activated carbon, after water is evaporated, it forms a film and exhibits adhesiveness. Aqueous emulsion (A) and crosslinkable liquid resin (B) Microcapsule-added charcoal using an aqueous composition obtained by diluting liquid-mixed resinous resin with water as a binder, its production method, and microcapsule-added charcoal It relates to canisters using. Hereinafter, the microcapsule is abbreviated as MC.
背景技術  Background art
[0002] 従来から、活性炭等の多孔質吸着材を用いて蒸散燃料ガスを吸着させ、蒸散燃料 ガスの大気への放出を防止することが知られており、自動車に搭載してキヤ-スター として使用されている。しかしながら、自動車などにおいて生じる蒸散燃料ガスを活性 炭等の多孔質吸着材で吸着すると吸着性能は低下傾向となり、逆に脱着する際、脱 着性能は低下傾向となる。これは、活性炭が蒸散燃料ガスを吸着するときは発熱し、 一方脱着するときは吸熱するため、活性炭の吸着性能は温度が低いほど向上し、脱 着性能は温度が高いほど向上するという本質的な特性と相反することに起因する。  [0002] Conventionally, it has been known that a vaporized fuel gas is adsorbed using a porous adsorbent such as activated carbon to prevent the vaporized fuel gas from being released into the atmosphere. in use. However, if the vaporized fuel gas generated in automobiles is adsorbed with a porous adsorbent such as activated charcoal, the adsorption performance tends to decrease. Conversely, when desorbing, the desorption performance tends to decrease. This is because when activated carbon adsorbs the vaporized fuel gas, it generates heat, while when desorbed, it absorbs heat, so the adsorption performance of activated carbon improves as the temperature decreases, and the desorption performance increases as the temperature increases. This is due to the contradictory nature.
[0003] したがって、活性炭等の多孔質吸着材をそのまま蒸散燃料ガス吸着材として使用 すると、活性炭の吸脱着性能が充分に発揮されず非効率的なものとなる。このような 問題を解決する一つの方法として潜熱型蓄熱材の特性を利用する方法があり、これ まで多くの提案がなされている。  [0003] Therefore, if a porous adsorbent such as activated carbon is used as a transpiration fuel gas adsorbent as it is, the adsorption / desorption performance of the activated carbon is not fully exhibited, which is inefficient. One way to solve these problems is to use the characteristics of latent heat storage materials, and many proposals have been made so far.
[0004] 例えば、好ましくは 50〜70°Cの温度で動作する潜熱蓄熱材を含ませた蓄熱材混 入活性炭を使用した蒸発燃料捕集装置が開示されている (特許文献 1)。しかしなが ら、ここに開示された蓄熱材混入活性炭は活性炭の多孔内に無機塩類などの蓄熱 材を有するようにしたものであり、ノリア一がないため蓄熱材の相変化により無機塩 類などの蓄熱材が流出する恐れがある。 特許文献 1 :実開昭 63— 057351号公報 [0004] For example, an evaporative fuel collecting apparatus using a heat storage material mixed activated carbon containing a latent heat storage material that preferably operates at a temperature of 50 to 70 ° C is disclosed (Patent Document 1). However, the heat storage material-mixed activated carbon disclosed here has a heat storage material such as inorganic salts in the pores of the activated carbon, and since there is no noria, inorganic salts and the like due to the phase change of the heat storage material. There is a risk that the heat storage material. Patent Document 1: Japanese Utility Model Publication No. 63-057351
[0005] 蓄熱材の流出を防ぐためには蓄熱材を多孔質体に封じ込めることが有用であり、例 えば温度変化に応じて潜熱の吸収及び放出を生じる物質を MCに封入した蓄熱材と 吸着材カもなる潜熱蓄熱型吸着材をキヤ-スターに使用することが知られている (特 許文献 2)。特許文献 2に開示された潜熱蓄熱型吸着材によれば、吸脱着に伴う熱の 出入りによる性能低下、すなわち吸着時の発熱による温度上昇及び脱着時の吸熱に よる温度降下を防止することができ、蓄熱材の漏出もないので実用的であり、吸脱着 に伴って熱の出入りが不可欠なキヤニスターの性能向上に有用であることが想定さ れる。 [0005] To prevent the heat storage material from flowing out, it is useful to contain the heat storage material in a porous body. For example, a heat storage material and an adsorbent in which a substance that absorbs and releases latent heat in response to temperature changes is enclosed in MC. It is known to use a latent heat storage type adsorbent for the caster (Patent Document 2). According to the latent heat storage type adsorbent disclosed in Patent Document 2, it is possible to prevent performance degradation due to heat entering and exiting due to adsorption / desorption, that is, temperature rise due to heat generation during adsorption and temperature drop due to heat absorption during desorption. In addition, it is practical because there is no leakage of the heat storage material, and it is expected to be useful for improving the performance of canisters where heat in and out is indispensable with adsorption and desorption.
特許文献 2 :国際公開 WO 03/106833 A1公報  Patent Document 2: International Publication WO 03/106833 A1 Publication
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 特許文献 2に記載された MCを用いた吸着材は、温度に応じて潜熱の吸収及び放 出を生じる相変化物質を蓄熱材として使用しているため少量の蓄熱材を混入させる ことにより、潜熱蓄熱型吸着材として蒸発燃料の吸脱着に効果を発現することが期待 される。そして、特許文献 2には、粉末状の蓄熱材を封入した MCと吸着材を混合し て圧縮成形する方法も提案されており、この方法によれば蓄熱材と吸着材とが密着 することにより伝熱効率の観点力 有効であると思われる。  [0006] The adsorbent using MC described in Patent Document 2 uses a phase change material that absorbs and releases latent heat according to temperature as a heat storage material, and therefore, a small amount of heat storage material is mixed. Therefore, it is expected that the latent heat storage type adsorbent will be effective in adsorbing and desorbing evaporated fuel. Patent Document 2 also proposes a method of compressing and molding MC encapsulating a powdered heat storage material and an adsorbent, and according to this method, the heat storage material and the adsorbent are brought into close contact with each other. Perspective of heat transfer efficiency It seems to be effective.
[0007] し力しながら、圧縮成形する方法によれば、圧縮成形時に MCが破壊され蓄熟成 分が漏れ出す恐れがあり、したがって、 MCを破壊しないように成形するためには成 形圧力を低下させる必要がある。そして、成形圧力を低下させて成形すれば単位体 積あたりの活性炭量を増加させることができず、吸着量が増カロしな 、と 、う問題があ る。  [0007] However, according to the compression molding method, the MC may be destroyed during the compression molding, and the accumulated components may leak out. Therefore, in order to mold the MC so as not to break down, the molding pressure is required. It needs to be lowered. If molding is performed at a reduced molding pressure, the amount of activated carbon per unit volume cannot be increased, and there is a problem that the amount of adsorption does not increase.
[0008] また、特許文献 2には、吸着材の表面に蓄熱材が付着及び Z又は添着されたキヤ ニスター用潜熱蓄熱型吸着材も開示されており、吸着材の表面に蓄熱材を付着させ ることで吸脱着性能が向上することは公知である。しかしながら、ここに開示された付 着及び Z又は添着とは、 MCを分散させた液と吸着材とを均一に混合し乾燥させた だけのものである力 又は MCを分散させた液とメチルセルロース、カルボキシルメチ ルセルロース（以下 CMC)等のセルロース、フエノール榭脂、ポリビュルアルコール、 酢酸ビュル等のバインダーを混ぜた溶液をスプレーして乾燥させるものであり、この ような吸着材は使用時に吸着材の細孔が閉塞され、吸着性能が減少したり、振動等 により蓄熱材を封入した MCと吸着材が分離しやすぐ本来の吸発熱能力を発揮でき なくなる、又は脱落した MCがキヤニスター内での除塵フィルターに詰まって通気抵 抗を上昇させるなど実用上の問題がある。 [0008] Further, Patent Document 2 discloses a latent heat storage type adsorbent for canisters in which a heat storage material is attached and Z or attached to the surface of the adsorbent, and the heat storage material is attached to the surface of the adsorbent. It is known that the adsorption / desorption performance is improved. However, the adhesion and Z or adhesion disclosed herein are the force that is simply mixed and dried with the liquid in which MC is dispersed and the adsorbent or the liquid in which MC is dispersed and methylcellulose, Carboxyl methyl A solution containing cellulose such as cellulose (hereinafter referred to as CMC), phenol resin, polybulal alcohol, and acetic acid butter is sprayed and dried. The adsorption performance decreases, or the MC that encloses the heat storage material due to vibration or the like is separated from the adsorbent, and the original heat absorption / heat generation capability cannot be displayed or the dropped MC becomes a dust filter in the canister. There are practical problems such as clogging and increasing ventilation resistance.
[0009] したがって、本発明の目的は、蒸散燃料ガスの吸脱着に伴う温度上昇と温度降下 を防止することができるとともに、優れた吸脱着性能を安定に維持することができ、 M Cと吸着材とが分離しにくい MC添着炭とその製造方法、並びにそれを用いたキヤ- スターを提供することにある。 Accordingly, an object of the present invention is to prevent temperature rise and temperature drop accompanying adsorption / desorption of the vaporized fuel gas, and to stably maintain excellent adsorption / desorption performance. MC and adsorbent It is an object of the present invention to provide MC-impregnated coal that is difficult to separate and a method for producing the same, and a caster using the same.
課題を解決するための手段  Means for solving the problem
[0010] 本発明者らは、 MCと活性炭を強固に結合するための結合剤について鋭意検討を 重ねた結果、液混合型の榭脂を水で希釈した水性組成物を使用することにより上記 目的を達成することができることを見出し本発明に到達した。すなわち、本発明は、 相変化により熱の吸収及び放出を生じる物質を封入したマイクロカプセルを活性炭 に添着したマイクロカプセル添着炭において、水を蒸発させた後に皮膜状になって 接着性を発現する水性ェマルジヨン (A)と架橋性の液状榭脂 (B)カゝらなる液混合型 榭脂を水で希釈した水性組成物を結合剤とすることを特徴とするマイクロカプセル添 着炭である。以下、水を蒸発させた後に皮膜状になって接着性を発現する水性エマ ルジョン（A)を単に水性ェマルジヨン (A) t 、うことがある。  [0010] As a result of intensive investigations on a binder for strongly binding MC and activated carbon, the present inventors have used the above-mentioned object by using an aqueous composition obtained by diluting a liquid-mixed type of resin with water. The present invention has been found. That is, the present invention relates to a microcapsule-added carbon in which a microcapsule encapsulating a substance that absorbs and releases heat due to a phase change is impregnated with activated carbon. A microcapsule-impregnated charcoal characterized in that an aqueous composition obtained by diluting a liquid-mixed resin consisting of emulsion (A) and crosslinkable liquid resin (B) is used as a binder. Hereinafter, the aqueous emulsion (A) that forms a film after water is evaporated and develops an adhesive property may be simply referred to as an aqueous emulsion (A) t.
[0011] 本発明のもう一つの発明は、 MCに水性組成物を添加し混合した混合物に活性炭 を添加し、実質的に水分がなくなるまで攪拌した後乾燥する MC添着炭の製造方法 である。  [0011] Another invention of the present invention is a method for producing MC-impregnated coal in which activated carbon is added to a mixture obtained by adding an aqueous composition to MC and mixed, and the mixture is stirred until substantially free of moisture and then dried.
[0012] そして、本発明のさらにもう一つの発明は、このような MC添着炭を蒸散燃料ガス吸 着材とするキヤ-スターである。  [0012] Still another invention of the present invention is a caster using such MC-impregnated coal as a transpiration fuel gas adsorbent.
発明の効果  The invention's effect
[0013] 本発明により、相変化により熱の吸収及び放出を生じる物質を封入した MCを、水 性ェマルジヨン (A)と架橋性の液状榭脂 (B)からなる液混合型榭脂を水で希釈した 水性組成物を結合剤として用いて活性炭に添着した MC添着炭とその製造方法、並 びに MC添着炭を用いたキヤニスターを提供することができる。本発明の MC添着炭 を蒸散燃料ガス吸着材として使用すると、蒸散燃料ガスの吸脱着に伴って生じる発 熱及び吸熱を効率的に管理することができるので蒸散燃料ガス吸着材としての性能 を高度に保持することが可能となり、しかも本発明の MC添着炭は、 MCと活性炭とが 分離しにくいので耐久性に優れ、キヤ-スター、 ORVR (Onboard Refueling Va por Recovery：給油中に排出されるガソリン蒸気の回収装置)などの用途に好まし く使用される。 [0013] According to the present invention, MC in which a substance that absorbs and releases heat due to phase change is encapsulated is mixed with a liquid mixed type resin composed of aqueous emulsion (A) and crosslinkable liquid resin (B) with water. Diluted It is possible to provide MC-added coal adsorbed on activated carbon using an aqueous composition as a binder, a method for producing the same, and a canister using MC-added coal. When the MC-impregnated coal of the present invention is used as a transpiration fuel gas adsorbent, the heat generation and heat absorption that accompanies the absorption and desorption of the transpiration fuel gas can be managed efficiently, so the performance as a transpiration fuel gas adsorbent In addition, the MC-impregnated coal of the present invention is excellent in durability because MC and activated carbon are difficult to separate, and canister, ORVR (Onboard Refueling Vapor Recovery: gasoline discharged during refueling) It is preferably used for applications such as steam recovery equipment.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 本発明において、 MCを添着するための担体となる活性炭の原料としてはとくに限 定されず、賦活して活性炭を形成する炭素質材料であればよい。このような炭素質材 料は、植物系、鉱物系、天然素材及び合成素材など力も広く選択することができる。 具体的には、植物系の炭素質材料として、木材、木炭、ヤシ殻などの果実殻、鉱物 系の炭素質材料として、石炭、石油系及び Z又は石炭系ピッチ、コータス、天然素材 として、木綿、麻などの天然繊維、レーヨン、ビスコースレーヨンなどの再生繊維、ァ セテート、トリアセテートなどの半合成繊維、合成素材として、ナイロンなどのポリアミド 系、ビニロンなどのポリビュルアルコール系、アクリルなどのポリアクリロニトリル系、ポ リエチレン、ポリプロピレンなどのポリオレフイン系、ポリウレタン、フエノール系榭脂、 塩ィ匕ビュル系榭脂などを挙げることができる。なかでも、 MCを添着しやすい点で石 炭が好ましい。 [0014] In the present invention, the raw material of activated carbon that becomes a carrier for attaching MC is not particularly limited, and any carbonaceous material that can be activated to form activated carbon may be used. Such carbonaceous materials can be widely selected from plant-based, mineral-based, natural and synthetic materials. Specifically, as plant-based carbonaceous materials, fruit shells such as wood, charcoal, and coconut shells, as mineral-based carbonaceous materials, as coal, petroleum-based and Z or coal-based pitch, coatas, and natural materials as cotton Natural fibers such as hemp, regenerated fibers such as rayon and viscose rayon, semi-synthetic fibers such as acetate and triacetate, and polyamides such as nylon, polybulal alcohols such as vinylon, and polyacrylonitrile such as acrylic And polyolefins such as polyethylene, polypropylene, and polypropylene, polyurethane, phenolic resin, and salt-based resinous resin. Of these, charcoal is preferred because it is easy to attach MC.
[0015] 炭素質材料及び該炭素質材料を賦活して得られる活性炭の形状はとくに限定され るものではなぐ粒状、粉状、繊維状、シート状など種々の形状のものを使用すること ができる。繊維状又はシート状の炭素質材料としては、木綿などの天然セルロース繊 維、ビスコースレーヨン、ポリノジックレーヨンなどの再生セルロース繊維、パルプ繊維 、ポリビュルアルコール繊維、エチレンビュルアルコール繊維、フヱノール繊維などの 合成繊維などの織布又は不織布、フィルム、フェルト、シート状物を例示することがで きる。  [0015] The shape of the carbonaceous material and the activated carbon obtained by activating the carbonaceous material is not particularly limited, and various shapes such as granular, powdery, fibrous, and sheet-like can be used. . As the fibrous or sheet-like carbonaceous material, natural cellulose fibers such as cotton, regenerated cellulose fibers such as viscose rayon and polynosic rayon, synthetic fibers such as pulp fibers, polybutanol alcohol fibers, ethylene butanol alcohol fibers and phenol fibers. Examples thereof include woven or non-woven fabrics such as fibers, films, felts, and sheet-like materials.
[0016] 炭素質材料は炭化、賦活されて活性炭となるが、炭化条件としては、例えば回分式 ロータリーキルンに少量の不活性ガスを流しながら 300°C以上で処理するなどの条 件を採用することができる。賦活方法としては、ガス賦活、薬剤賦活など如何なる賦 活方法を使用しても構わない。ガス賦活による方法において使用するガスとしては、 水蒸気、炭酸ガス、酸素、 LPG燃焼排ガス、又はこれらの混合ガスなどを挙げること ができる。これらの賦活温度は、通常 300°C〜1200°C、好ましくは 900°Cまで昇温 すること〖こよって実施される。 [0016] The carbonaceous material is carbonized and activated to become activated carbon. Conditions such as processing at 300 ° C or higher while flowing a small amount of inert gas through the rotary kiln can be adopted. As the activation method, any activation method such as gas activation or drug activation may be used. Examples of the gas used in the gas activation method include water vapor, carbon dioxide gas, oxygen, LPG combustion exhaust gas, or a mixed gas thereof. These activation temperatures are usually carried out by raising the temperature to 300 ° C to 1200 ° C, preferably 900 ° C.
[0017] 薬剤賦活による方法において使用される薬剤としては、硫酸、燐酸、硝酸などの酸 、水酸化ナトリウム、水酸ィ匕カリウム、水酸ィ匕セシウム、水酸ィ匕カルシウム、水酸化マ グネシゥムなどの金属水酸ィ匕物、塩ィ匕カルシウム、塩ィ匕亜鉛などの金属塩ィ匕物など を挙げることができる。これらの賦活温度としては、使用する薬剤にもよるが、通常、 3 00°C〜800°Cの範囲で実施される。  [0017] Drugs used in the method of drug activation include acids such as sulfuric acid, phosphoric acid, nitric acid, sodium hydroxide, potassium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, magnesium hydroxide Examples thereof include metal hydroxides such as salts of metal hydroxides such as salts of calcium and salts of zinc. These activation temperatures are usually in the range of 300 ° C. to 800 ° C., although depending on the drug used.
[0018] 活性炭としては、同一種類の活性炭を単独で使用してもよぐ異なる種類の活性炭 を混合して使用してもよい。活性炭の表面には潜熱蓄熱体を封入した MCが、水性 ェマルジヨン (A)と、架橋性の液状榭脂 (B)からなる液混合型榭脂を水で希釈した水 性組成物により添着されるが、粒状の活性炭を用いる場合、活性炭の平均粒径は 0. 5〜5mmであることが好まし!/、。  [0018] As the activated carbon, the same type of activated carbon may be used alone, or different types of activated carbon may be mixed and used. MC on which the latent heat storage material is sealed is attached to the surface of the activated carbon with a water-based composition obtained by diluting a liquid-mixed resin consisting of an aqueous emulsion (A) and a crosslinkable liquid resin (B) with water. However, when granular activated carbon is used, the average particle size of the activated carbon is preferably 0.5-5 mm! /.
[0019] MCが活性炭に均一に添着されるためには成型した活性炭を用いるのが好ましい 。このような成型活性炭を得るには、公知の方法を採用することができ、例えば粉末 活性炭 100重量部に、ピッチ、コールタールなどの粘結剤 30〜35重量部を配合し 混合した混合物をペレツターなどで、例えば直径 2. 5〜4mm、長さ 5〜8mm程度の 円柱状に押出し成型すればよい。具体的には、クラレケミカル株式会社製の商品名 3 GXが好適である。  [0019] In order to uniformly attach MC to activated carbon, it is preferable to use molded activated carbon. In order to obtain such a molded activated carbon, a known method can be employed. For example, 100 parts by weight of powdered activated carbon is mixed with 30 to 35 parts by weight of a binder such as pitch and coal tar, and a mixture is mixed with a pelleter. For example, it may be extruded into a cylindrical shape having a diameter of about 2.5 to 4 mm and a length of about 5 to 8 mm. Specifically, trade name 3 GX manufactured by Kuraray Chemical Co., Ltd. is suitable.
[0020] 潜熱蓄熱体を封入するための MCは公知の物を使用すればよいが、潜熱蓄熱体が 溶融温度に達したときに容易に漏れ出さないものを使用すべきことは勿論である。潜 熱蓄熱体が封入された MCとしては、例えば前記特許文献 2に開示された方法により 得られる MCや三木理研工業株式会社から販売されて 、る MCなどが使用可能であ るが、その他蓄熱材を高分子膜材料で MC化したものや、ポリオレフイン等に有機系 潜熱蓄熱体を吸収させ表面を榭脂コートした蓄熱カプセルも使用可能である。 MC の平均粒子径としては 0. 1〜500 mが好ましい。 [0020] A known MC may be used as the MC for enclosing the latent heat storage body, but it should be understood that a MC that does not easily leak when the latent heat storage body reaches the melting temperature should be used. For example, MC obtained by the method disclosed in Patent Document 2 or MC sold by Miki Riken Kogyo Co., Ltd. can be used as the MC in which the latent heat storage body is enclosed. It is also possible to use a material made of MC with a polymer film material, or a heat storage capsule in which an organic latent heat storage material is absorbed in polyolefin or the like and the surface is coated with a resin. MC The average particle size is preferably from 0.1 to 500 m.
[0021] MCには、相変化により熱の吸収及び放出を生じる物質 (以下、潜熱蓄熱体というこ とがある）が封入されるが、潜熱蓄熱体としては、 10°C〜100°C、より好ましくは 20 °C〜70°Cで相変化する有機化合物を使用するのがエネルギー効率の点から好まし い。このような有機化合物としてはデカン、ドデカン、テトラデカン、ペンタデカン、へ キサデカン、ォクタデカン、エイコサン、ノ ラフィンなどの炭化水素化合物、ラウリルァ ノレコーノレ、ミリスチノレアノレコーノレ、セチノレアノレコーノレ、ステアリノレアノレコーノレ、エイコサ ノール、セリルアルコールなどの高級アルコール、ラウリン酸、ミリスチン酸、ステアリン 酸、ォレイン酸、ベヘン酸などの高級脂肪酸やこのグリセリド、プロピオンアミドなどの アミド類、 PEG400、 PEG600、 PEG1000、 PEG2000、 PEG4000、 PEG6000な どのポリエチレングリコール類、フエノールなどのフエノール類、これらの混合物等を ί列示することができる。 [0021] MC encloses a substance that absorbs and releases heat due to phase change (hereinafter sometimes referred to as a latent heat storage body), and the latent heat storage body has a temperature of 10 ° C to 100 ° C. More preferably, from the viewpoint of energy efficiency, it is preferable to use an organic compound that undergoes a phase change at 20 ° C to 70 ° C. Examples of such organic compounds include hydrocarbon compounds such as decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, eicosane, and norafine, lauryla norconole, myristinolenolenole, cetinoleanorenorenole, stearinorenoleolecole. Nore, higher alcohols such as eicosanol and seryl alcohol, higher fatty acids such as lauric acid, myristic acid, stearic acid, oleic acid and behenic acid, glycerides, amides such as propionamide, PEG400, PEG600, PEG1000, PEG2000, PEG4000 Polyethylene glycols such as PEG6000, phenols such as phenol, and mixtures thereof can be displayed.
[0022] 潜熱蓄熱体の過冷却現象を防止するため、その蓄熱体の融点よりも高い融点を有 する化合物を蓄熱体に含有させてもよ!、。このような高融点化合物の含有割合は、 蓄熱体に対して 0. 5〜30重量％とするのが好ましぐ 1〜15重量％とするのがさらに 好ましい。高融点化合物としては、例えば脂肪族炭化水素化合物、芳香族化合物、 エステル類、カルボン酸類、アルコール類、アミド類などを挙げることができる。  [0022] In order to prevent the supercooling phenomenon of the latent heat storage body, the heat storage body may contain a compound having a melting point higher than that of the heat storage body! The content of such a high melting point compound is preferably 0.5 to 30% by weight, more preferably 1 to 15% by weight with respect to the heat storage body. Examples of the high melting point compound include aliphatic hydrocarbon compounds, aromatic compounds, esters, carboxylic acids, alcohols, amides and the like.
[0023] さらに潜熱蓄熱体と高融点化合物との組み合わせの具体例を示すと、例えば潜熱 蓄熱体としてォクタデカンを用いた場合、高融点化合物としてセチルアルコール、ス テアリルアルコール、エイコサノール、ミリスチン酸、ベヘン酸、ステアリン酸アミドを含 有させるとよい。これらの高融点化合物は 2種類以上組み合わせて使用しても構わな い。  [0023] Further, specific examples of the combination of the latent heat storage body and the high melting point compound are shown. For example, when octadecane is used as the latent heat storage body, the high melting point compound is cetyl alcohol, stearyl alcohol, eicosanol, myristic acid, behen. Acid and stearamide may be included. Two or more of these high melting point compounds may be used in combination.
[0024] 潜熱蓄熱体の過冷却現象を防止するために含有させてもよ!、上記以外の物質とし ては、タルク、シリカ、二酸化チタン、珪酸カルシウム、三酸ィ匕アンチモン等の無機化 合物の微粒子、ステアリン酸マグネシウムや安息香酸ナトリウム等の有機酸塩の微粒 子等を例示することができる。潜熱蓄熱体としてポリエチレングリコール類を用いた場 合は特に降温結晶化温度の低下が著しいため、結晶化促進のためこれら過冷却現 象を防止する物質を添加することが好まし 、。 [0025] 実用上充分な熱量を吸収、放出する必要性から、潜熱蓄熱体を封入した MCの潜 熱は 50mjZmg以上が好ましぐ lOOmiZmg以上がさらに好ましい。ここでいう潜熱 とは潜熱蓄熱体を封入した MC全体の見かけ上の潜熱をいい、示差走査熱量計によ り容易に測定することができる。 [0024] It may be contained to prevent the supercooling phenomenon of the latent heat storage body! As materials other than the above, inorganic compounds such as talc, silica, titanium dioxide, calcium silicate, and antimony trioxide are used. And fine particles of organic acid salts such as magnesium stearate and sodium benzoate. When polyethylene glycols are used as the latent heat storage material, the temperature drop crystallization temperature is particularly low, so it is preferable to add substances that prevent these supercooling phenomena to promote crystallization. [0025] In view of the necessity of absorbing and releasing a sufficient amount of heat for practical use, the latent heat of MC enclosing a latent heat accumulator is preferably 50 mjZmg or more, more preferably lOOmiZmg or more. The latent heat here refers to the apparent latent heat of the entire MC enclosing the latent heat accumulator, and can be easily measured with a differential scanning calorimeter.
[0026] キヤ-スターに用いるための MC添着炭に使用される結合剤としては、活性炭の微 細孔を閉塞せずに、強固な接着効果を少量で発揮できることが重要であり、本発明 における最大の特徴は、活性炭表面に MCを担持させるために、水を蒸発させた後 に皮膜状になって接着性を発現する水性ェマルジヨン (A)と架橋性の液状榭脂 (B) 力もなる液混合型榭脂を水で希釈した水性組成物を結合剤として使用したことにある  [0026] As a binder used in MC-added carbon for use in a caster, it is important that a strong adhesive effect can be exhibited in a small amount without blocking fine pores of activated carbon. The biggest feature is that the aqueous activated carbon (A) that forms a film after water is evaporated and develops adhesive properties to support MC on the activated carbon surface (B) and a liquid that can also be crosslinked (B) An aqueous composition obtained by diluting mixed type rosin with water is used as a binder.
[0027] 本発明において、通常は接着剤として使用される液混合型の榭脂を水で希釈した 水性組成物を結合剤として使用することにより、 MCを活性炭表面に強固に添着する ことができ、蒸散燃料ガス吸着材としてキヤニスターに使用したときでも振動により活 性炭から MCが脱落せず、耐久性に優れた蒸散燃料ガス吸着材とすることができるこ とは全く意外であり、驚くべき効果である。以下、水を蒸発させた後に皮膜状になって 接着性を発現する水性ェマルジヨン (A)を主剤、架橋性の液状榭脂 (B)を副剤と!/ヽ うことがある。本発明で使用する液混合型の榭脂は、このような主剤 (A)と副剤 (B)か らなっており、主剤としてはアクリル系又はポリウレタン系の榭脂を使用するのが好ま しい。これらは混合して使用してちょい。 [0027] In the present invention, MC can be firmly attached to the activated carbon surface by using, as a binder, an aqueous composition obtained by diluting a liquid-mixed type of resin usually used as an adhesive with water. Even when used as a transpiration fuel gas adsorbent in a canister, MC does not fall off from activated charcoal due to vibration, and it is quite surprising and surprising that a transpiration fuel gas adsorbent with excellent durability can be obtained. It is an effect. Hereinafter, the aqueous emulsion (A), which forms a film after water is evaporated and exhibits adhesiveness, may be referred to as the main agent, and the crosslinkable liquid resin (B) may be referred to as the auxiliary agent. The liquid-mixed type of resin used in the present invention comprises such a main agent (A) and an auxiliary agent (B), and it is preferable to use acrylic or polyurethane-based resin as the main agent. . Use a mixture of these.
[0028] 副剤 (B)としては、接着性向上剤として機能する反応性の官能基を有する架橋剤 を含有する榭脂を使用するのが好ましい。反応性の官能基としては、該反応性の官 能基が、イソシァネート基、ブロックイソシァネート基、エポキシ基、ォキサゾリン基、力 ルボジイミド基、アジリジン基、カルボ-ル基、ヒドラジド基力 なる群より選ばれる少 なくとも 1種の官能基であるのが好ましぐなかでもイソシァネート基又はエポキシ基が 好ましい。これらは混合物で使用してもよい。液混合型榭脂の使用割合は、固形分 比率として主剤 70〜95重量％、副剤 5〜30重量％で使用するのが好ましいが、これ らの使用量は極力少量に止めるのがよい。ここで言う固形分割合とは、主剤及び副 剤の固形分の合計を分母としたとき、主剤又は副剤の固形分を分子として重量％で 表した主剤又は副剤の比率である。 [0028] As the auxiliary agent (B), it is preferable to use a resin containing a crosslinking agent having a reactive functional group that functions as an adhesion improver. As the reactive functional group, the reactive functional group is selected from the group consisting of an isocyanate group, a block isocyanate group, an epoxy group, an oxazoline group, a carbodiimide group, an aziridine group, a carbonyl group, and a hydrazide group. Of these, an isocyanate group or an epoxy group is preferred, although at least one selected functional group is preferred. These may be used in a mixture. It is preferable to use the liquid-mixed coagulant at a solid content ratio of 70 to 95% by weight of the main agent and 5 to 30% by weight of the auxiliary agent, but it is recommended that these amounts be kept as small as possible. The solid content ratio here refers to the percentage by weight with the solid content of the main agent or auxiliary agent as the numerator when the total solid content of the main agent and auxiliary agent is used as the denominator. It is the ratio of the main agent or auxiliary agent represented.
[0029] 本発明の MC添着炭において、 MCの含有量は、あまり少ないと蓄熱能力が十分 ではなぐまたあまり多いと活性炭量が不十分であるので、活性炭 100重量部に対し て 5〜65重量部とするのが好まし!/、。  [0029] In the MC impregnated coal of the present invention, if the content of MC is too small, the heat storage capacity is not sufficient, and if it is too large, the amount of activated carbon is insufficient, so 5 to 65 weights with respect to 100 parts by weight of activated carbon. It ’s better to be a part! /
[0030] さらに、蒸散燃料ガス吸着時の発熱や脱着時の吸熱を抑え、吸脱着性能を向上さ せるためには MC添着炭の見かけ上の潜熱が 7mjZmg以上が好ましぐ 15mj/m g以上がより好ましぐ 30miZmg以上がさらに好ましい。  [0030] Further, in order to suppress heat generation during transpiration fuel gas adsorption and heat absorption during desorption, and improve adsorption and desorption performance, the apparent latent heat of MC-added coal is preferably 7mjZmg or more, and 15mj / mg or more is preferred. More preferred is 30 miZmg or more.
[0031] 次に MC添着炭の好ま 、製造方法につ!、て述べる。先ず、 MCを分散媒に投入 しょく攪拌し分散させる (混合液 1)。分散媒としては、水、アルコール、アセトンなどの 炭化水素類が使用されるが、取扱い性、安全性の点で水が好ましい。分散媒はあま り多いと分散媒を除去する手間がかかり、あまり少ないと分散性がよくないので、活性 炭 100重量部に対して 50〜65重量部程度の分散媒を使用するのが好ましい。  [0031] Next, the preferred method for producing MC-impregnated coal will be described. First, MC is put into a dispersion medium and dispersed by stirring (mixed solution 1). As the dispersion medium, hydrocarbons such as water, alcohol, and acetone are used, but water is preferable from the viewpoint of handleability and safety. If the dispersion medium is too much, it takes time to remove the dispersion medium, and if it is too small, the dispersibility is not good. Therefore, it is preferable to use about 50 to 65 parts by weight of the dispersion medium with respect to 100 parts by weight of the activated carbon.
[0032] 次 ヽで混合液 1に、主剤 (A)と副剤 (B)カゝらなる液混合型榭脂を水で希釈した水性 組成物を添加し、 MCが凝集しないように攪拌して混合する (混合液 2)。活性炭を混 合液 2に、又は混合液 2を活性炭に添加混合し、実質的に水分が認められなくなるま で充分攪拌した後乾燥し、本発明の MC添着炭を製造することができる。 MCに水性 組成物を添加し混合物を調製する際、 MCが凝集しな ヽように高速攪拌するのが好 ましい。混合液 2の活性炭に対する配合割合は、活性炭 100重量部に対し、 MC〖こ 水性組成物を添加したものを固形分として 5〜70重量部で実施するのが好ましい。 乾燥条件はとくに限定されるものではないが、通常、温度 80〜120°Cで 12〜24時 間程度で実施される。  [0032] Next, an aqueous composition obtained by diluting the liquid mixture type resin consisting of the main agent (A) and the auxiliary agent (B) with water is added to the mixed solution 1 and stirred so that MC does not aggregate. And mix (mixture 2). The MC-added coal of the present invention can be produced by adding activated carbon to the mixed solution 2 or mixing and mixing the mixed solution 2 with the activated carbon, stirring sufficiently until water is substantially not observed, and drying. When preparing a mixture by adding an aqueous composition to MC, it is preferable to stir at high speed so that MC does not aggregate. The mixing ratio of the mixed liquid 2 with respect to the activated carbon is preferably 5 to 70 parts by weight based on 100 parts by weight of the activated carbon with the MC coconut water-based composition added as a solid content. The drying conditions are not particularly limited, but are usually carried out at a temperature of 80 to 120 ° C for about 12 to 24 hours.
[0033] 本発明の MC添着炭によれば、蒸散燃料ガスの吸脱着に伴って生じる発熱及び吸 熱を効率的に管理することができるので蒸散燃料ガス吸着材としての性能を高度に 保持することが可能となる。また、 MCと活性炭が分離しにくいので耐久性に優れた 蒸散燃料ガス吸着材としてキヤニスターなどの用途に好ましく使用される。  [0033] According to the MC-impregnated coal of the present invention, it is possible to efficiently manage the heat generation and heat absorption caused by the adsorption and desorption of the vaporized fuel gas, so that the performance as the vaporized fuel gas adsorbent is highly maintained. It becomes possible. In addition, since MC and activated carbon are difficult to separate, it is preferably used in applications such as canisters as a vaporized fuel gas adsorbent with excellent durability.
[0034] 以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらに限定さ れるものではない。なお、潜熱蓄熱体の融点、融解熱、降温結晶化温度、結晶化熱 はセイコーインスツルメンッ株式会社製の示差走査熱量計（EXSTAR6000 RDC 220U)で昇温速度、降温速度とも 5°CZ分で測定した。潜熱は融解熱と結晶化熱の 平均値で表示した。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. The melting point, melting heat, temperature drop crystallization temperature, and crystallization heat of the latent heat accumulator are the differential scanning calorimeter (EXSTAR6000 RDC manufactured by Seiko Instruments Inc.). In 220U), the temperature increase rate and temperature decrease rate were measured at 5 ° CZ minutes. The latent heat was expressed as the average value of heat of fusion and heat of crystallization.
[0035] 実施例 1 [0035] Example 1
MCの調製：  MC preparation:
国際公開 WO 03/106833 A1公報の実施例 1に準じて、メラミン粉末 5gに 37 %ホルムアルデヒド水溶液 6. 5gと水 10gを加え、 pHを 8に調整した後、約 70°Cまで 加熱しメラミン—ホルムアルデヒド初期縮合物水溶液を得た。 pHを 4. 5に調整したス チレン無水酸共重合体のナトリウム塩水溶液 100g中に相変化を伴う化合物として n —ォクタデカン 70gを溶解した液を上記水溶液に激しく攪拌しながら添加し、粒子径 が約 1. 3 mになるまで乳化を行った。得られた乳化液に上記メラミン ホルムアル デヒド水溶液を全量添加し、 70°Cで 2時間攪拌を行った後、 pHを 9に調整しカプセ ル化を行った。反応終了後、カプセルを吸引ろ過し、乾燥すること〖こより約 2 mの粒 径を有する MCを得た。この時得られた MCの潜熱は 195mjZmgであった。  According to Example 1 of International Publication WO 03/106833 A1, 37 g of formaldehyde aqueous solution 6.5 g and 10 g of water were added to 5 g of melamine powder, pH was adjusted to 8, and the mixture was heated to about 70 ° C. A formaldehyde precondensate aqueous solution was obtained. A solution prepared by dissolving 70 g of n-octadecane as a compound with phase change in 100 g of a sodium salt aqueous solution of styrene anhydride copolymer adjusted to pH 4.5 was added to the above aqueous solution with vigorous stirring, and the particle size was reduced. Emulsification was carried out to about 1.3 m. The whole amount of the above melamine formaldehyde aqueous solution was added to the obtained emulsion and stirred at 70 ° C. for 2 hours, and then the pH was adjusted to 9 to effect encapsulation. After completion of the reaction, the capsule was suction filtered and dried to obtain MC having a particle size of about 2 m. The latent heat of MC obtained at this time was 195mjZmg.
[0036] MC添着炭の作製：  [0036] Production of MC-impregnated charcoal:
上記 MC41gを 118gの水に分散させ、主剤として日本カーノイド工業株式会社ァ クリル系ェマルジヨン-力ゾール FX—672 (固形分 50%) 4. 7gと、副剤 1として固形 分が 10%となるよう水で希釈した日本ポリウレタン工業株式会社製ポリイソシァネート AQ210を 4. 7g及び副剤 2として固形分が 10%となるように水で希釈したナガセケム テックス株式会社製エポキシィ匕合物デナコール EX— 614を 2. 4gカ卩えてよく攪拌し た。この時、主剤：副剤の固形分割合は、重量比で 76. 8 : 23. 2であり、 MC100重 量部に対する混合型榭脂の固形分比率は 7. 5重量部であった。  MC41g above is dispersed in 118g of water, and Nippon Carnoid Industry Co., Ltd., Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 4.7g, and secondary agent 1 solid content 10% 4.7g of Polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water and Epoxy compound Denacor EX-614 manufactured by Nagase ChemteX Corporation diluted with water to a solid content of 10% as secondary agent 2. 2.4 g was added and stirred well. At this time, the ratio of the solid content of the main agent: secondary agent was 76.8: 23.2 by weight, and the solid content ratio of the mixed resin to 100 parts by weight of MC was 7.5 parts by weight.
[0037] 得られた混合液 170. 8gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 32mJ Zmgであった。得られた MC添着炭の断面写真 (倍率 200倍)を図 1に示す。図 1に おいて、 1は活性炭、 2は添着された MCである。 [0038] 脱落微粉量の測定： [0037] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 170.8 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed. The resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 32 mJ Zmg. Figure 1 shows a cross-sectional photograph (magnification 200 times) of the obtained MC-impregnated coal. In Fig. 1, 1 is activated carbon and 2 is MC attached. [0038] Measurement of the amount of fine powder falling off:
300mL分液ロートに上記 MC添着炭 50gを入れ、ァズワン株式会社製万能シエー カー AS— 1Nにセットし、上下振とう 300回 Z分で 30分間振とう後、 MC添着炭を取 り出し、分液ロート内を 20mLの n—へキサンで洗浄し、更に取り出した MC添着炭を 150mLの n—へキサンで 3回洗浄した後、溶剤を蒸発させて脱落した微粉量 Wl (g) を測定し、次式より MC添着炭 lg当たりの脱落微粉量 Wを求めたところ 1. 7mg/g であった。  Place 50g of the above MC-impregnated coal into a 300mL separatory funnel, set it on the all-purpose shaker AS-1N manufactured by AZONE CO., LTD. The inside of the liquid funnel was washed with 20 mL of n-hexane, and the taken MC-impregnated coal was washed with 150 mL of n-hexane three times, and then the amount of fine powder Wl (g) dropped off by evaporation of the solvent was measured. Based on the following formula, the amount of fine powder fallen out per lg MC-added coal was determined to be 1.7 mg / g.
W= (Wl/50) X 1000  W = (Wl / 50) X 1000
[0039] 蒸散燃料ガス吸着材の性能評価：  [0039] Performance evaluation of transpiration fuel gas adsorbent:
図 2は MC添着炭の性能を見るために使用したキヤ-スターである。図 2において、 3はキヤニスター、 4はパージ空気口、 5は金網などの分散板、 6は MC添着炭、 7は n —ブタン供給口、 8は温度計、 9は断熱材である。  Figure 2 shows the caster used to see the performance of MC-impregnated coal. In Fig. 2, 3 is a canister, 4 is a purge air port, 5 is a dispersion plate such as a wire mesh, 6 is MC-added charcoal, 7 is an n-butane supply port, 8 is a thermometer, and 9 is a heat insulating material.
[0040] 図 2に示すような 63mm角、高さ 300mm (有効充填高さ 252mm)、充填容積 100 OmLのポリ塩化ビュル製キヤ-スターに、得られた MC添着炭 lOOOmL相当分 360 gを充填し、 25°Cで 99%の n—ブタンを 1リットル (L)Z分でアップフローにて供給し て MC添着炭に吸着させ、出口の n—ブタン濃度が 3000ppmに達した時点で停止 した。  [0040] A 63mm sq., 300mm high (effective filling height 252mm), polychlorinated bule caster with a filling volume of 100 OmL as shown in Fig. 2 is filled with 360 g equivalent of the obtained MC-impregnated coal lOOOOmL. Then, 99% of n-butane was supplied at 25 ° C in an up-flow of 1 liter (L) Z, adsorbed on MC-impregnated coal, and stopped when the outlet n-butane concentration reached 3000 ppm. .
[0041] 次いで、室温の空気を 15LZ分で 20分ダウンフローにて流し、 n—ブタンを脱着さ せた。この吸脱着操作を繰り返し 10回行い、 10回目のキヤ-スター内の最高温度及 び最低温度を計測した結果、最高温度 58°C、最低温度 12. 5°Cであった。同様にク ラレケミカル株式会社製の石炭系活性炭 3GXを lOOOmL相当分 350gのみを充填し たところ、最高温度 64°C、最低温度 6°Cであったことから、 MC添着炭によりキヤニス ター内の温度変化が抑制されていることは明らかである。  [0041] Next, n-butane was desorbed by flowing air at room temperature at a flow rate of 15 LZ for 20 minutes. This adsorption / desorption operation was repeated 10 times, and the maximum temperature and the minimum temperature in the tenth caster were measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 12.5 ° C. Similarly, 350g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was filled with only 350g equivalent of lOOOOmL, and the maximum temperature was 64 ° C and the minimum temperature was 6 ° C. It is clear that the change is suppressed.
[0042] 実施例 2  [0042] Example 2
実施例 1と同様にして MCを作製し、該 MC35. 3gを 118gの水に分散させ、主剤と して日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672(固形 分 50%)4. 7gと、副剤 1として固形分 10%となるように水で希釈した日本ポリウレタン 工業株式会社製ポリイソシァネート AQ210を 0. 9g及び副剤 2として固形分 10%と なるように水で希釈したナガセケムテックス株式会社製エポキシ化合物デナコール E X— 614を 0. 5g加えてよく攪拌した。この時、主剤：副剤の固形分割合は、重量比で 94. 4 : 5. 6であり、 MC100重量部に対する混合型榭脂の固形分比率は 7. 1重量 部であった。 MC was prepared in the same manner as in Example 1, and 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) 4. 9 g of polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent 1 and 10% solid content as an auxiliary agent 2 0.5 g of epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 94.4: 5.6 in weight ratio, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 7.1 parts by weight.
[0043] 得られた混合液 159. 4gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 29mJ / mgであった。  [0043] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 49.4 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 29 mJ / mg.
[0044] 実施例 1と同様に脱落微粉量を求めたところ 1. 9mgZgであった。実施例 1と同様 に lOOOmL相当分 355gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 58°C、最低温度 13°Cであり、キヤニスター内の温度変化が抑制さ れていることは明らかである。  [0044] The amount of fine powder falling off was determined in the same manner as in Example 1, and found to be 1.9 mgZg. As in Example 1, 355 g of lOOOOmL equivalent was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 13 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
[0045] 実施例 3  [0045] Example 3
カプセル力 Sメラミン榭脂である MC三木理研工業株式会社製 PMDC— 32SP (粒 径 10 m、 MC潜熱 50miZmg) 35. 3gを 118gの水に分散させ、主剤として日本力 一バイドエ業株式会社アクリル系ェマルジヨン-力ゾール FX— 672 (固形分 50%) 9 . 4gと、副剤 1として固形分が 10%となるよう水で希釈した日本ポリウレタン工業株式 会社製ポリイソシァネート AQ210を 9. 4g及び副剤 2として固形分が 10%となるよう 水で希釈したナガセケムテックス株式会社製エポキシィ匕合物デナコール EX— 614を 4. 7g加えてよく攪拌した。この時、主剤：副剤の固形分割合は、重量比で 76. 9 : 23 . 18であり、 MC100重量部に対する混合型榭脂の固形分比率は 17. 3重量部であ つた o  Capsule strength S Melamine sachet MCDC manufactured by MC Miki Riken Kogyo Co., Ltd. PMDC 32SP (particle size 10 m, MC latent heat 50 miZmg) 35. 3 g is dispersed in 118 g of water. Emargillon-Rikizor FX— 672 (solid content 50%) 9.4 g and 9.4 g of polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent 1. 4.7 g of the epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water so as to have a solid content of 10% as an adjunct 2 was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 76.9: 23.18 by weight, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 17.3 parts by weight.
[0046] 得られた混合液 176. 8gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 7. 3m JZ mgで 3Dつ 7こ [0046] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 176. 8 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. Repeat the above operation 3 times, 120 After drying at ° C for 14 hours, MC-impregnated coal was obtained. The latent heat of the MC-impregnated coal obtained at this time is 7 m at 7.3 m JZ mg.
[0047] 実施例 1と同様に脱落微粉量を求めたところ 1. 3mgZgであった。実施例 1と同様 に lOOOmL分 353gをキヤ-スターに充填し、キヤ-スター内の温度を測定したところ 、最高温度 60°C、最低温度 8°Cであり、キヤニスター内の温度変化が抑制されている ことは明らかである。  [0047] When the amount of fine powder falling off was determined in the same manner as in Example 1, it was 1.3 mgZg. As in Example 1, 353 g of lOOOOmL was charged into a canister and the temperature in the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 8 ° C, and the temperature change in the canister was suppressed. Obviously.
[0048] 実施例 4  [0048] Example 4
カプセル力 Sメラミン榭脂である MC三木理研工業株式会社製 PMDC— 32SP (粒 径 10 m、 MC潜熱 50miZmg) 35. 3gを 118gの水に分散させ、主剤として株式 会社クラレ製ポリウレタンェマルジヨン KMN—NOc (固形分 40%) 9. 6gと、副剤 1と して固形分が 10%となるよう水で希釈した日本ポリウレタン工業株式会社製ポリイソ シァネート AQ210を 4. 8g及び副剤 2として固形分が 10%となるよう水で希釈したナ ガセケムテックス株式会社製エポキシ化合物デナコール EX— 614を 2. 4g加えてよ く攪拌した。この時、主剤：副剤の固形分割合は、重量比で 84. 2 : 15. 8であった。 MC 100重量部に対する混合型榭脂の固形分比率は 12. 9重量部であった。  Capsule strength S Melamine resin PMDC manufactured by MC Miki Riken Kogyo Co., Ltd. 32SP (particle size 10 m, MC latent heat 50 miZmg) 35. Disperse 3 g in 118 g water and use Kuraray Co., Ltd. polyurethane emulsion KMN —NOc (solid content 40%) 9.6 g and 4.8 g of polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water so that the solid content is 10% as secondary agent 1 and solid as secondary agent 2 2.4 g of the epoxy compound Denacol EX-614, manufactured by Nagase ChemteX Corporation, diluted with water to a 10% content, was added and stirred well. At this time, the solid content ratio of the main agent to the auxiliary agent was 84.2: 15.8 in weight ratio. The solid content ratio of the mixed type resin to 100 parts by weight of MC was 12.9 parts by weight.
[0049] 得られた混合液 170. lgにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 2回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 7. 3m JZ mgで 3Dつ 7こ [0049] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 170. lg of the obtained mixed liquid, and vigorously stirred until no surface moisture was observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time is 7 m at 7.3 m JZ mg.
[0050] 実施例 1と同様に脱落微粉量を求めたところ 1. 9mgZgであった。実施例 1と同様 に lOOOmL相当分 35 lgをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 60°C、最低温度 8°Cであり、キヤニスター内の温度変化が抑制され ていることは明らかである。  [0050] The amount of fine powder fallen off as determined in Example 1 was 1.9 mgZg. As in Example 1, 35 lg equivalent to lOOOOmL was filled into a canister, and the temperature in the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 8 ° C. It is clear that it has been suppressed.
[0051] 実施例 5  [0051] Example 5
実施例 1と同様にして MCを作製し、該 MC35. 3gを 118gの水に分散させ、主剤と して日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672 (固形 分 50%) 2. 4gと副剤として固形分が 10%となるよう水で希釈した第一工業製薬製ブ ロックイソシァネートエラストロン BN— 4の 2. 4gをカ卩えてよく攪拌した。この時、主剤： 副剤の固形分割合は、重量比で 83. 3 : 16. 7であり、 MC100重量部に対する混合 型榭脂の固形分比率は 4. 1重量部であった。 MC was prepared in the same manner as in Example 1, 33.5 g of MC3 was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid (50% min.) 2.4 g and 2.4 g of block isocyanate elastolone BN-4 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. diluted with water to a solid content of 10% as an adjunct were added and stirred well. At this time, the solid content ratio of the main agent: the secondary agent was 83.3: 16.7 in weight ratio, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 4.1 parts by weight.
[0052] 得られた混合液 158. lgにクラレケミカル株式会社製の石炭系活性炭 3GX200g をすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固 形物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エア 一ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 12 0°Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 29m JZ mgで 3Dつ 7こ [0052] To 158. lg of the obtained mixed solution, quickly add 3GX200g of coal-based activated carbon manufactured by Kuraray Chemical Co., Ltd., and vigorously stir until no surface moisture is observed. The resulting solid product is JIS standard 4Z7. Sifted into 5 meshes, air was blown for 1 minute at a flow rate of 30 LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time is 3m, 7 pieces at 29m JZ mg.
[0053] 実施例 1と同様に脱落微粉量を求めたところ 1. 8mgZgであった。実施例 1と同様 に lOOOmL相当分 356gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 58°C、最低温度 13°Cであり、キヤニスター内の温度変化が抑制さ れていることは明らかである。  [0053] The amount of fine powder falling off was determined in the same manner as in Example 1, and found to be 1.8 mgZg. As in Example 1, 356 g of lOOOOmL equivalent was filled into a canister, and the temperature in the canister was measured. The maximum temperature was 58 ° C and the minimum temperature was 13 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
[0054] 実施例 6  [0054] Example 6
実施例 1と同様にして MCを作製し、該 MC35. 3gを 118gの水に分散させ、主剤と して日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672 (固形 分 50%) 2. 4gと副剤として固形分が 10%となるよう水で希釈した株式会社日本触媒 製ォキサゾリン基含有水溶性ポリマーェポクロス WS— 700を 2. 4gカ卩えてよく攪拌し た。このとき、主剤：副剤の固形分割合は、重量比で 83. 3 : 16. 7であり、 MCIOO重 量部に対する混合型榭脂の固形分比率は 4. 1重量部であった。  MC was prepared in the same manner as in Example 1, 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) 2. 2.4 g of oxazoline group-containing water-soluble polymer Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 83.3: 16.7 in weight ratio, and the solid content ratio of the mixed resin to MCIOO weight part was 4.1 parts by weight.
[0055] 得られた混合液 158. lgにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 29mJ に lOOOmL相当分 359gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 59°C、最低温度 11°Cであり、キヤニスター内の温度変化が抑制さ れていることは明らかである。 [0055] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 158. lg of the obtained mixed liquid, and vigorously stirred until no surface moisture was observed, and the resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC impregnated coal obtained at this time is 29mJ When the temperature in the canister was measured by filling 359 g of the equivalent of lOOOOmL into the canister, the maximum temperature was 59 ° C and the minimum temperature was 11 ° C, and the temperature change in the canister was suppressed. Is clear.
[0057] 実施例 7 [0057] Example 7
実施例 1と同様にして MCを作製し、該 MC35. 3gを 118gの水に分散させ、主剤と して日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672 (固形 分 50%)を 4. 7gと副剤として固形分が 10%となるよう水で希釈した日清紡株式会社 製カルポジイミド榭脂カルポジライト V— 04の 4. 8gをカ卩えてよく攪拌した。この時、主 剤：副剤の固形分割合は、重量比で 83 : 17であり、 MC100重量部に対する混合型 榭脂の固形分は 8重量部であった。  MC was prepared in the same manner as in Example 1, and 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 4 7 g and 4.8 g of Carposimide Imabsorb Calpolite V-04 manufactured by Nisshinbo Co., Ltd. diluted with water to a solid content of 10% as an auxiliary agent were added and stirred well. At this time, the ratio of the solid content of the main agent to the auxiliary agent was 83:17 in terms of weight ratio, and the solid content of the mixed resin with respect to 100 parts by weight of MC was 8 parts by weight.
[0058] 得られた混合液 162. 8gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 29mJ / mgであった。 [0058] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 162.8 g of the obtained mixed liquid, and the mixture was vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 29 mJ / mg.
[0059] 実施例 1と同様に脱落微粉量を求めたところ 2. OmgZgであった。実施例 1と同様 に lOOOmL相当分 358gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 58°C、最低温度 11°Cであり、キヤニスター内の温度変化が抑制さ れていることは明らかである。  [0059] The amount of fine powder falling off was determined in the same manner as in Example 1, and it was 2. OmgZg. As in Example 1, 358 g of lOOOmL equivalent was filled into a canister and the temperature in the canister was measured. The maximum temperature was 58 ° C and the minimum temperature was 11 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
[0060] 実施例 8  [0060] Example 8
カプセル力 Sメラミン榭脂である MC三木理研工業株式会社製 PMDC— 32SP (粒 径 10 m、 MC潜熱 50miZmg) 35. 3gを 118gの水に分散させ、主剤として株式 会社クラレ製ポリウレタンェマルジヨン KMN—NOc (固形分 40%) 9. 4gと、副剤 1と して固形分が 10%となるよう水で希釈したアジリジン基含有試薬ポリエチレンィミン 4 . 7g及び副剤 2として固形分が 10%となるよう水で希釈したナガセケムテックス株式 会社製エポキシィ匕合物デナコール EX— 614を 4. 7gカ卩えてよく攪拌した。この時、 主剤：副剤の固形分割合は、重量比で 80 : 20であった。 MC100重量部に対する混 合型榭脂の固形分比率は 13. 3重量部であった。 Capsule strength S Melamine resin PMDC manufactured by MC Miki Riken Kogyo Co., Ltd. 32SP (particle size 10 m, MC latent heat 50 miZmg) 35. —NOc (solid content 40%) 9.4 g and 4.7 g of aziridine group-containing reagent polyethyleneimine diluted with water so that the solid content of secondary agent 1 is 10% and 10% of solid content as secondary agent 2 4.7 g of Epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water to a concentration of 4.7% was stirred well. At this time, the solid content ratio of the main agent: the auxiliary agent was 80:20 by weight. MC100 parts by weight The solid content ratio of the composite type resin was 13.3 parts by weight.
[0061] 得られた混合液 172. lgにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 2回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 7. 5m JZ mgで 3Dつ 7こ [0061] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 172. lg of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC impregnated coal obtained at this time is 7.5m JZ mg, 3D 7 pieces.
[0062] 実施例 1と同様に脱落微粉量を求めたところ 1. 8mgZgであった。実施例 1と同様 に lOOOmL相当分 352gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 60°C、最低温度 8°Cであり、キヤニスター内の温度変化が抑制され ていることは明らかである。  [0062] The amount of fine powder falling off was determined in the same manner as in Example 1, and found to be 1.8 mgZg. Similar to Example 1, 352 g equivalent of lOOOOmL was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 8 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
[0063] 実施例 9  [0063] Example 9
実施例 1と同様にして MCを作製し、該 MC35. 3gを 118gの水に分散させ、主剤と して日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672 (固形 分 50%)を 4. 7gと、副剤 1として固形分が 10%となるよう水で希釈したカルボ-ル基 を有する日本酢ビ 'ポバール株式会社製 Dポリマー DF— 17を 9. 4g及び副剤 2とし て 10%に希釈したヒドラジド基を有する試薬アジピン酸ジヒドラジドを 0. 5gカ卩えてよく 攪拌した。この時、主剤：副剤の固形分割合は、重量比で 70. 4 : 29. 6であり、 MC1 00重量部に対する混合型榭脂の固形分比率は 9. 5重量部であった。  MC was prepared in the same manner as in Example 1, and 33.5 g of the MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 4 7.4 g of Nippon Polyvinyl acetate 'Poval Co., Ltd.' D-Polymer DF-17, which has a carboxylic group diluted with water so that the solid content is 10% as secondary agent 1 and 10% as secondary agent 2 0.5 g of adipic acid dihydrazide having a hydrazide group diluted to% was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 70.4: 29.6 in weight ratio, and the solid content ratio of the mixed type resin to 1.00 parts by weight of MC was 9.5 parts by weight.
[0064] 得られた混合液 167. 9gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 29mJ / mgであった。 [0064] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 97.9 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 29 mJ / mg.
[0065] 実施例 1と同様に脱落微粉量を求めたところ 1. 9mgZgであった。実施例 1と同様 に lOOOmL相当分 357gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 58°C、最低温度 11°Cであり、キヤニスター内の温度変化が抑制さ れていることは明らかである。 [0065] The amount of fine powder falling off was determined in the same manner as in Example 1, and it was 1.9 mgZg. Similar to Example 1, 357 g equivalent of lOOOOmL was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 11 ° C, and the temperature change in the canister was suppressed. The It is clear that
[0066] 実施例 10  [0066] Example 10
実施例 1と同様にして MCを作製し、該 MC130gを 118gの水に分散させ、主剤とし て日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672(固形分 50%)を 13. 3gと、副剤 1として固形分 10%となるように水で希釈した日本ポリウレタ ン工業株式会社製ポリイソシァネート AQ210を 13. 3g及び副剤 2として固形分 10% となるように水で希釈したナガセケムテックス株式会社製エポキシィ匕合物デナコール EX— 614を 6. 7g加えてよく攪拌した。この時、主剤：副剤の固形分割合は、重量比 で 76. 9 : 23. 1であり、 MC100重量部に対する混合型榭脂の固形分比率は 6. 5重 量部であった。  MC was prepared in the same manner as in Example 1, 130 g of MC was dispersed in 118 g of water, and Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) was 13.3 g. , 13.3 g of polyisocyanate AQ210 manufactured by Nippon Polyuretan Kogyo Co., Ltd. diluted with water to a solid content of 10% as side agent 1 and diluted with water to a solid content of 10% as side agent 2 6.7 g of Epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 76.9: 23.1 by weight, and the solid content ratio of the mixed resin to 100 parts by weight of MC was 6.5 parts by weight.
[0067] 得られた混合液 281. 3gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 2回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 76mJ / mgであった。  [0067] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 31.8 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed. The resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 76 mJ / mg.
[0068] 実施例 1と同様に脱落微粉量を求めたところ 2. lmgZgであった。実施例 1と同様 に lOOOmL相当分 375gをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 56°C、最低温度 14°Cであり、キヤニスター内の温度変化が抑制さ れていることは明らかである。  [0068] The amount of fine powder falling off was determined in the same manner as in Example 1. The result was 2. lmgZg. Similar to Example 1, 375 g equivalent of lOOOOmL was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 56 ° C and the minimum temperature was 14 ° C, and the temperature change in the canister was suppressed. It is clear that this has been done.
[0069] 実施例 11  [0069] Example 11
実施例 1と同様にして MCを作製し、該 MC10. 4gを 118gの水に分散させ、主剤と して日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672(固形 分 50%)を 2. lgと、副剤 1として固形分 10%となるように水で希釈した日本ポリウレタ ン工業株式会社製ポリイソシァネート AQ210を 2. lg及び副剤 2として固形分 10% となるように水で希釈したナガセケムテックス株式会社製エポキシィ匕合物デナコール EX— 614を 1. lg加えてよく攪拌した。この時、主剤：副剤の固形分割合は、重量比 で 76. 6 : 23. 4であり、 MC100重量部に対する混合型榭脂の固形分比率は 13. 2 重量部であった。 MC was prepared in the same manner as in Example 1, and 10.4 g of the MC was dispersed in 118 g of water. Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strength Sol FX-672 (solid content 50%) 2 lg and polyisocyanate AQ210 manufactured by Nippon Polyuretan Kogyo Co., Ltd. diluted with water to a solid content of 10% as adjunct 1 2. Water to a solid content of 10% as lg and adjunct 2 1. 1 lg of epoxy compound Denacol EX-614, manufactured by Nagase ChemteX Corporation, was added and stirred well. At this time, the ratio of the solid content of the main agent to the auxiliary agent is 76.6: 23.4 by weight, and the solid content ratio of the mixed type resin to 100 parts by weight of MC is 13.2. Part by weight.
[0070] 得られた混合液 133. 7gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 2回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 9. 2m JZ mgで 3Dつ 7こ  [0070] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 133.7 g of the obtained mixed solution, and vigorously stirred until surface moisture was not observed. The resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC impregnated coal obtained at this time is 9.2m JZ mg, 3D 7 pieces.
[0071] 実施例 1と同様に脱落微粉量を求めたところ 0. 9mgZgであった。実施例 1と同様 に lOOOmL相当分 35 lgをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 61°C、最低温度 8°Cであり、キヤニスター内の温度変化が抑制され ていることは明らかである。  [0071] When the amount of fine powder falling off was determined in the same manner as in Example 1, it was 0.9 mgZg. As in Example 1, 35 lg equivalent to lOOOOmL was filled into a canister and the temperature in the canister was measured. The maximum temperature was 61 ° C and the minimum temperature was 8 ° C. The temperature change in the canister was It is clear that it has been suppressed.
[0072] 実施例 12  [0072] Example 12
実施例 1と同様にして MCを作製し、該 MC41gを 118gの水に分散させ、主剤 1とし て日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672(固形分 50%)を 2. 4g及び主剤 2として株式会社クラレ製ポリウレタンェマルジヨン KMN—N Oc (固形分 40%) 3gと、副剤 1として固形分 10%となるように水で希釈した日本ポリゥ レタン工業株式会社製ポリイソシァネート AQ210を 4. 7g及び副剤 2として固形分 10 %となるように水で希釈したナガセケムテックス株式会社製エポキシィ匕合物デナコー ル EX— 614を 2. 4g加えてよく攪拌した。この時、主剤：副剤の固形分割合は、重量 比で 77. 2 : 22. 8であり、 MCIOO重量部に対する混合型榭脂の固形分比率は 7. 6 重量部であった。  MC was prepared in the same manner as in Example 1, 41 g of MC was dispersed in 118 g of water, and 2.4 g of Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Strengsol sol FX-672 (solid content 50%) was used as the main agent 1. And Kuraray Co., Ltd., polyurethane emulsion KMN-N Oc (solid content 40%) as the main agent 2 and polyisolated from Nippon Polytane Kogyo Co., Ltd. diluted with water to a solid content of 10% as the auxiliary agent 1. 4.7 g of cyanate AQ210 and 2.4 g of epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water to a solid content of 10% as adjunct 2 were added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 77.2: 22.8 in weight ratio, and the solid content ratio of the mixed type resin to MCIOO parts by weight was 7.6 parts by weight.
[0073] 得られた混合液 171. 5gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 2回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 32mJ に lOOOmL相当分 35 lgをキヤ-スターに充填し、キヤ-スター内の温度を測定した ところ、最高温度 58°C、最低温度 12. 5°Cであり、キヤニスター内の温度変化が抑制 されていることは明らかである。 [0073] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 171.5 g of the obtained mixed liquid, and vigorously stirred until no surface moisture was observed, and the resulting solid was JIS standard 4Z7 . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC impregnated coal obtained at this time is 32mJ When the temperature inside the canister was measured by filling 35 lg equivalent to lOOOOmL into the canister, the maximum temperature was 58 ° C and the minimum temperature was 12.5 ° C, and the temperature change inside the canister was suppressed. Obviously.
[0075] 実施例 13 [0075] Example 13
実施例 1と同様にして MCを作製し、該 MC6gを 118gの水に分散させ、主剤 1とし て日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672(固形分 50%)2. lgと、副剤 1として固形分 10%となるように水で希釈した日本ポリウレタンェ 業株式会社製ポリイソシァネート AQ210を 2. lg及び副剤 2として固形分 10%となる ように水で希釈したナガセケムテックス株式会社製エポキシィ匕合物デナコール EX— 614を 1. lg加えてよく攪拌した。この時、主剤：副剤の固形分割合は、重量比で 76 . 6 : 23. 4であり、 MC100重量部に対する混合型榭脂の固形分比率は 22. 8重量 部であった。  MC was prepared in the same manner as in Example 1, and 6 g of the MC was dispersed in 118 g of water. Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Power Sol FX-672 (solid content 50%) 2.lg Polyisocyanate AQ210 manufactured by Nippon Polyurethane Industry Co., Ltd. diluted with water to a solid content of 10% as Adjunct 1 and diluted with water to a solid content of 10% as Adjunct 2 1. 1 lg of Epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation was added and stirred well. At this time, the solid content ratio of the main agent: secondary agent was 76.6: 23.4 in weight ratio, and the solid content ratio of the mixed type resin to 100 parts by weight of MC was 22.8 parts by weight.
[0076] 得られた混合液 129. 3gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 2回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 5. 6m JZ mgで 3Dつ 7こ  [0076] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 129. 3 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated twice and dried at 120 ° C. for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time is 3D, 7 pieces at 5.6m JZ mg.
[0077] 実施例 1と同様に脱落微粉量を求めたところ 0. 8mgZgであったが、実施例 1と同 様に lOOOmL相当分 350gをキヤ-スターに充填し、キヤ-スター内の温度を測定し たところ、最高温度 64°C、最低温度 6°Cであり、キヤニスター内の温度変化は抑制さ れていなかった。  [0077] The amount of fine powder falling off was determined in the same manner as in Example 1. The amount was 0.8 mgZg. As in Example 1, 350 g equivalent to lOOOOmL was charged into the caster, and the temperature in the caster was adjusted. When measured, the maximum temperature was 64 ° C and the minimum temperature was 6 ° C, and the temperature change in the canister was not suppressed.
[0078] 比較例 1  [0078] Comparative Example 1
主剤と副剤を使用しない以外は実施例 1と同様にして MCを作製し、該 MC35. 3g を 118gの水に分散させよく攪拌した。得られた混合液 153. 3gにクラレケミカル株式 会社製の石炭系活性炭 3GXを 200gすばやく添加し、表面水分が認められなくなる まで激しく攪拌を行い、得られた固形物を JIS規格 4Z7. 5メッシュに篩い分け、上方 力も 30LZ分の流量で 1分間エアーブローを行い、表面に付着している微粉を除去 した。上記操作を 3回繰り返し、 120°Cで 14時間乾燥して MC添着炭を得た。この時 得られた MC添着炭の潜熱は 29. lmiZmgであった。 MC was prepared in the same manner as in Example 1 except that the main agent and the auxiliary agent were not used, and 35.3 g of the MC was dispersed in 118 g of water and stirred well. Quickly add 200g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. to 33.3g of the resulting mixture, stir vigorously until no surface moisture is observed, and convert the resulting solid to JIS standard 4Z7.5 mesh Sieve and air blow for 1 minute at a flow rate of 30LZ to remove fine powder adhering to the surface. did. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 29. lmiZmg.
[0079] 実施例 1と同様に lOOOmL相当分 345gをキヤ-スターに充填し、キヤ-スター内 の温度を測定したところ、最高温度 58°C、最低温度 12°Cであり、キヤニスター内の温 度変化は抑制されていたが、実施例 1と同様に脱落微粉量を求めたところ 122. 7m gZgで多かった。 [0079] In the same manner as in Example 1, 345 g equivalent of lOOOOmL was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 12 ° C. Although the change in the degree was suppressed, the amount of fine powder falling off was determined in the same manner as in Example 1, and it was large at 122.7 mgZg.
[0080] 比較例 2 [0080] Comparative Example 2
実施例 1と同様にして MCを作製し、該 MC35. 3gを 118gの水に分散させ、副剤 は使用せず、主剤として水で 50%に希釈した CMCである第一工業製薬株式会社 製セロゲン WS— Aを 4. 7gカ卩えてよく攪拌した。このとき、 MC100重量部に対する 混合型榭脂の固形分比率は 6. 7重量部であった。  MC was produced in the same manner as in Example 1, 33.5 g of MC3 was dispersed in 118 g of water, no secondary agent was used, and CMC diluted to 50% with water as the main agent, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 4.7 g of Serogen WS-A was added and stirred well. At this time, the ratio of the solid content of the mixed resin to 100 parts by weight of MC was 6.7 parts by weight.
[0081] 得られた混合液 158gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200gす ばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形物 を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアーブ ローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120°C で 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 29mjZ mgであった。 [0081] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 158 g of the obtained mixed liquid, and the mixture was vigorously stirred until surface moisture was not observed, and the resulting solid was JIS standard 4Z7. Sieve into 5 mesh and air blow for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 29 mjZ mg.
[0082] 実施例 1と同様に lOOOmL相当分 348gをキヤ-スターに充填し、キヤニスター内 の温度を測定したところ、最高温度 58°C、最低温度 12°Cであり、キヤニスター内の温 度変化が抑制されていたが、実施例 1と同様に脱落微粉量を求めたところ 14. 6mg Zgと多力つた。  [0082] Similarly to Example 1, 348 g of lOOOOmL equivalent was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 58 ° C and the minimum temperature was 12 ° C. However, when the amount of fine powder falling off was determined in the same manner as in Example 1, it was 14.6 mg Zg.
[0083] 比較例 3  [0083] Comparative Example 3
カプセル力 Sメラミン榭脂である MC三木理研工業株式会社製 PMDC— 32SP (粒 径 10 /ζ πι、 MC潜熱 50miZmg) 35. 3gを 118gの水に分散させ、副剤は使用せず 、主剤 1として日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 672 (固形分 50%)を 4. 7g及び主剤 2として固形分が 50%となるように水で希釈し た CMCである第一工業製薬株式会社製セロゲン WS— A4. 7gを加えてよく攪拌し た。このとき、 MCIOO重量部に対する混合型榭脂の固形分比率は 13. 3重量部で あった。 Capsule strength S Melamine slag MCMC Miki Riken Kogyo Co., Ltd. PMDC—32SP (particle size 10 / ζ πι, MC latent heat 50miZmg) 35. Nippon Carbide Industries Co., Ltd. Acrylic Emulsion-Rikizol FX—672 (solid content 50%) 4.7g and main ingredient 2 as CMC, Daiichi Kogyo Seiyaku, diluted with water to a solid content of 50% Serogen WS—A4. At this time, the solid content ratio of the mixed type resin to MCIOO parts by weight was 13.3 parts by weight. there were.
[0084] 得られた混合液 162. 7gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 7. 5m JZ mgで 3Dつ 7こ  [0084] 200 g of coal-based activated carbon 3GX manufactured by Kuraray Chemical Co., Ltd. was quickly added to 162. 7 g of the obtained mixed liquid, and vigorously stirred until surface moisture was not observed. The resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC impregnated coal obtained at this time is 7.5m JZ mg, 3D 7 pieces.
[0085] 実施例 1と同様に lOOOmL相当分 351gをキヤ-スターに充填し、キヤニスター内 の温度を測定したところ、最高温度 61°C、最低温度 9°Cであり、キヤニスター内の温 度変化は抑制されていたが、実施例 1と同様に脱落微粉量を求めたところ 11. lmg Zgと多力つた。  [0085] In the same manner as in Example 1, 351 g of lOOOOmL equivalent was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 61 ° C and the minimum temperature was 9 ° C. However, when the amount of fine powder falling off was determined in the same manner as in Example 1, it was 11. lmg Zg.
[0086] 比較例 4  [0086] Comparative Example 4
カプセル力 Sメラミン榭脂である MC三木理研工業株式会社製 PMDC— 32SP (粒 径 10 /ζ πι、 MC潜熱 50miZmg) 35. 3gを 118gの水に分散させ、副剤は使用せず 、主剤 1として日本カーバイド工業株式会社アクリル系ェマルジヨン-力ゾール FX— 6074 (固形分 50%)を 9. 4gカ卩えてよく攪拌した。このとき、 MCIOO重量部に対する 混合型榭脂の固形分比率は 13. 3重量部であった。  Capsule strength S Melamine slag MCMC Miki Riken Kogyo Co., Ltd. PMDC—32SP (particle size 10 / ζ πι, MC latent heat 50miZmg) 35. Disperse 3g in 118g of water, no adjunct used, main agent 1 As a result, 9.4 g of Nippon Carbide Industries Co., Ltd. acrylic emulsion-strength sol FX-6074 (solid content 50%) was added and stirred well. At this time, the solid content ratio of the mixed type resin to MCIOO parts by weight was 13.3 parts by weight.
[0087] 得られた混合液 162. 7gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 7. 5m JZ mgで 3Dつ 7こ [0087] 200 g of Kuraray Chemical Co., Ltd. 3GX coal-based activated carbon was quickly added to 162. 7 g of the obtained mixed liquid, and vigorously stirred until no surface moisture was observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC impregnated coal obtained at this time is 7.5m JZ mg, 3D 7 pieces.
[0088] 実施例 1と同様に lOOOmL相当分 356gをキヤ-スターに充填し、キヤニスター内 の温度を測定したところ、最高温度 60°C、最低温度 10°Cであり、キヤニスター内の温 度変化は抑制されていたが、実施例 1と同様に脱落微粉量を求めたところ 12. 8mg Zgと多力つた。  [0088] Similar to Example 1, 356 g of lOOOOmL equivalent was filled into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 60 ° C and the minimum temperature was 10 ° C. However, when the amount of fine powder falling off was determined in the same manner as in Example 1, it was 12.8 mg Zg.
[0089] 比較例 5 主剤を使用しない以外は実施例 1と同様にして MCを作製し、該 MC35. 3gを 118 gの水に分散させ、副剤 1として固形分 10%となるように水で希釈した日本ポリウレタ ン工業株式会社製ポリイソシァネート AQ210を 4. 7g及び副剤 2として固形分 10% となるように水で希釈したナガセケムテックス株式会社製エポキシィ匕合物デナコール EX— 614を 2. 4gカ卩えてよく攪拌した。このとき、 MC100重量部に対する混合型榭 脂の固形分比率は 2重量部であった。 [0089] Comparative Example 5 MC was prepared in the same manner as in Example 1 except that the main agent was not used, and 33.5 g of the MC was dispersed in 118 g of water and diluted with water to a solid content of 10%. 2.7 g of Polyisocyanate AQ210 manufactured by Kogyo Co., Ltd. and 2.4 g of Epoxy compound Denacol EX-614 manufactured by Nagase ChemteX Corporation diluted with water to a solid content of 10% as secondary agent 2 Stir well. At this time, the solid content ratio of the mixed resin to 100 parts by weight of MC was 2 parts by weight.
[0090] 得られた混合液 160. 4gにクラレケミカル株式会社製の石炭系活性炭 3GXを 200 gすばやく添加し、表面水分が認められなくなるまで激しく攪拌を行い、得られた固形 物を JIS規格 4Z7. 5メッシュに篩い分け、上方から 30LZ分の流量で 1分間エアー ブローを行い、表面に付着している微粉を除去した。上記操作を 3回繰り返し、 120 °Cで 14時間乾燥して MC添着炭を得た。この時得られた MC添着炭の潜熱は 28mJ / mgであった。 [0090] 200 g of coal-based activated carbon 3GX made by Kuraray Chemical Co., Ltd. was quickly added to 160. 4 g of the obtained mixed liquid, and vigorously stirred until no surface moisture was observed, and the resulting solid was JIS standard 4Z7. . Sifted to 5 mesh and air blown for 1 minute at a flow rate of 30LZ from above to remove fine powder adhering to the surface. The above operation was repeated three times and dried at 120 ° C for 14 hours to obtain MC-impregnated coal. The latent heat of the MC-impregnated coal obtained at this time was 28 mJ / mg.
[0091] 実施例 1と同様に lOOOmL分 375gをキヤ-スターに充填し、キヤ-スター内の温 度を測定したところ、最高温度 56°C、最低温度 14°Cであり、キヤニスター内の温度変 化が抑制されて 、たが実施例 1と同様に脱落微粉量を求めたところ 12. lmgZgと多 かった。  [0091] As in Example 1, 375 g of lOOOOmL was charged into a canister, and the temperature inside the canister was measured. As a result, the maximum temperature was 56 ° C and the minimum temperature was 14 ° C. Although the change was suppressed, the amount of fine powder falling off was determined in the same manner as in Example 1, and it was as large as 12. lmgZg.
産業上の利用可能性  Industrial applicability
[0092] 本発明の MC添着炭を蒸散燃料ガス吸着材として使用すると、蒸散燃料ガスの吸 脱着に伴って生じる発熱及び吸熱を効率的に管理することができるので蒸散燃料ガ ス吸着材としての性能を高度に保持することが可能となり、しかも MCと活性炭が分離 しにく 、ので耐久性に優れた実用性の高 、キヤ-スターを実現することができる。 図面の簡単な説明 [0092] When the MC-impregnated coal of the present invention is used as a transpiration fuel gas adsorbent, heat generation and heat absorption caused by the adsorption and desorption of the transpiration fuel gas can be efficiently managed. High performance can be maintained, and MC and activated carbon are difficult to separate. Therefore, a practical and highly practical star with excellent durability can be realized. Brief Description of Drawings
[0093] [図 1]実施例 1で得られた MC添着炭断面の 200倍顕微鏡写真である。 [0093] FIG. 1 is a 200 × micrograph of an MC-added carbon cross section obtained in Example 1.
[図 2]本発明の MC添着炭の性能を見るために使用したキヤ-スターの断面概略図 である。  FIG. 2 is a schematic cross-sectional view of a caster used to see the performance of MC-added coal of the present invention.
符号の説明  Explanation of symbols
[0094] 1 活性炭 [0094] 1 Activated carbon
2 MC キヤニスター パージ空気口 分散板 2 MC Canister Purge air port Dispersion plate
MC添着炭 n—ブタン供給口 温度計 断熱材 MC-impregnated coal n-butane supply port Thermometer Thermal insulation

Claims

請求の範囲 The scope of the claims
[I] 相変化により熱の吸収及び放出を生じる物質を封入したマイクロカプセルを活性炭 に添着したマイクロカプセル添着炭において、水を蒸発させた後に皮膜状になって 接着性を発現する水性ェマルジヨン (A)と架橋性の液状榭脂 (B)カゝらなる液混合型 榭脂を水で希釈した水性組成物を結合剤とすることを特徴とするマイクロカプセル添 着炭。  [I] A water-based emulsion (A) in which microcapsules encapsulating substances that absorb and release heat due to phase change are attached to activated carbon. ) And a crosslinkable liquid resin (B) A microcapsule-impregnated charcoal, characterized in that an aqueous composition obtained by diluting a liquid mixed type resin made of citrus with water is used as a binder.
[2] 該相変化により熱の吸収及び放出を生じる物質を封入したマイクロカプセルの潜熱 が 50mjZmg以上である請求項 1記載のマイクロカプセル添着炭。  [2] The microcapsule-impregnated carbon according to [1], wherein the latent heat of the microcapsule encapsulating a substance that absorbs and releases heat by the phase change is 50 mjZmg or more.
[3] 該水性ェマルジヨン (A) 1S アクリル系及び Z又はポリウレタン系の榭脂である請求 項 1又は 2記載のマイクロカプセル添着炭。  [3] The microcapsule-impregnated charcoal according to claim 1 or 2, wherein the aqueous emulsion (A) is a 1S acrylic and Z or polyurethane based resin.
[4] 該架橋性の液状榭脂 (B)の官能基が、イソシァネート基、ブロックイソシァネート基、 エポキシ基、ォキサゾリン基、カルポジイミド基、アジリジン基、カルボニル基、ヒドラジ ド基力 なる群より選ばれる少なくとも 1種の官能基である請求項 1〜3いずれかに記 載のマイクロカプセル添着炭。  [4] The functional group of the crosslinkable liquid resin (B) is selected from the group consisting of isocyanate groups, block isocyanate groups, epoxy groups, oxazoline groups, carpositimide groups, aziridine groups, carbonyl groups, and hydrazide groups. The microcapsule-impregnated carbon according to any one of claims 1 to 3, which is at least one kind of functional group.
[5] 該架橋性の液状榭脂 (B)の官能基が、イソシァネート基および Zまたはエポキシ基 である請求項 1〜3いずれかに記載のマイクロカプセル添着炭。  5. The microcapsule-impregnated carbon according to any one of claims 1 to 3, wherein the functional group of the crosslinkable liquid resin (B) is an isocyanate group, Z or an epoxy group.
[6] 該液混合型榭脂における固形分の割合が、水性ェマルジヨン (A) 70〜95重量％と 架橋性の液状榭脂 (B) 5〜30重量％とからなる請求項 1〜5いずれかに記載のマイ クロカプセル添着炭。  [6] The composition according to any one of claims 1 to 5, wherein the ratio of the solid content in the liquid-mixed resin is 70 to 95% by weight of aqueous emulsion (A) and 5 to 30% by weight of crosslinkable liquid resin (B). The microcapsule-attached charcoal described in Crab.
[7] 該添着されたマイクロカプセルが活性炭 100重量部に対し 5〜65重量部である請求 項 1〜6いずれかに記載のマイクロカプセル添着炭。  7. The microcapsule-impregnated charcoal according to any one of claims 1 to 6, wherein the impregnated microcapsule is 5 to 65 parts by weight with respect to 100 parts by weight of activated carbon.
[8] 該マイクロカプセル添着炭の潜熱が 7mjZmg以上である請求項 1〜7いずれかに記 載のマイクロカプセル添着炭。 8. The microcapsule-impregnated charcoal according to any one of claims 1 to 7, wherein the latent heat of the microcapsule-impregnated charcoal is 7 mjZmg or more.
[9] マイクロカプセルに水性組成物を添加し混合した混合物に活性炭を添加し、実質的 に水分がなくなるまで攪拌した後乾燥するマイクロカプセル添着炭の製造方法。  [9] A method for producing microcapsule-added charcoal, wherein activated carbon is added to a mixture obtained by adding an aqueous composition to microcapsules and mixed, and the mixture is stirred until substantially free of moisture and then dried.
[10] マイクロカプセルに水性組成物を添加し混合物を調製する際、マイクロカプセルが凝 集しな 、ように高速攪拌する請求項 9記載のマイクロカプセル添着炭の製造方法。  [10] The method for producing microcapsule-added charcoal according to claim 9, wherein when the aqueous composition is added to the microcapsule to prepare a mixture, the microcapsule is stirred at a high speed so that the microcapsule does not aggregate.
[II] 活性炭 100重量部に対し、マイクロカプセルと水性組成物の混合物を固形分として 5 〜70重量部添加する請求項 9又は 10記載のマイクロカプセル添着炭の製造方法。 [II] For 100 parts by weight of activated carbon, the mixture of microcapsules and aqueous composition is 5 The method for producing a microcapsule-impregnated carbon according to claim 9 or 10, wherein -70 parts by weight is added.
[12] 請求項 1〜1 、ずれか〖こ記載のマイクロカプセル添着炭を蒸散燃料ガス吸着材とす るキヤニスター。 [12] A canister using the microcapsule-impregnated coal according to any one of claims 1 to 1 as a transpiration fuel gas adsorbent.
PCT/JP2007/060207 2006-05-23 2007-05-18 Carbon with adherent microcapsule, process for producing the same, and canister WO2007135978A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006142253 2006-05-23
JP2006-142253 2006-05-23

Publications (1)

Publication Number Publication Date
WO2007135978A1 true WO2007135978A1 (en) 2007-11-29

Family

ID=38723290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/060207 WO2007135978A1 (en) 2006-05-23 2007-05-18 Carbon with adherent microcapsule, process for producing the same, and canister

Country Status (1)

Country Link
WO (1) WO2007135978A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009145020A1 (en) * 2008-05-27 2009-12-03 大阪ガスケミカル株式会社 Process for producing heat storage material, heat storage material, adsorbent material with heat storage function and canister

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10339218A (en) * 1997-06-04 1998-12-22 Tennex:Kk Treatment device of evaporative fuel
WO2003106833A1 (en) * 2002-06-18 2003-12-24 大阪瓦斯株式会社 Adsorbent of latent-heat storage type for canister and process for producing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10339218A (en) * 1997-06-04 1998-12-22 Tennex:Kk Treatment device of evaporative fuel
WO2003106833A1 (en) * 2002-06-18 2003-12-24 大阪瓦斯株式会社 Adsorbent of latent-heat storage type for canister and process for producing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009145020A1 (en) * 2008-05-27 2009-12-03 大阪ガスケミカル株式会社 Process for producing heat storage material, heat storage material, adsorbent material with heat storage function and canister
JP5002054B2 (en) * 2008-05-27 2012-08-15 大阪ガスケミカル株式会社 Manufacturing method of heat storage material, heat storage material, adsorbent with heat storage function, canister
US8323450B2 (en) 2008-05-27 2012-12-04 Osaka Gas Chemicals Co., Ltd. Method of manufacturing heat storage material, heat storage material, and heat storage adsorbent material and canister

Similar Documents

Publication Publication Date Title
EP1536128B1 (en) Adsorbent of latent-heat storage type for canister and process for producing the same
JP4099714B2 (en) Adsorbent sheet and air cleaning filter
JP5428857B2 (en) Deodorizing fiber structure and air filter
JP3728475B2 (en) Adsorbent with dust filter function
JP6988477B2 (en) Filter media for air purification
RU2008107713A (en) ABSORBING SYSTEMS CONTAINING A GAS-ABSORBING PHASE IN THE PORES OF A POROUS MATERIAL DISTRIBUTED IN THE PERMITTED MEANS
US20100212496A1 (en) Adsorbent, process for producing the same, canister and method for using the same
JP2009019572A (en) Canister, adsorbent for canister and method of manufacturing its adsorbent
JP2012508646A (en) Adsorbent structures and their use
JP4674199B2 (en) PSA equipment
US20130295197A1 (en) Formed lyocell articles for selective binding of monovalent heavy metal ions, especially thallium and cesium ions and radioactive isotopes thereof
CN111683745A (en) Gas adsorbent, deodorizing fiber sheet, and method for producing gas adsorbent
JP2015029770A (en) Air cleaning filter medium
US20070277788A1 (en) Transpiration Fuel Gas Adsorbent and Process for Producing the Same
JP4526333B2 (en) Canister adsorbent, method for producing the same, and canister for preventing fuel evaporation
WO2007135978A1 (en) Carbon with adherent microcapsule, process for producing the same, and canister
JP2008206550A (en) Absorbent sheet
CN114797748B (en) Air purification adsorption material and preparation method and application thereof
JP2006063859A (en) Evaporating fuel gas adsorbent and evaporating fuel gas collecting device
JP4707683B2 (en) Manufacturing method of adsorbent with heat storage function, adsorbent with heat storage function, and canister
WO2021210386A1 (en) Latent heat storage material-integrated active carbon and production method thereof
JP2010142679A (en) Heat storage medium-imparted combined adsorbing material and method for producing the same
JPWO2017086177A1 (en) Composite gas adsorbent, adsorption filter using the same, and method for producing composite gas adsorbent
JP3712084B2 (en) Adsorbent
JP5250060B2 (en) Manufacturing method of adsorbent with heat storage function, adsorbent with heat storage function, and canister

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07743642

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07743642

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP