JP4956232B2 - Manufacturing method of adsorbent with heat storage function, adsorbent with heat storage function, and canister - Google Patents

Description

  The present invention mixes a heat storage material including a heat storage capsule formed by enclosing a phase change material that absorbs and releases latent heat in response to a temperature change in an outer shell made of a polymer compound, and an adsorbent. The present invention relates to a method for manufacturing an adsorbent with a heat storage function, an adsorbent with a heat storage function, and a canister filled with the adsorbent with a heat storage function in a case.

As a canister used to prevent the vaporized fuel (gasoline etc.) supplied to an internal combustion engine such as a vehicle from being released to the outside (in the atmosphere, etc.), for example, an adsorption canister, that is, when the vehicle is stopped An adsorbent canister that adsorbs excess vaporized fuel to the adsorbent in the case, introduces the atmosphere into the case as a purge gas, removes the adsorbed vaporized fuel, and supplies it to the internal combustion engine, etc. is there. As an adsorbent used in such an adsorption canister, for example, Patent Document 1 is configured by a heat storage capsule in which a phase change material that absorbs and releases latent heat according to a temperature change is enclosed in an outer shell. An adsorbent with a heat storage function formed by mixing a heat storage material and an adsorbent and a method for manufacturing the adsorbent are disclosed.
According to the adsorbent with a heat storage function described in Patent Document 1, the heat storage function of the heat storage material prevents the temperature from rising and falling due to the heat of adsorption and desorption of the adsorbent, thereby preventing the adsorption / desorption performance of the adsorbent from deteriorating. can do.

  That is, in general, the adsorption performance of the adsorbent decreases as the temperature of the adsorbent increases, and the desorption performance of the adsorbent decreases as the temperature of the adsorbent decreases. Therefore, when the temperature of the adsorbent rises due to the heat of adsorption generated when gas or the like is adsorbed on the adsorbent, the adsorption performance is reduced. On the other hand, when gas or the like is desorbed from the adsorbent, heat absorption due to desorption occurs, and when the temperature of the adsorbent decreases, the desorption performance is reduced. Such a decrease in adsorption / desorption performance includes a heat storage capsule (microcapsule, the same applies hereinafter) in which a phase change material that absorbs and releases latent heat in response to temperature changes is enclosed in the outer shell. It is possible to absorb or release latent heat when the phase change material undergoes a phase change, thereby suppressing the temperature change of the adsorbent to a minimum, and higher adsorption / Desorption performance can be obtained.

  Conventionally, the above heat storage capsule is generally obtained by encapsulating in a medium, and then drying and solidifying the medium. Such a solidified heat storage capsule is easy to handle and easy to use, and is used for a wide range of applications (for example, canisters).

  However, when encapsulating in a medium as described above, polymerization of a polymer compound (for example, melamine resin) constituting the outer shell of the heat storage capsule proceeds to some extent, but the degree of polymerization is relatively low, and the polymer There are a considerable number of unreacted groups in the compound, and it cannot be said that the strength of the heat storage capsule is sufficient depending on the application. When such a heat storage capsule having a relatively low strength is used in the water slurry, there is no need to consider the possibility of the heat storage capsule being destroyed, but the heat storage capsule is dried and solidified. If the heat storage capsule is mixed with an adsorbent with a relatively high strength, etc., the heat storage capsule may be destroyed, and the heat storage performance is reduced as the heat storage capsule is broken. Therefore, the adsorption / desorption performance may be reduced.

In addition, when the adsorbent with a heat storage function in which the solidified heat storage capsule and the adsorbent are mixed is filled in a canister case, for example, gasoline adsorbed by the adsorbent in the case The vaporized fuel (organic solvent) may destroy or permeate the outer shell of the heat storage capsule and leak the phase change material enclosed in the outer shell to the outside. Furthermore, moisture, moisture, etc. present in the case may deteriorate the outer shell of the heat storage capsule, destroy the outer shell, and leak the phase change material enclosed in the outer shell to the outside.
Such leakage of the phase change material to the outside may cause deterioration in heat storage performance and decrease in adsorption / desorption performance.

  In addition, due to the expansion and contraction caused by the phase change of the phase change material enclosed in the outer shell of the solidified heat storage capsule, repeated stress is applied to the solid outer shell, and the outer shell of the heat storage capsule is fatigued due to long-term use. As a result, the phase change material leaks out (decrease in heat history durability), which may reduce the heat storage performance and decrease the adsorption / desorption performance.

  In order to solve the above-mentioned problem, Patent Document 2 discloses a heat storage in which the average particle diameter of the solidified heat storage capsule is 3.5 μm or more, and the film thickness of the outer shell of the heat storage capsule is in the range of 5 nm to 150 nm. A capsule invention is disclosed.

  Similarly, Patent Document 3 discloses a thermal storage capsule having a solidified thermal storage capsule with an average particle diameter of less than 3.5 μm and an outer shell thickness of the thermal storage capsule of 1 nm to 100 nm. The invention is disclosed.

  According to the inventions described in Patent Documents 2 and 3, when the heat storage material including the heat storage capsule and the adsorbent are mixed, the heat storage capsule is repeatedly subjected to stress and external pressure by appropriately setting the average particle diameter and the film thickness. Even when the heat storage capsule is added, it is supposed that the heat storage capsule can be prevented from being broken, and even when the expansion and contraction are repeated by long-term use, the outer shape of the heat storage capsule can be prevented from being deformed to prevent the outer shell from being broken.

JP 2001-145832 A JP 2006-63328 A JP 2006-63327 A

  However, in the inventions described in Patent Documents 2 and 3, the average particle diameter and film thickness of the heat storage capsule are appropriately set to prevent the heat storage capsule from being destroyed to some extent during mixing and long-term continuous use within the set range. Although it is possible, there is a limit to properly preventing the thermal storage capsule from being destroyed outside the set range. Specifically, as for the film thickness of the outer shell of the heat storage capsule, a thicker film is advantageous from the viewpoint of strength and solvent resistance at the time of mixing, but in the invention described in Patent Document 2 or 3, the film thickness is 150 nm at the maximum. If it is relatively thin and thicker than this, it cannot cope with repeated stress due to expansion and contraction of the phase change material during continuous use for a long period of time, and induces fatigue failure of the outer shell of the heat storage capsule, thereby improving the heat storage performance. This may lead to a decrease in adsorption / desorption performance as well as a decrease (decrease in heat history durability).

  The present invention has been made in view of the above-mentioned problems, and its purpose is to destroy the heat storage capsule during mixing in the adsorbent with a heat storage function in which the heat storage material including the heat storage capsule and the adsorbent are mixed. The present invention provides a technique capable of appropriately preventing deterioration in heat resistance, deterioration in heat storage performance during long-term continuous use (decrease in heat history durability), and the like, and maintaining good adsorption / desorption performance.

[First configuration]
In order to achieve the above object, a method for producing an adsorbent with a heat storage function according to the present invention comprises a phase change material that absorbs and releases latent heat in accordance with a change in temperature as described in claim 1 of the claims. A method for producing an adsorbent with a heat storage function in which a heat storage material comprising a heat storage capsule enclosed in an outer shell made of a polymer compound and an adsorbent are mixed, and the thickness of the outer shell of the heat storage capsule Is formed in a range of 151 nm to 300 nm, and then the outer surface is coated with a resin having a group that reacts with an unreacted group of the polymer compound, and the heat storage material including the heat storage capsule that has been coated The molded heat storage material is molded with a binder, and the adsorbent is molded with a binder, and the molded heat storage material and the molded adsorbent are mixed. Having.

  The adsorbent with a heat storage function according to the present invention for achieving the above object is preferably manufactured by the manufacturing method of the adsorbent with a heat storage function of the first configuration. Claim 5 of the Claims As described, a heat storage material comprising a heat storage capsule formed by enclosing a phase change material that absorbs and releases latent heat in response to a temperature change in an outer shell made of a polymer compound and an adsorbent are mixed. A heat storage function-adsorbing material, wherein the outer shell of the heat storage capsule has a thickness of 151 nm or more and 300 nm or less, and a group that reacts with an unreacted group of the polymer compound on the surface of the outer shell. A molded heat storage material in which the heat storage material including the heat storage capsule having the coating layer is molded with a binder and a molded adsorption material in which the adsorbent is molded with a binder are mixed. It is characterized in that comprising.

According to the first configuration, the outer shell of the heat storage capsule is made as thick as possible, and a coating layer made of a resin is provided on the outer shell to improve solvent resistance and water resistance, and heat history durability. It will be sufficient.
That is, the outer shell of the heat storage capsule is formed by forming a film of a polymer compound around the phase change material and increasing the degree of polymerization of the film by a polymerization reaction. If the film is too thin, it is mixed with the adsorbent. In this case, the film (outer shell) is destroyed (breakage at the time of mixing), and when it comes into contact with an organic solvent, the organic solvent etc. breaks or permeates the film (reduced solvent resistance) and enters the outer shell. The encapsulated phase change material may leak and heat storage performance may be reduced. On the other hand, when the phase change material encapsulated in the outer shell of the heat storage capsule undergoes a temperature change, the phase change repeats the expansion and contraction, and the outer shell of the heat storage capsule repeatedly expands and contracts due to this influence. If the thickness is too thick, the outer shell is deformed and destroyed by the expansion and contraction, the phase change material enclosed in the outer shell leaks out, and there is a possibility that the heat storage performance is lowered (heat history durability is lowered).

Therefore, the outer shell of the heat storage capsule needs to be set to a thickness that does not lower both the solvent resistance and the heat history durability. Here, in order to make the solvent resistance more sufficient, it is necessary to set the outer shell of the heat storage capsule as thick as possible. Conventionally, it is difficult to adopt it because it causes a decrease in the heat history durability. In other words, the lower limit of the outer shell thickness of the heat storage capsule is set to 151 nm. Thereby, since an outline becomes thick, the intensity | strength at the time of mixing and solvent resistance improve. And in order for the heat history durability to be sufficient under the condition that the lower limit value of the outer shell thickness of the heat storage capsule is 151 nm, the upper limit of the outer shell of the heat storage capsule is set to 300 nm. As a result, the strength and solvent resistance during mixing due to being thinner than 151 nm can be made sufficient, and the heat history durability due to being thicker than 300 nm can be made sufficient.
Furthermore, when the outer shell of the heat storage capsule has a thickness within the above range, since the outer shell is relatively thick, a decrease in heat storage performance from the viewpoint of strength and solvent resistance during mixing is prevented. However, it cannot be said that the deterioration of the heat storage performance from the viewpoint of heat history durability is sufficiently prevented. Therefore, it is possible to improve the heat history durability by providing a resin coating layer on the outer surface of the heat storage capsule. That is, the outer shell of the heat storage capsule is composed of a polymer compound, and the polymer compound has a considerable number of unreacted groups that have not undergone a polymerization reaction at the encapsulation stage. The outer shell of the heat storage capsule is coated with a resin having a group that reacts with the unreacted group, and a coating layer is provided to advance the polymerization reaction of the unreacted group and increase the degree of polymerization of the polymer compound, thereby increasing the strength of the outer shell The outer layer of the thermal storage capsule restrains the outer surface of the thermal storage capsule, and the outer shell of the thermal storage capsule is subjected to fatigue failure even when repeated stress is caused by expansion and contraction of the phase change material. Can be prevented.
In addition, the heat storage materials including the heat storage capsules are preliminarily molded with a binder and used as a molded heat storage material, so that when the heat storage material is mixed with a high-strength adsorbent later, the area where the heat storage material comes into contact is reduced. Capsule breakage can be prevented. Similarly, by adsorbing the adsorbents in advance with a binder to form a molded adsorbent, the adsorbent can be prevented from being destroyed when it is mixed with the heat storage material later.
Furthermore, since the molded heat storage material and the molded adsorbent are both molded and have a certain size, the contact area between the two is created while creating a void that does not hinder the flow of gas adsorbed in the mixed state. Therefore, it is possible to prevent a decrease in adsorption performance due to the inability of gas or the like to reach the adsorbent while preventing a decrease in heat storage performance due to a decrease in the contact area.

[Second configuration]
In order to achieve the above object, a method for producing an adsorbent with a heat storage function according to the present invention comprises a phase change substance that absorbs and releases latent heat in accordance with a temperature change, as described in claim 2 of the claims. A method for producing an adsorbent with a heat storage function in which a heat storage material configured to include a heat storage capsule enclosed in an outer shell made of a polymer compound and an adsorbent are mixed, and the volume of the outer shell with respect to the heat storage capsule The ratio is formed in the range of 5% to 30% and the average particle diameter of the heat storage capsule is formed in the range of 2.8 μm to 15 μm. The heat storage material including the heat storage capsule that has been coated with a resin having a group that reacts with a reactive group is formed into a molded heat storage material using a binder, and the adsorbent is formed using a binder. The molded adsorbent is characterized in that the molded heat storage material and the molded adsorbent are mixed.

  The adsorbent with a heat storage function according to the present invention for achieving the above object is preferably manufactured by the method for manufacturing the adsorbent with a heat storage function of the second configuration. As described, a heat storage material comprising a heat storage capsule formed by enclosing a phase change material that absorbs and releases latent heat in response to a temperature change in an outer shell made of a polymer compound and an adsorbent are mixed. An adsorbent with a heat storage function, wherein a volume ratio of the outer shell to the heat storage capsule is formed in a range of 5% to 30%, and an average particle diameter of the heat storage capsule is 2.8 μm to 15 μm. The heat storage material including a heat storage capsule having a coating layer of resin that has a resin layer having a group that reacts with an unreacted group of the polymer compound is formed on a surface of the outer shell using a binder. The molded heat storage material and the molded adsorbent obtained by molding the adsorbent with a binder are characterized in that they are mixed.

According to the second configuration, the average particle diameter of the heat storage capsule and the volume ratio of the outer shell in the heat storage capsule are within an appropriate range, and the coating layer made of resin is provided on the surface of the outer shell. Solvent resistance and water resistance are improved, and heat history durability is sufficient.
That is, if the average particle size of the heat storage capsule is too small, the amount of phase change material that can be enclosed in the outer shell is reduced and heat storage performance is deteriorated, and strength and solvent resistance during mixing may be decreased. . If the average particle size of the heat storage capsule is too large, the outer shell of the heat storage capsule is also thickened, and the outer shell is destroyed by repeated stress due to the expansion and contraction of the phase change material, which may reduce the heat history durability. Therefore, the average particle size needs to be appropriately set within a range in which the heat storage performance, the strength at the time of mixing, and the solvent resistance are not lowered and the heat history durability is not lowered. Specifically, when the average particle size is smaller than 2.8 μm, the heat storage performance, strength at the time of mixing, and solvent resistance are lowered, and when the average particle size is larger than 15 μm, the heat history durability is lowered.
Therefore, the average particle diameter is set in the range of 2.8 μm to 15 μm.
Even if the average particle diameter is in the above range, if the volume ratio of the outer shell in the heat storage capsule changes, the heat storage performance, strength at the time of mixing, solvent resistance, and heat history durability may be lowered. Therefore, the volume ratio of the outer shell in the heat storage capsule is set in the range of 5% or more and 30% or less as the range in which the heat storage performance, the strength at the time of mixing, the solvent resistance, and the heat history durability are not lowered in the range of the average particle diameter. To do.
Furthermore, when the heat storage capsule is within the above range, the thickness of the outer shell of the heat storage capsule is relatively thick, so that deterioration in heat storage performance from the viewpoint of mixing strength and solvent resistance is prevented, It cannot be said that the deterioration of the heat storage performance from the viewpoint of heat history durability is sufficiently prevented. Therefore, it is possible to improve the heat history durability by providing a resin coating layer on the outer surface of the heat storage capsule. That is, the outer shell of the heat storage capsule is composed of a polymer compound, and the polymer compound has a considerable number of unreacted groups that have not undergone a polymerization reaction at the encapsulation stage. The outer shell of the heat storage capsule is coated with a resin having a group that reacts with the unreacted group, and a coating layer is provided to advance the polymerization reaction of the unreacted group and increase the degree of polymerization of the polymer compound, thereby increasing the strength of the outer shell. The outer layer of the thermal storage capsule restrains the outer surface of the thermal storage capsule, and the outer shell of the thermal storage capsule is subjected to fatigue failure even when repeated stress is caused by expansion and contraction of the phase change material. Can be prevented.
In addition, the heat storage materials including the heat storage capsules are preliminarily molded with a binder and used as a molded heat storage material, so that when the heat storage material is mixed with a high-strength adsorbent later, the area where the heat storage material comes into contact is reduced. Capsule breakage can be prevented. Similarly, by adsorbing the adsorbents in advance with a binder to form a molded adsorbent, the adsorbent can be prevented from being destroyed when it is mixed with the heat storage material later.
Furthermore, since the molded heat storage material and the molded adsorbent are both molded and have a certain size, the contact area between the two is created while creating a void that does not hinder the flow of gas adsorbed in the mixed state. Therefore, it is possible to prevent a decrease in adsorption performance due to the inability of gas or the like to reach the adsorbent while preventing a decrease in heat storage performance due to a decrease in the contact area.

[Third configuration]
The manufacturing method of the adsorbent with a heat storage function according to the present invention includes an initial stage in addition to the configuration of the manufacturing method of the adsorbent with a heat storage function according to the first or second configuration. After encapsulating through an outer shell forming process for forming the outer shell by heating at a heating temperature, the completed heat storage capsule is reheated at a reheating temperature higher than the initial heating temperature.

  The adsorbent with a heat storage function according to the present invention is preferably manufactured by the method for manufacturing the adsorbent with a heat storage function of the third configuration, and as described in claim 7 of the claims, the first Alternatively, in addition to the configuration of the adsorbent with a heat storage function of the second configuration, after the capsule is encapsulated through an outer shell forming process for forming the outer shell by heating at an initial heating temperature, the initial heating temperature is It is characterized by comprising the heat storage capsule reheated at a higher reheating temperature.

According to the said 3rd structure, the high molecular compound which comprises the outline of a thermal storage capsule is heated by initial heating temperature (generally about 70 degreeC-80 degreeC), and an outline is raised by raising the polymerization degree of the said high molecular compound. Encapsulate by forming the outer shell to be formed, and then perform a reheating treatment at a reheating temperature higher than the initial heating temperature in order to further improve the polymerization degree of the polymer compound constituting the outer shell of the completed heat storage capsule. Can do.
That is, even when the degree of polymerization of the polymer compound formed in the outer shell forming process is low, the completed heat storage capsule is reheated at a reheating temperature (about 100 ° C. to 140 ° C.) higher than the initial heating temperature. By performing the treatment, the degree of polymerization of the polymer compound can be further improved to form a dense and strong outer shell.
Thereby, the degree of polymerization of the polymer compound constituting the outer shell can be improved, and not only the strength of the heat storage capsule, but also the heat storage capsule with improved solvent resistance, water resistance, and heat history durability can be obtained, The heat storage performance can be made sufficient.
The reheating process can also be performed by forming the outer shell of the heat storage capsule at the initial heating temperature (relatively low temperature) in the outer shell forming process and reheating the completed solid heat storage capsule at the reheating temperature. it can.
[Fourth configuration]
The method for producing an adsorbent with a heat storage function according to the present invention is the method for producing an adsorbent with a heat storage function according to any one of the first to third configurations as described in claim 4 of the claims. In addition to the configuration, the polymer compound is a melamine resin, and the resin having a group that reacts with an unreacted group of the polymer compound is polyvinyl alcohol.
The adsorbent with a heat storage function according to the present invention is preferably manufactured by the method for manufacturing the adsorbent with a heat storage function of the fourth configuration, and as described in claim 8 of the claims, the first In addition to the configuration of the adsorbent with a heat storage function according to any one of -3 configurations, the polymer compound is a melamine resin, and a resin having a group that reacts with an unreacted group of the polymer compound, It is characterized in that it is polyvinyl alcohol.

According to said 4th structure, it reacts with the unreacted unreacted group, although polymerization reaction was performed in the surface of the melamine resin as a high molecular compound which comprises the outline of a thermal storage capsule. When polyvinyl alcohol as a resin having a group is coated and the unreacted group and the reactive group react and the polymerization reaction proceeds, the bond between the melamine resin and polyvinyl alcohol is strengthened, and the strength of the outer shell of the heat storage capsule is increased. Will be improved.
In particular, polyvinyl alcohol is a thermoplastic resin that contains a large amount of hydroxyl groups among hydrophilic resins and is coated on the surface of the melamine resin, so that the gas barrier properties, flexibility, and composition of the coated layer are covered. The film property can be further enhanced. Melamine resin is a hydrophobic resin having high mechanical strength and high gas barrier properties. Therefore, the strength of the outer shell of the heat storage capsule can be further strengthened to sufficiently counter the repeated stress caused by the expansion and contraction of the phase change material.
Therefore, not only the strength at the time of mixing and solvent resistance can be improved, but also the heat history durability can be improved.

[Fifth configuration]
A canister according to the present invention is, as described in claim 9 of the claims, filled with a heat storage function adsorbent according to any one of the first to fourth configurations in a case. Has characteristics.

According to the fifth configuration, the heat storage material (molded heat storage material) including the heat storage capsule with enhanced strength and the adsorbent (molded adsorbent) can be mixed and filled in the case of the canister, Good heat storage performance and adsorption / desorption performance can be achieved without destroying the heat storage capsule when mixing the heat storage material (molded heat storage material) and adsorbent (molded adsorbent) and filling the case. .
In addition, even if transpiration fuel such as gasoline or moisture is introduced into the canister case, the heat storage capsule has improved solvent resistance and water resistance, so the heat storage capsule is destroyed and phase change substances leak out. Therefore, there is no decrease in heat storage performance, and good heat storage performance and adsorption / desorption performance can be exhibited.
Furthermore, even if repeated stress due to expansion and contraction of the phase change material due to temperature change in the canister case is applied to the outer shell of the heat storage capsule, the outer shell has the strength to withstand this force and is not destroyed. Therefore, even if expansion and contraction are repeated after long-term use, the heat storage performance is not lowered, and good heat storage performance and adsorption / desorption performance can be exhibited.
Therefore, the adsorbent with a heat storage function can be suitably used for a canister.

An embodiment of a method for producing the adsorbent with heat storage function 7 according to the present invention (hereinafter abbreviated as the present method) will be described with reference to the drawings.
[First Embodiment]
In this method, as shown in FIGS. 1 and 2, a heat storage capsule 4 in which a phase change material 1 that absorbs and releases latent heat according to a temperature change is enclosed in a shell 2 made of a polymer compound 8 is used. It is a manufacturing method of the adsorbent 7 with a heat storage function which mixes the heat storage material 5 comprised and the adsorbent 6, and the thickness of the outer shell 2 of the heat storage capsule 4 is a thickness within a predetermined range for the heat storage capsule 4 Then, the coating layer 3 of the resin 9 is provided on the surface of the outer shell 2, and the heat storage material 5 including the heat storage capsule 4 that has been coated is formed into a molded heat storage material 5 a formed by the binder 10, and the adsorbent 6 The molded heat storage material 5a and the molded adsorbent 6a are mixed together with the molded adsorbent 6a molded by the binder 10.
FIG. 1 is a diagram showing a schematic configuration of the heat storage capsule 4, and FIG. 2 is a diagram in which a powdery heat storage capsule 4 (substantially the heat storage capsule 4 fulfills a heat storage function) described later is molded by a binder 10. Production process of heat storage material 5a, production process of molded adsorbent 6a in which powdered adsorbent 6 is molded by binder 10, adsorbent with heat storage function produced by mixing molded heat storage material 5a and molded adsorbent 6a FIG.

[Heat storage capsule 4]
As shown in FIG. 1, the heat storage capsule 4 is configured by a microcapsule in which a phase change material 1 that absorbs and releases latent heat according to a temperature change is enclosed in an outer shell 2.
The phase change material 1 is not particularly limited as long as it is a compound that absorbs and releases latent heat in accordance with the phase change, but the temperature at which the phase change occurs corresponding to the use of the adsorbent 7 with a heat storage function (for example, the melting point) The freezing point may be selected from organic compounds and inorganic compounds having a melting point of about −150 ° C. to 100 ° C., preferably about 0 ° C. to 50 ° C. Specific examples include straight-chain aliphatic hydrocarbons such as tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heikosan, docosan, natural wax, petroleum wax, LiNO ₃ .3H ₂ O, Na ₂ SO _4.・ Hydrates of inorganic compounds such as 10H ₂ O and Na ₂ HPO ₄ · 12H ₂ O, fatty acids such as capric acid and lauric acid, higher alcohols having 12 to 15 carbon atoms, ester compounds such as methyl palmitate, etc. Can be used. In addition, as a phase change, phase changes, such as between solid-liquid, can be illustrated.
The phase change material 1 may be used in combination of two or more compounds selected from the above. When two or more kinds of phase change materials 1 are used in combination, the difference in temperature causing the phase change of each phase change material 1 is about 0 ° C. to 100 ° C., preferably 0 ° C. to 15 ° C. for canisters. A combination is preferred.
Further, in order to prevent the supercooling phenomenon of the phase change material 1, a compound having a melting point higher than that of the phase change material 1 may be added as necessary.

And these can be used as the heat storage capsule 4 by using these as core materials, for example, microcapsules by a known method such as a coacervation method or an in-situ method (interface reaction method). For example, the phase change material 1 is emulsified in a medium using an emulsifier such as a surfactant, and an initial condensate (prepolymer) corresponding to a desired polymer compound 8 described later is added thereto, and then about 70 ° C. The heat storage capsule 4 which has the outer shell 2 by heating the polymer and reacting the polymerization reaction (corresponding to the outer shell forming process for forming the outer shell 2 by heating at the initial heating temperature) and enclosing the phase change material 1 in the outer shell 2. The dispersion liquid (slurry) can be adjusted.
After completion of the reaction, polyvinyl alcohol is added to the dispersion liquid of the heat storage capsule 4, stirred again, and dried by a spray drying method, whereby the coating layer 3 made of polyvinyl alcohol is formed on the surface of the outer shell 2 made of melamine resin. Can be obtained.

The thickness (film thickness) of the outer shell 2 of the heat storage capsule 4 adjusts the amount of the phase change material 1 and the polymer compound 8 constituting the outer shell 2, the stirring speed when emulsifying the phase change material 1, time, temperature, and the like. Accordingly, the range is set to 151 nm or more and 300 nm or less.
When the lower limit of the thickness of the outer shell 2 of the heat storage capsule 4 is set to 151 nm, the outer shell 2 is made as thick as possible, and in the range that has conventionally been difficult to adopt due to the relationship with thermal history durability, Strength and solvent resistance can be improved. And in order to make heat history durability sufficient under the conditions that the lower limit of the thickness of the outer shell 2 of the heat storage capsule 4 is 151 nm, the upper limit of the thickness of the outer shell 2 of the heat storage capsule 4 is set to 300 nm. . Accordingly, it is possible to prevent a decrease in heat history durability due to being thicker than 300 nm while preventing a decrease in strength and solvent resistance during mixing due to being thinner than 151 nm.
The thickness (film thickness) of the outer shell 2 of the heat storage capsule 4 is preferably 185 nm to 250 nm, more preferably 200 nm to 240 nm, and most preferably 220 nm. By setting this range, it is possible to improve the strength and solvent resistance at the time of mixing while making the heat history durability sufficient even when the film thickness that has been conventionally difficult to adopt is relatively thick. it can. Specifically, by setting the lower limit of the thickness of the outer shell 2 to preferably 185 nm, more preferably 200 nm, the strength and solvent resistance during mixing can be further improved, and the thickness of the outer shell 2 is increased. By making the upper limit of preferably 250 nm, more preferably 240 nm, it is possible to further prevent the heat history durability from being lowered. In particular, by setting the thickness of the outer shell 2 to 220 nm, it was possible to achieve both the improvement in strength and solvent resistance at the time of mixing and the prevention of a decrease in heat history durability, and the best state.
Here, when the thickness (film thickness) of the outer shell 2 of the heat storage capsule 4 is 151 nm, the volume ratio of the outer shell 2 to the heat storage capsule 4 is 30%, and the average particle diameter of the heat storage capsule 4 is 3.6 μm, When the thickness of the outer shell 2 was 160 nm, the volume ratio was about 20%, and the average particle size was about 3.5 μm. Similarly, when the thickness of the outer shell 2 is 185 nm, the volume ratio is about 16%, the average particle diameter is about 6 μm, and when the outer shell 2 thickness is 200 nm, the volume ratio is about 14%, The average particle size was about 7 μm. Similarly, when the thickness of the outer shell 2 is 220 nm, the volume ratio is about 17% and the average particle diameter is about 7 μm.
In addition, the thickness (film thickness) of the outer shell 2 was measured by observing a cross section obtained by cutting the solid of the heat storage capsule 4 with a microtome with a scanning microscope.
The time for performing the polymerization reaction is 1 hour or more and 5 hours or less, and the temperature is 70 ° C. or more and 90 ° C. or less. The thickness (film thickness) of the outer shell 2 is controlled by emulsifying the phase change material 1 so as to have a desired capsule particle diameter, and adding a predetermined amount of the polymer compound 8 constituting the outer shell 2 thereto. Can do. The amount of the polymer compound 8 to be added was determined by calculation based on the desired average particle diameter of the heat storage capsule 4, the thickness (film thickness) of the outer shell 2, and the volume ratio of the outer shell 2 to the heat storage capsule 4.

As the outer shell 2 of the heat storage capsule 4 (microcapsule), a known polymer compound 8 can be used without particular limitation. For example, formaldehyde-melamine resin, melamine resin, formaldehyde-urea resin, urea resin, urea-formaldehyde -Polyacrylic acid copolymer, polystyrene, polyvinyl acetate, polyacrylonitrile, polyethylene, polybutyl methacrylate, gelatin and the like can be used. Preferably, a thermosetting resin, particularly a melamine resin is used.
The weight ratio of the outer shell 2 of the heat storage capsule 4 to the phase change material 1 (outer shell 2: phase change material 1) is not particularly limited, but is usually about 40:60 to 5:95, preferably 30:70 to 10:90. Degree.
The average particle diameter of the heat storage capsule 4 can be appropriately selected from the necessary heat storage amount and capsule strength, but it is possible to prevent the heat storage capsule 4 from being destroyed while ensuring the desired heat storage performance. An average particle size of 15 μm or less is good. At this time, the volume ratio of the outer shell 2 to the heat storage capsule 4 is preferably 5% to 30%. The average particle size represents the average particle size in terms of volume of the heat storage capsule particles, and when a certain volume of particles is sieved in order from the smallest, the particles corresponding to 50% volume are separated. The particle diameter of
The coating layer 3 is not particularly limited as long as it is a resin 9 having a group that reacts with an unreacted group of the polymer compound 8, but is not limited to polyvinyl alcohol, polyacrylamide, ethylene vinyl alcohol, polyvinyl acetate, polyvinyl which are hydrophilic resins. Alcohol-polyvinyl acetate copolymer, polyethylene-polyvinyl acetate copolymer, polyethylene-polyvinyl alcohol copolymer and the like are preferable, and polyvinyl alcohol is particularly preferable. In the case where the polymer compound 8 is a melamine resin, the unreacted group is a methylol group, and the group that the polyvinyl alcohol that reacts with the unreacted group has is a hydroxyl group, an acetate group (the raw material polyvinyl acetate). Residue group). Moreover, as the resin 9 having a group that reacts with an unreacted group when the polymer compound 8 is a melamine resin, a methylol compound, a phenol resin, an isocyanate compound, an epoxy compound, acrylic acid, an aldehyde compound, or the like can be used. .
As addition amount of resin 9 which forms the coating layer 3, 1 mass%-5 mass% with respect to the thermal storage capsule 4, Preferably, 1 mass%-3 mass% are good.

[Heat storage material 5 (molded heat storage material 5a)]
As shown in FIG. 2, the heat storage material 5 is configured to include the heat storage capsule 4 and can be mixed with the adsorbent 6. In the case of the present embodiment, the powder heat storage capsule 4 is used. That is, by drying the dispersion containing the heat storage capsule 4, the powder heat storage capsule 4 can be obtained. Further, as shown in FIG. 2, the powder heat storage capsule 4 is kneaded with the binder 10 and is known. It can be set as the shaping | molding heat storage material 5a with this granulator.
As the binder 10, a known binder can be used, but it can be appropriately selected according to the use application and conditions of the adsorbent 7 with a heat storage function. For example, cellulose such as methyl cellulose and carboxymethyl cellulose, phenol resin, Polyvinyl alcohol, vinyl acetate, amide ester and the like can be used. In particular, when the adsorbent with heat storage function 7 is used in a canister, solvent resistance (transpiration fuel resistance) and water resistance are required, and therefore it is necessary to use a binder 10 that satisfies this requirement. For example, a thermosetting resin such as phenol, acrylic, isocyanate, melamine, urethane, amide ester, etc., which has a JIS hardness (JIS K 1474) of the molded heat storage material 5a of 90% or more. Is preferred.
The shape of the molded heat storage material 5a is not particularly limited, but can be molded into an arbitrary shape such as a pellet (columnar or spherical), a disk, a block, or a honeycomb. Further, the average particle diameter is not particularly limited, but can be generally selected from about 0.1 mm to 4 mm, preferably about 0.3 mm to 3.5 mm, more preferably about 0.5 mm to 2.5 mm.

[Adsorbent 6]
The adsorbent 6 can be a known adsorbent capable of adsorbing gas or the like, and in the case of a canister, a known adsorbent capable of adsorbing a vaporized fuel can be used. For example, activated carbon, zeolite, silica gel, An organometallic complex (copper fumarate, copper terephthalate, copper cyclohexanedicarboxylate, or the like) or a mixture thereof can be used.
Examples of gases that are adsorbed by the adsorbent 6 include methane, methane-based gas (natural gas, digestion gas, etc.), ethane, propane, dimethyl ether, CO ₂ , hydrogen sulfide, oxygen, nitrogen, NO _x , SO _x , CO, acetylene, ethylene, ammonia, methanol, ethanol, water, chloroform, aldehyde, etc. are exemplified, but when the adsorbent 6 is filled in a canister case, a vaporized fuel, particularly gasoline, Become.
As the adsorbent 6, for example, a material obtained by pulverizing activated carbon or the like may be used, and such activated carbon is molded and used as the molded adsorbent 6a. About this shaping | molding, as shown in FIG. 2, it can knead | mix with the binder 10 similarly to the case of the shaping | molding heat storage material 5a, and can shape | mold to the same shape and average particle diameter.

[Adsorbent with heat storage function 7]
The heat storage function-equipped adsorbent 7 is configured by mixing a molded heat storage material 5a including the heat storage capsule 4 and a molded adsorbent 6a. Here, the mixing method is not particularly limited. For example, as shown in FIG. 2, the adsorbent 7 with a heat storage function can be obtained by mixing the molded heat storage material 5a and the molded adsorbent 6a.

Hereinafter, this method will be specifically described with reference to examples.
In addition, although this method is a manufacturing method of the adsorbent 7 with a heat storage function which mixes the heat storage material 5 (molded heat storage material 5a) comprised including the heat storage capsule 4, and the adsorbent 6 (molded adsorbent 6a). In the following examples, when evaluating the heat storage performance and the like of the adsorbent 7 with the heat storage function, the heat storage performance and the like of the heat storage capsule 4 are evaluated.
Example 1
6.5 g of 37% formaldehyde aqueous solution and 10 g of water were added to 5 g of melamine powder and the pH was adjusted to 8, followed by heating to about 70 ° C. to obtain a melamine-formaldehyde initial condensate aqueous solution. To 100 g of an aqueous sodium salt solution of a styrene maleic anhydride copolymer adjusted to pH 4.5, a mixed solution in which 68 g of hexadecane as phase change material 1 was dissolved was added with vigorous stirring, so that the average particle size became about 7 μm. Emulsification was performed until The total amount of the above melamine-formaldehyde initial condensate aqueous solution was added to this emulsified aqueous solution, and the mixture was stirred at 70 ° C. for 2 hours, and then adjusted to pH 9 and encapsulated (heated at the initial heating temperature). This corresponds to an outline forming process for forming the outline 2). By this encapsulation treatment, a dispersion liquid of the heat storage capsule 4 in which hexadecane as the phase change material 1 was enclosed in the outer shell 2 made of melamine resin was obtained. After completion of the reaction, melamine is added to the dispersion liquid of the heat storage capsule 4 by adding polyvinyl alcohol so as to be 1% by mass with respect to the heat storage capsule 4 and stirring again, followed by drying by a spray drying method. A powdery heat storage capsule 4 in which the coating layer 3 made of polyvinyl alcohol was formed on the surface of the outer shell 2 made of resin was obtained. In addition, the adsorbent 7 with a heat accumulating function can be obtained by mixing a molded heat storage material 5a obtained by molding the powder heat storage capsule 4 with a binder 10 and a molded adsorbent 6a obtained by molding the adsorbent 6 with a binder 10. it can.
The average particle diameter of the heat storage capsule 4 at this time was about 7 μm, and the volume ratio of the outer shell 2 to the heat storage capsule 4 was 17%. The thickness of the outer shell 2 was 220 nm.

In FIG. 3, the heat storage capsule 4 is immersed in E10 gasoline (a solvent in which 90% by weight of ethanol is mixed with ethanol at a ratio of 10% by weight), and the immersed heat storage capsule 4 is washed with hexane and vacuumed at 80 ° C. The relationship with the result (calorie | heat amount) evaluated by the differential scanning calorimetry (DSC) after the drying is shown.
As a result, as shown in FIG. 3, in the case of the heat storage capsule 4 provided with the polyvinyl alcohol coating layer 3 (Example 1), the heat storage performance is hardly deteriorated even after 600 hours of immersion. There was found. This is because the coating layer 3 is present on the surface of the outer shell 2, and the destruction and permeation of the outer shell 2 does not proceed substantially depending on E10 gasoline, and the phase change material 1 is prevented from leaking to the outside. It is thought that the decline of the is prevented.

(Comparative Example 1)
A heat storage capsule 4 was obtained by preparing a dispersion liquid of the heat storage capsule 4 by the same method as in Example 1 and then drying by a spray drying method without adding polyvinyl alcohol to the dispersion liquid.
As a result, as shown in FIG. 3, in the case of the heat storage capsule 4 not provided with the coating layer 3 (Comparative Example 1), it was found that the heat storage performance was lowered before 300 hours of immersion time. This is considered that the outer shell 2 made of the polymer compound 8 is destroyed or permeated by E10 gasoline, the phase change material 1 leaks to the outside, and the heat storage performance is lowered.

  Therefore, the resistance to E10 gasoline is different between the case where the coating layer 3 is provided on the surface of the outer shell 2 of the heat storage capsule 4 and the case where the coating layer 3 is not provided. It has been found that the heat storage performance can be prevented from lowering.

(Example 2)
FIG. 4 shows a case where a heat storage capsule 4 manufactured by the same method as in Example 1 is used to repeatedly apply a thermal history so as to cross the phase change temperature, and a phase change between the liquid phase and the solid phase occurs a predetermined number of times. The result (heat amount) of evaluating the amount of heat that can be stored by differential scanning calorimetry (DSC) is shown.
As shown in FIG. 4, when the heat storage capsule 4 manufactured so as to have an average particle diameter of 7 μm by the same method as in Example 1 (Example 2), the heat history is repeated 2500 times or more. However, it was found that the amount of stored heat hardly decreased. This is because the thickness of the outer shell 2 of the heat storage capsule 4, the average particle diameter, and the volume ratio of the outer shell 2 to the heat storage capsule 4 are appropriate, so that it can counter the repeated stress due to the expansion and contraction of the phase change material 1. Thus, it is considered that the strength of the outer shell 2 is appropriately maintained, and the deterioration of the heat storage performance is prevented. In addition, the thickness of the outer shell 2 of the heat storage capsule 4 having an average particle diameter of 7 μm used in Example 2 was 220 nm, and the volume ratio of the outer shell 2 to the heat storage capsule 4 was 17%.

(Comparative Example 2)
As shown in FIG. 4, when the heat storage capsule 4 manufactured so as to have an average particle diameter of 16 μm by the same method as in Example 1 (Comparative Example 2), the heat history is repeated about 1000 times. It was found that the amount of stored heat decreased. In addition, the thickness of the outer shell 2 of the heat storage capsule 4 having an average particle diameter of 16 μm used in Comparative Example 2 was 510 nm, and the volume ratio of the outer shell 2 to the heat storage capsule 4 was 17%.

  Therefore, when the average particle diameter of the heat storage capsule 4 is 16 μm or more, the outer shell 2 becomes too thick to cope with the expansion and contraction due to the phase change of the phase change material 1, and the outer shell 2 is destroyed, and the phase change material 1 It is considered that the heat storage performance deteriorates due to leakage to the outside. Therefore, it is desirable that the average particle diameter is 15 μm or less to prevent the heat history durability from being lowered.

(Example 3)
FIG. 5 shows a differential scanning of the time during which the heat storage capsule 4 manufactured by the same method as in Example 1 is immersed in gasoline and the amount of heat that can be stored after washing the immersed heat storage capsule 4 with hexane and vacuum drying at 80 ° C. The relationship with the result (calorie | heat amount) evaluated by calorimetry (DSC) is shown.
As shown in FIG. 5, when the heat storage capsule 4 manufactured so as to have an average particle diameter of 7 μm by the same method as in Example 1 (Example 3), it was immersed in gasoline for 500 hours or more. It turned out that the amount of heat storage has hardly decreased. This is because the thickness of the outer shell 2 of the heat storage capsule 4, the average particle diameter, and the volume ratio of the outer shell 2 to the heat storage capsule 4 are appropriate, thereby improving the strength of the outer shell 2 of the heat storage capsule 4, particularly the solvent resistance. It is considered that the heat storage performance is prevented from being lowered. The thickness of the outer shell 2 of the heat storage capsule 4 having an average particle size of 7 μm used in Example 3 was 220 nm, and the volume ratio of the outer shell 2 to the heat storage capsule 4 was 17%.

Example 4
As shown in FIG. 5, when the heat storage capsule 4 manufactured so as to have an average particle diameter of 3.5 μm by the same method as in Example 1 (Example 4) is immersed in gasoline for 370 hours or more. However, it turned out that the amount of heat storage has hardly decreased. As in the case of Example 3, the strength, the average particle diameter, and the volume ratio of the outer shell 2 with respect to the thermal storage capsule 4 are appropriate because the thickness of the outer shell 2 of the thermal storage capsule 4 is appropriate. In particular, it is considered that the solvent resistance is improved and the deterioration of the heat storage performance is prevented. In addition, the thickness of the outer shell 2 of the heat storage capsule 4 having an average particle diameter of 3.5 μm used in Example 4 was 160 nm, and the volume ratio of the outer shell 2 to the heat storage capsule 4 was 30%.

(Comparative Example 3)
As shown in FIG. 5, when the heat storage capsule 4 manufactured so as to have an average particle diameter of 2 μm by the same method as in Example 1 (Comparative Example 3) is immersed in gasoline for about 20 hours or more. It was found that the amount of heat storage decreased. In addition, the thickness of the outer shell 2 of the heat storage capsule 4 having an average particle diameter of 16 μm used in Comparative Example 3 was 500 nm, and the volume ratio of the outer shell 2 to the heat storage capsule 4 was 14%.

  Therefore, when the average particle diameter of the heat storage capsule 4 is 2 μm or less, the outer shell 2 becomes too thin to resist destruction and penetration of the outer shell 2 by gasoline, and the phase change material 1 leaks to the outside, and the heat storage performance is improved. It is thought to decrease. On the other hand, when the average particle size is 3.5 μm or more, it is considered that the thickness of the outer shell 2 is sufficiently secured and the heat storage performance is not deteriorated due to the phase change material 1 leaking to the outside. It is done. Therefore, it is desirable to prevent the heat storage performance from being lowered by setting the average particle diameter to 2.8 μm or more, which is near the midpoint of each of the average particle diameters.

[Another embodiment]
(1)
In the first embodiment, the use of the adsorbent with heat storage function 7 manufactured by the present method is not particularly limited, but the adsorbent with heat storage function 7 can also be used particularly for a canister.
Here, the canister is generally used when the vehicle is stopped in order to prevent vaporized fuel (organic solvent, etc.) supplied to an internal combustion engine such as a vehicle from being released to the outside (in the atmosphere, etc.). Excess vaporized fuel is adsorbed by the adsorbent 6 in the case, and the air is introduced into the case as a purge gas during running, and the adsorbed vaporized fuel is desorbed and supplied to the internal combustion engine or the like again. .

In a canister, a heat storage function adsorbent 7 in which a solidified heat storage material 5 and an adsorbent 6 are mixed may be used by filling the case with a solid, and in this case, the adsorbent 6 having a relatively high strength is solid. There is a possibility that the heat storage material 5 is destroyed and the heat storage performance is deteriorated.
In addition, the adsorbent 7 with a heat storage function filled in the case of the canister is in contact with the vaporized fuel such as gasoline and is also in contact with moisture contained in the atmosphere, so that it has solvent resistance (for example, gasoline resistance). Water resistance is required.
Furthermore, the heat storage function adsorbent 7 filled in the case of the canister repeats expansion and contraction due to the phase change of the phase change material 1 contained in the heat storage material 5, so that heat history durability is required. The

  Therefore, the adsorbent 7 with a heat storage function constituted by the heat storage capsule 4 having high strength, excellent solvent resistance, water resistance, and excellent heat history durability described in the first embodiment is used for the canister. When used in a case, it is possible to obtain a canister that can prevent a decrease in adsorption / desorption performance over a long period of time.

The canister is provided with a flow passage through which the vaporized fuel such as gasoline flows in the case, and an inlet into which the vaporized fuel flows and an outlet from which the vaporized fuel flows out are formed on the wall on one end side of the flow passage. The wall on the other end side of the flow passage is provided with an air inlet through which air flows.
In such a canister, the vaporized fuel that has flowed in from the fuel tank through the inlet when the vehicle is stopped is adsorbed to the adsorbent with heat storage function 7 filled in the flow passage in the case, and is adsorbed when the vehicle is running. The vaporized fuel is adsorbed and desorbed so that the vaporized fuel is desorbed by the air flowing in from the air inlet, and the vaporized fuel is supplied to the internal combustion engine from the outlet and burned.

(2)
In the first embodiment, the resin 9 that is not crosslinked with a crosslinking agent is used as the resin 9. However, when the coating layer 3 is formed with a resin, a resin crosslinked with a crosslinking agent can be used. In particular, when polyvinyl alcohol is used as the resin, as a crosslinking agent, an amine compound such as ethylenediamine or urea, an aldehyde compound such as glyoxal or formalin, a methylol compound such as a water-soluble melamine resin, an epoxy compound such as a polyfunctional epoxy resin, Isocyanate compounds such as polyfunctional isocyanate, metal salts such as zirconia nitrate, zirconia chloride, and titanium alkoxide can be used.
In this case, the dispersion liquid of the heat storage capsule 4 is prepared in the same manner as in the first embodiment, and after adding polyvinyl alcohol as a resin to the dispersion liquid, the crosslinking agent is added in an amount of 0.1% by mass with respect to the heat storage capsule. The coating layer 3 made of a crosslinked resin can be formed by mixing ˜3 mass% and drying the dispersion by spray drying.
If necessary, the dispersion layer mixed with the crosslinking agent can be heated and stirred at room temperature to 80 ° C. before the spray drying to form the coating layer 3 of the crosslinked resin.

(3)
In the first embodiment, in order to increase the degree of polymerization of the polymer compound 8 constituting the outer shell 2 of the heat storage capsule 4, only the outer shell forming process is performed at the initial heating temperature (generally about 70 ° C. to 80 ° C.). Although the heat treatment was not performed, the outer shell 2 was formed and encapsulated by the outer shell formation processing, and then the regenerated heat capsule 4 was reheated at a temperature higher than the initial heating temperature (about 100 ° C. to 140 ° C.). be able to.
That is, even when the degree of polymerization of the polymer compound 8 formed in the outer shell forming process is low, the degree of polymerization of the polymer compound 8 is re-performed at a temperature higher than the initial heating temperature. Thus, a dense and strong outline can be formed.
As a result, the degree of polymerization of the polymer compound 8 constituting the outer shell 2 can be improved, and the heat storage capsule 4 with improved solvent resistance and water resistance as well as the strength of the heat storage capsule 4 can be obtained. The performance can be made sufficient.
In the reheating process, the outer shell 2 of the heat storage capsule 4 is formed at the initial heating temperature (relatively low temperature) in the outer shell forming process, and the completed solid heat storage capsule 4 is re-heated by the reheating temperature (relatively high temperature). It can also be performed by heating.
The reheating treatment may be performed before or after the coating layer 3 of the solid heat storage capsule 4 is formed.

  The method for producing an adsorbent with a heat storage function according to the present invention includes: a heat storage capsule containing a heat storage capsule and an adsorbent mixed with the adsorbent; It can be effectively used as a technique that can appropriately prevent a decrease in heat storage performance during continuous use (decrease in heat history durability) and maintain good adsorption / desorption performance.

Schematic configuration diagram of a heat storage capsule in the first embodiment The figure which shows the outline of the manufacturing method of the adsorbent with a heat storage function in 1st Embodiment. Graph showing the relationship between immersion time and heat storage in E10 gasoline A graph showing the relationship between the number of repeated heat histories and the amount of heat stored Graph showing the relationship between the immersion time in gasoline and the amount of heat storage

Explanation of symbols

1: phase change material 2: outer shell 3: coating layer 4: heat storage capsule 5: heat storage material 5a: molded heat storage material 6: adsorbent 6a: molded adsorbent 7: adsorbent with heat storage function 8: polymer compound 9: resin 10 :binder

Claims (9)

With a heat storage function that mixes a heat storage material that includes a heat storage capsule that encloses a phase change material that absorbs and releases latent heat in response to a temperature change in an outer shell made of a polymer compound, and an adsorbent. An adsorbent manufacturing method comprising:
After forming the outer shell thickness of the heat storage capsule in the range of 151 nm or more and 300 nm or less, the surface of the outer shell is covered with a resin having a group that reacts with an unreacted group of the polymer compound,
The heat storage material including the heat storage capsule that has been coated is used as a molded heat storage material molded with a binder, and the adsorbent is formed into a molded adsorbent molded with a binder. Manufacturing method of adsorbent with heat storage function. With a heat storage function that mixes a heat storage material that includes a heat storage capsule that encloses a phase change material that absorbs and releases latent heat in response to a temperature change in an outer shell made of a polymer compound, and an adsorbent. An adsorbent manufacturing method comprising:
The volume ratio of the outer shell to the heat storage capsule is formed in the range of 5% to 30%, and the average particle diameter of the heat storage capsule is formed in the range of 2.8 μm to 15 μm. , Coated with a resin having a group that reacts with an unreacted group of the polymer compound,
The heat storage material including the heat storage capsule that has been coated is used as a molded heat storage material molded with a binder, and the adsorbent is formed into a molded adsorbent molded with a binder. Manufacturing method of adsorbent with heat storage function. After encapsulating through an outer shell forming process to form the outer shell by heating at an initial heating temperature,
The manufacturing method of the adsorbent with a heat storage function of Claim 1 or 2 which reheats the completed said heat storage capsule at the reheating temperature higher than the said initial heating temperature.   The adsorbent with a heat storage function according to any one of claims 1 to 3, wherein the polymer compound is a melamine resin, and the resin having a group that reacts with an unreacted group of the polymer compound is polyvinyl alcohol. Manufacturing method. With a heat storage function that mixes a heat storage material composed of a heat storage capsule formed by enclosing a phase change material that absorbs and releases latent heat in response to temperature changes in an outer shell made of a polymer compound, and an adsorbent. An adsorbent material,
The outer thickness of the heat storage capsule is formed in a range of 151 nm or more and 300 nm or less, and has a resin coating layer having a group that reacts with an unreacted group of the polymer compound on the surface of the outer shell,
An adsorbent with a heat storage function obtained by mixing a molded heat storage material obtained by molding the heat storage material including the heat storage capsule having the coating layer with a binder and a molded adsorbent obtained by molding the adsorbent with a binder. With a heat storage function that mixes a heat storage material composed of a heat storage capsule formed by enclosing a phase change material that absorbs and releases latent heat in response to temperature changes in an outer shell made of a polymer compound, and an adsorbent. An adsorbent material,
A volume ratio of the outer shell to the heat storage capsule is formed in a range of 5% to 30%, and an average particle diameter of the heat storage capsule is formed in a range of 2.8 μm to 15 μm. And a resin coating layer having a group that reacts with an unreacted group of the polymer compound,
An adsorbent with a heat storage function obtained by mixing a molded heat storage material obtained by molding the heat storage material including the heat storage capsule having the coating layer with a binder and a molded adsorbent obtained by molding the adsorbent with a binder. After encapsulating through an outer shell forming process to form the outer shell by heating at an initial heating temperature, the heat storage capsule is completed,
The adsorbent with a heat storage function according to claim 5 or 6, comprising the heat storage capsule reheated at a reheating temperature higher than the initial heating temperature.   The adsorbent with a heat storage function according to any one of claims 5 to 7, wherein the polymer compound is a melamine resin, and the resin having a group that reacts with an unreacted group of the polymer compound is polyvinyl alcohol. .   A canister formed by filling the adsorbent with a heat storage function according to any one of claims 5 to 8 in a case.

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