CN111629979A - Coating film for vacuum container, coating liquid, and vacuum heat-insulating container - Google Patents
Coating film for vacuum container, coating liquid, and vacuum heat-insulating container Download PDFInfo
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- CN111629979A CN111629979A CN201980009185.3A CN201980009185A CN111629979A CN 111629979 A CN111629979 A CN 111629979A CN 201980009185 A CN201980009185 A CN 201980009185A CN 111629979 A CN111629979 A CN 111629979A
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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Abstract
A coating film (4, 5) of a vacuum container (1), wherein the vacuum container (1) comprises a bottomed cylindrical outer cylinder (3), a bottomed cylindrical inner cylinder (2) disposed inside the outer cylinder (3), and a coating film (4, 5). A hollow section (S1) that is depressurized compared with the atmospheric pressure is formed between the outer surface of the inner cylinder (2) and the inner surface of the outer cylinder (3). The inner cylinder (2) and the outer cylinder (3) are joined to seal the hollow section (S1), and the coating film (4, 5) is formed on at least one of the inner surface of the outer cylinder (3) and the outer surface of the inner cylinder (2) in the hollow section (S1). The coating films (4, 5) contain copper ion-exchanged ZSM-5 zeolite as a gas adsorbent.
Description
Technical Field
The present invention relates to a vacuum container such as a vacuum heat insulating container.
Background
As disclosed in patent document 1, a vacuum heat insulating container is known, which includes, for example, an inner tube and an outer tube, and a hollow portion that is depressurized compared with the atmospheric pressure is formed between the outer tube and the inner tube. An adsorbent is disposed in the hollow portion.
In the vacuum vessel having such a structure, there is a case where it is required to further improve the adsorption performance of the adsorbent according to the specification.
Further, as a method for producing a copper ion-exchanged ZSM-5-type zeolite used for a gas adsorbent, for example, a technique disclosed in patent document 2 is known.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 7-148078
Patent document 2: japanese patent No. 5719995 publication
Disclosure of Invention
The invention provides a coating film, a coating liquid and a vacuum heat insulation container of a vacuum container, which can improve the adsorption performance of a gas adsorption material in the vacuum container.
The film of the present invention is a film of a vacuum container. The vacuum container includes a bottomed cylindrical outer tube, a bottomed cylindrical inner tube disposed inside the outer tube, and a coating film. A hollow portion decompressed compared with the atmospheric pressure is formed between the outer surface of the inner cylinder and the inner surface of the outer cylinder. The inner cylinder is engaged with the outer cylinder to seal the hollow portion. The coating film is formed on at least one of the inner surface of the outer cylinder and the outer surface of the inner cylinder in the hollow portion. The coating film contains copper ion-exchanged ZSM-5 zeolite as a gas adsorbent.
According to such a structure, the coating contains a gas adsorbent having high gas adsorption performance, i.e., copper ion-exchanged ZSM-5 type zeolite. This allows the gas adsorbent to favorably adsorb the unnecessary gas present in the hollow portion. This can improve the adsorption performance of the gas adsorbent.
The coating liquid of the present invention contains at least the gas adsorbent and the binder, and is used for coating and forming the coating film.
The vacuum heat insulation container of the present invention has the above-described coating film.
According to the present invention, it is possible to provide a coating film, a coating liquid, and a vacuum heat insulating container for a vacuum container, which can improve the adsorption performance of a gas adsorbent in the vacuum container.
Drawings
Fig. 1 is a sectional view of a vacuum insulated container according to an embodiment of the present invention.
Fig. 2A is a sectional view showing a part of a method for forming a coating film according to an embodiment of the present invention.
Fig. 2B is a sectional view showing a part of the method for forming a coating film according to the embodiment of the present invention.
Detailed Description
(example of embodiment of the present invention)
An example of the coating film according to the aspect of the present invention is a coating film of a vacuum container. The vacuum container includes a bottomed cylindrical outer tube, a bottomed cylindrical inner tube disposed inside the outer tube, and a coating film. A hollow portion decompressed compared with the atmospheric pressure is formed between the outer surface of the inner cylinder and the inner surface of the outer cylinder. The inner cylinder is engaged with the outer cylinder to seal the hollow portion. The coating film is formed on at least one of the inner surface of the outer cylinder and the outer surface of the inner cylinder in the hollow portion. The coating film contains copper ion-exchanged ZSM-5 zeolite as a gas adsorbent.
According to such a structure, the coating contains a gas adsorbent having high gas adsorption performance, i.e., copper ion-exchanged ZSM-5 type zeolite. This allows the gas adsorbent to favorably adsorb the unnecessary gas present in the hollow portion. Therefore, the adsorption performance of the gas adsorbent can be improved.
Further, the coating film may have a foamed structure.
This makes it possible to expose the surface of the gas adsorbent contained in the coating film to a large amount in the hollow portion, and easily ensure a large adsorption amount of the gas adsorbent.
The particle size of the copper ion-exchanged ZSM-5 zeolite may be set to a value of 300 μm or less.
When the copper ion-exchanged ZSM-5-type zeolite is formed to have such a particle size, the gas adsorbent can be easily disposed in the hollow portion even when the volume of the hollow portion is limited. Further, even when the gas adsorbent detached from the coating moves in the hollow portion, it is possible to make it difficult to generate noise caused by the gas adsorbent colliding with the outer cylinder or the inner cylinder.
Further, the coating film may contain an inorganic binder.
By using the inorganic binder, it is also possible to prevent the loss of the gas adsorption activity of the copper ion-exchanged ZSM-5-type zeolite as a gas adsorbent due to the binder contained in the coating film.
The weight of the inorganic binder in the coating film may be set to a value in a range of more than 0 wt% and not more than 20 wt% of the weight of the coating film.
By setting the weight of the inorganic binder to a value within the above range, it is possible to prevent the adsorption performance of the copper ion-exchanged ZSM-5-type zeolite contained in the gas adsorbent from being hindered by a large amount of the inorganic binder, and to satisfactorily hold the gas adsorbent in the coating with the inorganic binder.
The nitrogen adsorption amount of the gas adsorbent may be set to a value of 10ml/g or more at normal temperature and normal pressure.
According to this configuration, it is possible to adsorb and remove a gas such as nitrogen remaining in the hollow portion during the production of the vacuum container and a gas such as nitrogen permeating into the hollow portion after the production of the container. Therefore, the adsorption performance of the gas adsorbent at the beginning after production can be improved, and the adsorption performance can be maintained well.
The coating liquid according to an aspect of the present invention contains at least the gas adsorbent and the binder, and is used for coating and forming the coating film.
According to this configuration, when manufacturing the vacuum container, the coating liquid is applied to at least one of the inner surface of the outer cylinder and the outer surface of the inner cylinder in the hollow portion and dried, whereby the coating film can be formed relatively easily.
Further, the coating liquid may contain a thermal decomposition type foaming agent.
In this way, a coating film having a foamed structure can be formed by thermally decomposing the applied coating liquid.
The vacuum insulation container of the present invention has any one of the above-described coatings.
According to the aspects of the present invention, in the vacuum container having the inner cylinder and the outer cylinder, the hollow portion decompressed compared with the atmospheric pressure is formed between the outer cylinder and the inner cylinder, and the gas adsorbent is disposed in the hollow portion, the improvement of the adsorption performance of the gas adsorbent can be stably achieved.
(embodiment mode)
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Fig. 1 is a sectional view of a vacuum insulated container 1 (hereinafter, simply referred to as a container 1) according to an embodiment of the present invention.
As shown in fig. 1, the container 1 is formed in a bottle shape as a whole. In the present specification, vacuum refers to a state in which the pressure is reduced from the atmospheric pressure.
The container 1 includes an inner cylinder 2, an outer cylinder 3, and coating films 4, 5.
The outer cylinder 3 and the inner cylinder 2 are formed in a bottomed cylindrical shape. The outer cylinder 3 and the inner cylinder 2 are made of a gas impermeable material. In the present embodiment, the outer cylinder 3 and the inner cylinder 2 are made of a metal material, for example. Examples of the metal material include aluminum, iron, stainless steel, and copper.
The outer cylinder 3 and the inner cylinder 2 are formed in a cylindrical shape. The inner cylinder 2 has a side portion 2a, a bottom portion 2b, a neck portion 2c, and a shoulder portion 2 d. The side portion 2a and the neck portion 2c are formed in a cylindrical shape extending in the cylinder axis direction of the inner cylinder 2. The bottom portion 2b is formed in a circular shape as viewed in the tube axis direction of the inner tube 2 (upward or downward direction in fig. 1), for example. The side portion 2a extends from the peripheral edge of the bottom portion 2b in the cylinder axial direction of the inner cylinder 2.
The neck portion 2c has an inner diameter smaller than that of the side portion 2 a. The neck portion 2c extends in the cylinder axial direction of the inner cylinder 2 from the side of the side portion 2a opposite to the bottom portion 2b side via a shoulder portion 2 d. The side of the neck portion 2c opposite to the bottom portion 2b is formed with an opening whose outside communicates with the inside of the inner cylinder 2. The neck 2c and the side 2a are connected by a shoulder 2 d. The bottle shoulder portion 2d is formed in an annular shape when viewed from the cylinder axis direction of the inner cylinder 2.
The outer cylinder 3 has a side portion 3a, a bottom portion 3b, a neck portion 3c, and a shoulder portion 3 d. The side portion 3a and the bottleneck portion 3c are formed in a cylindrical shape extending in the cylinder axial direction of the outer cylinder 3. The bottom portion 3b is formed in a circular shape as viewed from the cylinder axis direction of the outer cylinder 3, for example. The side portion 3a extends from the periphery of the bottom portion 3b in the cylinder axial direction of the outer cylinder 3.
The neck portion 3c has an inner diameter smaller than that of the side portion 3 a. The bottleneck portion 3c extends in the cylinder axial direction of the outer cylinder 3 from the side of the side portion 3a opposite to the bottom portion 3b side via the shoulder portion 3 d. On the side of the neck portion 3c opposite to the bottom portion 3b, an opening is formed through which the inside of the container 1 communicates with the outside. The neck portion 3c and the side portion 3a are connected by a bottle shoulder portion 3 d. The bottle shoulder portion 3d is formed in a ring shape as viewed from the cylinder axis direction of the outer cylinder 3.
The side portion 3a has a larger inner diameter than the side portion 2 a. The inner diameter of the neck portion 3c is larger than that of the neck portion 2 c. The diameter of the bottom 3b is larger than the diameter of the bottom 2 b.
The inner tube 2 is disposed inside the outer tube 3 with a hollow portion S1 formed between the outer surface of the inner tube 2 and the inner surface of the outer tube 3. For example, the inner cylinder 2 is disposed inside the outer cylinder 3 in a state where the cylinder axis direction thereof coincides with the cylinder axis direction of the outer cylinder 3. The volume of the inner cylinder 2 is set to a value in the range of 400ml to 600ml, and is 500ml in this case.
In the container 1, in a state where the inner tube 2 is disposed inside the outer tube 3, the opening periphery of the opening of the inner tube 2 and the opening periphery of the opening of the outer tube 3 are integrally connected. Thereby, the inner cylinder 2 is joined to the outer cylinder 3 so as to seal the hollow portion S1.
Thus, in the container 1, the contact portion between the outer cylinder 3 and the inner cylinder 2 is defined at the opening peripheral edge of each opening. This can minimize the formation of a thermal bridge between the outer cylinder 3 and the inner cylinder 2, and can also exhibit a vacuum heat insulating effect between the outer cylinder 3 and the inner cylinder 2.
Further, if the thermal bridge is formed within the allowable range, the outer cylinder 3 and the inner cylinder 2 can be thermally bonded in the region other than the opening periphery of each opening.
The opening of the inner cylinder 2 is closed by a cap 6. The cap 6 is disposed, for example, so that a part of the inner region of the opening of the inner tube 2 is in close contact with a part of the outer region of the opening of the outer tube 3. Thereby, the inside S2 of the inner tube 2 is kept airtight.
The hollow portion S1 was depressurized compared with the atmospheric pressure, and the internal pressure of the hollow portion S1 was set to 1 × 10 as an example-3Pa or less, the internal pressure of the hollow section S1 is preferably 1 × 10-4Pa or less, the internal pressure of the hollow part S1 in the container 1 can be set to 1 × 10 by sufficiently reducing the pressure in the hollow part S1-4Pa or less.
The volume of the hollow portion S1 is set to a value in the range of 10ml to 20ml, and is 15ml in this case.
The bottle necks 2c and 3c are not essential and may be omitted. The outer cylinder 3 and the inner cylinder 2 may be formed in a square cylinder shape extending in the cylinder axial direction, or may be formed in different shapes from each other.
The coating films 4 and 5 are formed on at least one (here, both) of the inner surface of the outer cylinder 3 and the outer surface of the inner cylinder 2 in the hollow portion S1. The coating films 4 and 5 contain copper ion-exchanged ZSM-5 type zeolite as a gas adsorbent.
For example, the coating 4 is formed on the surfaces of the side portion 3a and the bottom portion 3b of the inner surface of the outer cylinder 3. Further, a coating film 5 is formed on the surfaces of the side portion 2a and the bottom portion 2b among the outer surfaces of the inner cylinder 2. The coating films 4, 5 have a foamed structure. This ensures that the surface area of the coating films 4 and 5 is large. The container 1 has a film structure 10 formed by the films 4 and 5.
The foam structure is a structure that is molded into a foam (foam) or porous shape in a state where the gas is dispersed in the film.
The thickness of the coatings 4 and 5 is set to a value in the range of 1 μm to 500 μm, for example. The thickness dimension is preferably in the range of 1 μm to 400 μm, and more preferably in the range of 100 μm to 300 μm.
The gas adsorbent adsorbs the gas in the hollow portion S1. The gas contains at least one of nitrogen, oxygen, hydrogen, and carbon dioxide, for example. In addition, the gas adsorbent adsorbs hydrocarbon gases having a relatively low molecular weight, such as methane and ethane.
For example, the particle size of the copper ion-exchanged ZSM-5 type zeolite is set to a value of 300 μm or less. The copper ion-exchanged ZSM-5 type zeolite has a plurality of pores whose pore diameter is set to
The above
The following ranges of values.
The diameter of the pores of the copper ion-exchanged ZSM-5-type zeolite is set to the value within the above range. Thus, according to the study of the inventors, when the hollow portion S1 is depressurized compared to the atmosphere, the copper ion-exchanged ZSM-5-type zeolite exists in the hollow portion S1, and gas molecules such as nitrogen and oxygen can be adsorbed well. The hollow portion S1 is in a state of gas concentration leaner than the atmosphere. Therefore, excellent adsorption performance due to the copper ion-exchanged ZSM-5-type zeolite can be expected.
As the value of the pore diameter of the copper ion-exchanged ZSM-5 type zeolite, for example, the one having a pore diameter of a copper ion-exchanged ZSM-5 type zeolite is preferable
Above and below
More preferably, the value of
The above
The following ranges of values. In addition, in another example, Z is exchanged as copper ionThe value of the pore diameter of the SM-5 type zeolite, for example, is preferably insufficient
A value of (d).
The gas adsorbent is molded so that the density is set to a value in the range of 2g/ml or less, which is greater than 0 g/ml. The density of the gas adsorbent is, for example, more preferably in the range of 0.5g/ml to 1.7g/ml, and still more preferably in the range of 0.9g/ml to 1.4 g/ml.
For example, when the density of the gas adsorbent is set to a value in the range of 0.9g/ml to 1.4g/ml, the porosity of the copper ion-exchanged ZSM-5-type zeolite in the gas adsorbent is in the range of about 40% to 60%. Thus, when degassing the hollow portion S1 using a vacuum pump or the like in the production of the container 1, the gas in the gas adsorbent can be quickly and appropriately removed. Further, the surface area of the gas adsorbent capable of adsorbing the gas can be easily ensured.
The nitrogen adsorption amount of the gas adsorbent is set to a value of 10ml/g or more at normal temperature (20. + -. 15 ℃ C.) and normal pressure (atmospheric pressure). The value of the nitrogen adsorption amount is preferably 2ml/g or more at room temperature under an equilibrium pressure of 10 Pa. The coating films 4 and 5 may contain a gas adsorbing component other than the copper ion-exchanged ZSM-5 type zeolite. Further, at least any one of a plurality of recesses and/or through holes may be formed on the surface of the coating films 4 and 5. This can further increase the surface area of the coating films 4 and 5.
The gas adsorbent material contains an inorganic binder. Examples of the inorganic binder include at least one of silica and alumina, and water-dispersed silica sol, water-dispersed alumina sol, colloidal silica, water glass, and the like can be used.
The weight of the inorganic binder in the coating 4 is set to a value in a range of more than 0 wt% and not more than 20 wt% of the weight of the coating 4. The weight of the inorganic binder in the coating 4 is preferably a value in a range of more than 0 wt% and not more than 10 wt% of the weight of the coating 4. The weight of the inorganic binder in the coating 5 is also the same, for example.
The gas adsorbent is disposed in the hollow portion S1 in an activated state. Specifically, the gas adsorbent is disposed in the hollow portion S1 in a state where the adsorbed gas is sufficiently released. As a method for activating the gas adsorbent, for example, a method of heating the gas adsorbent in a reduced pressure atmosphere can be cited. The gas adsorbent is disposed in the activated state in the hollow portion S1, the interior of which is depressurized when the container 1 is manufactured.
The internal pressure of the hollow portion S1 at this time is preferably a value of, for example, 10mPa or less, and more preferably a value of 1mPa or less. The heating temperature of the gas adsorbent is preferably 300 ℃ or higher, and more preferably 400 ℃ or higher and 700 ℃ or lower. By heating the gas adsorbent, the copper ions can be exchanged for the 2-valent copper ions (Cu) contained in the ZSM-5 zeolite2+) Reduction to 1-valent copper ion (Cu)+) Thereby, the copper ion-exchanged ZSM-5 zeolite can be activated.
The activated copper ion-exchanged ZSM-5-type zeolite well adsorbs the gas present in hollow S1 at room temperature. Thus, even when the hollow S1 is set to a high vacuum, the copper ion-exchanged ZSM-5-type zeolite can exhibit adsorption performance without releasing gas.
In the hollow portion S1 of the container 1 just manufactured, at least 60% or more of the copper sites of the copper ion-exchanged ZSM-5-type zeolite are, for example, copper 1 valence sites. The copper 1 valence site is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more of the copper sites in the copper ion-exchanged ZSM-5-type zeolite.
As a method for exchanging copper ions with ZSM-5 type zeolite, a known method can be used. For example, a method of impregnating a ZSM-5 type zeolite with a copper soluble salt aqueous solution such as a copper chloride aqueous solution or a copper ammine complex aqueous solution can be mentioned. For a method for producing a copper ion-exchanged ZSM-5-type zeolite, for example, japanese patent No. 5719995 (patent document 2) can be referred to.
Fig. 2A and 2B are sectional views showing a method of forming the coating films 4 and 5.
Fig. 2A and 2B show, as an example, a case where the coating 4 is formed on the surface of the outer tube 3, and the same applies to a method of forming the coating 5 on the surface of the inner tube 2. The method for forming the coating films 4 and 5 includes: an adjustment step of adjusting the coating liquid; a coating step of coating the adjusted coating liquid on the target surface of the container 1; and a drying step of drying the applied coating liquid.
In the adjustment step, the operator adjusts the coating liquid 14 using a plurality of materials. The coating liquid 14 is used to coat and form the coating films 4 and 5, and contains at least the gas adsorbent and the binder. In the present embodiment, the coating liquid 14 containing a thermal decomposition type foaming agent in addition to the gas adsorbent and the binder is adjusted. As the binder, the above inorganic binder can be used. As the thermal decomposition type foaming agent, known ones can be used. The coating liquid 14 may be adjusted to contain other components such as a viscosity adjuster.
In the coating step, the operator coats the target surface of the container 1 (the inner surface of the bottom 3b of the outer tube 3 in fig. 2A) with the coating liquid 14. At this time, the operator adjusts the number of times and the amount of coating of the coating liquid 14 in accordance with the final (after-drying) film thickness dimension of the coating films 4 and 5.
In the drying step, the operator heats the applied coating liquid 14 to volatilize volatile components of the coating liquid 14. Thereby, the coating liquid 14 is dried. The coating liquid 14 on the surface of the object may be heated all at once after coating, or may be heated in each of a plurality of coatings. That is, the coating step and the drying step may be alternately repeated a plurality of times.
When all the drying steps are finished, the coating liquid 14 is dried to form the coating films 4 and 5 (fig. 2B). Here, since the coating liquid 14 contains a thermal decomposition type foaming agent, the coating films 4 and 5 can be formed to have a foamed structure by heating the coating liquid 14.
As described above, in the container 1, the coating films 4 and 5 contain the copper ion-exchanged ZSM-5 type zeolite that is a gas adsorbent having high gas adsorption performance. This allows the unnecessary gas present in the hollow portion S1 to be satisfactorily adsorbed by the gas adsorbent. Therefore, the adsorption performance of the gas adsorbent can be improved. In the container 1 of the present embodiment, heat conduction due to unnecessary gas can be prevented, and the vacuum insulation between the outer cylinder 3 and the inner cylinder 2 can be improved.
The copper ion-exchanged ZSM-5-type zeolite can adsorb and remove gas remaining in the hollow portion S1 during the production of the container 1 and gas such as hydrogen permeating through the hollow portion S1 from the outside of the container 1 after the production. This improves the initial vacuum heat insulating performance after production, and can maintain the vacuum heat insulating performance well.
Further, the outer cylinder 3 and the inner cylinder 2 are formed of a metal material, and therefore the outer cylinder 3 and the inner cylinder 2 have good rigidity. Thus, even if the hollow portion S1 is set to a high vacuum, the shapes of the outer cylinder 3 and the inner cylinder 2 can be maintained without providing a reinforcement in the hollow portion S1. Therefore, the vacuum insulation between the outer cylinder 3 and the inner cylinder 2 can be stably obtained while the container 1 is kept lightweight. Further, since the reinforcement does not have to be disposed in the hollow portion S1, when the gas adsorbent of the coating films 4 and 5 adsorbs the gas in the hollow portion S1, the reinforcement can be prevented from being an obstacle.
Further, as for the thermal conductivity of the coatings 4 and 5, since the coatings 4 and 5 contain copper ion-exchanged ZSM-5 type zeolite, the thermal conductivity of each of the inner tube 2 and the outer tube 3 can be set to a low value. Thus, by disposing the coatings 4 and 5 in the hollow portion S1, it is possible to prevent an increase in heat conduction between the outer cylinder 3 and the inner cylinder 2, and to obtain excellent vacuum heat insulating performance of the container 1.
The thermal conductivity of the copper ion-exchanged ZSM-5-type zeolite is lower than that of a general gas adsorbent made of an alloy material, except for the inner tube 2 and the outer tube 3. Therefore, compared to the case of using a general gas adsorbent made of an alloy material, the degree of freedom in design can be improved while maintaining the excellent vacuum insulation performance of the container 1.
Here, the conventional alloy getter has a reduced adsorption performance when an oxide film is formed on the surface. Therefore, in the conventional alloy getter, the oxide film on the surface is removed by heat treatment, thereby obtaining a desired adsorption performance. Then, the adsorption performance of the conventional alloy getter is high at a high temperature in the heat treatment, but is reduced at a normal temperature.
In contrast, copper ion-exchanged ZSM-5 type zeolite does not form an oxide film on the surface unlike such a conventional alloy getter. Further, even at room temperature, excellent adsorption performance can be continuously exhibited. Therefore, hydrogen or the like permeating through and entering the metal case can be adsorbed continuously.
The particle size of the copper ion-exchanged ZSM-5 zeolite is set to a value of 300 μm or less. By setting the copper ion-exchanged ZSM-5 type zeolite to such a particle size, the gas adsorbent can be easily disposed in the hollow portion S1 even when the volume of the hollow portion S1 is limited. Further, even when the gas adsorbent detached from the coating films 4 and 5 moves in the hollow portion S1, it is possible to make it difficult to generate noise that the gas adsorbent collides with the outer cylinder 3 or the inner cylinder 2.
According to the studies of the inventors, it has been found that the pore diameter of the copper ion-exchanged ZSM-5-type zeolite is closer to the size of gas molecules to be adsorbed by the copper ion-exchanged ZSM-5-type zeolite in a reduced pressure atmosphere, and the copper ion-exchanged ZSM-5-type zeolite is more likely to adsorb gas.
It is considered that in hollow S1, nitrogen molecules are present (molecular size: about
) Oxygen molecules (molecular size: about
) And water molecules (molecular size: about
) At least any one of. By using such gas molecules, the pore diameters of the copper ion-exchanged ZSM-5-type zeolite are set to values in the range including the above-described molecular sizes, whereby the copper ion-exchanged ZSM-5-type zeolite can favorably adsorb the above-described gas molecules.
Further, by setting the pore diameter of the copper ion-exchanged ZSM-5-type zeolite contained in the gas adsorbent to a small value in the above range, it is possible to make it difficult for gas molecules to be desorbed from the copper ion-exchanged ZSM-5-type zeolite, as compared with the case where the pore diameter is set to a large value. This effect can be obtained well when the temperature of the container 1 rises and the kinetic energy of the gas molecules in the hollow portion S1 becomes high.
The gas adsorbent is molded so that the density is set to a value in the range of 2g/ml or less, which is greater than 0 g/ml. This makes it possible to expose the surface of the gas adsorbent to the hollow portion S1 more, and easily ensure a large amount of adsorption of the gas adsorbent.
Further, since the films 4 and 5 contain the inorganic binder, the inorganic binder can prevent the adsorption performance of the copper ion-exchanged ZSM-5 type zeolite as the gas adsorbent from being hindered by the inorganic binder, and the inorganic binder can hold the gas adsorbent in the films 4 and 5 well.
The weight of the inorganic binder in the coating films 4 and 5 is set to a value in the range of more than 0 wt% and not more than 20 wt% of the weight of the coating films 4 and 5. This prevents the adsorption performance of the copper ion-exchanged ZSM-5-type zeolite contained in the gas adsorbent from being impaired by a large amount of the inorganic binder, and allows the gas adsorbent to be favorably held by the inorganic binder in the membranes 4 and 5.
The nitrogen adsorption amount of the gas adsorbent is set to a value of 10ml/g or more at normal temperature and normal pressure. With this configuration, the gas such as nitrogen remaining in the hollow portion S1 and the gas such as nitrogen permeating into the hollow portion S1 after the production of the container 1 can be adsorbed and removed during the production of the container 1. This improves the adsorption performance of the gas adsorbent at the beginning after production, and can maintain the adsorption performance well.
As described above, in the container 1 of the present embodiment, the vacuum heat insulating performance at the initial stage after the production can be improved, and the vacuum heat insulating performance can be maintained well.
In the present embodiment, the thickness of the coatings 4 and 5 is set to a value in the range of 100 μm to 300 μm. Accordingly, a large amount of the gas adsorbent can be disposed in the hollow portion S1, and the gas present in the hollow portion S1 can be adsorbed and removed satisfactorily.
In addition, when manufacturing the container 1, the coating films 4 and 5 can be relatively easily formed by applying the coating liquid 14 to at least one of the inner surface of the outer tube 3 and the outer surface of the inner tube 2 in the hollow portion S1 and drying the same. Further, since the coating liquid 14 contains a thermal decomposition type foaming agent, the coating films 4 and 5 having a foamed structure can be formed by thermally decomposing the applied coating liquid 14.
The present invention is not limited to the above embodiments, and the configurations thereof may be changed, added, or deleted without departing from the scope of the present invention.
For example, the coating film may be disposed at a plurality of positions on at least one of the inner surface of the outer cylinder 3 and the outer surface of the inner cylinder 2 in the hollow portion S1. In this case, the coating films having different at least one of film thickness size and shape may be disposed at a plurality of positions. Further, a film having a large area may be disposed on at least one of the side portions 2a and 3a, and a film having a small area may be disposed on at least one of the bottom portions 2b and 3 b.
Further, a surface of the coating film may be disposed on the inner surface of the outer cylinder 3 and the outer surface of the inner cylinder 2 in the hollow portion S1, and a recess for holding the coating film may be formed. The recess may be formed to extend in the circumferential direction of the inner cylinder 2 and the outer cylinder 3, or may be formed to extend in the axial direction of the inner cylinder 2 and the outer cylinder 3. The container 1 does not need to be a vacuum heat insulating container, and may be a vacuum container which does not need heat insulation.
Industrial applicability of the invention
As described above, the present invention is a vacuum heat insulating container having an inner cylinder and an outer cylinder, and a hollow portion decompressed compared with the atmospheric pressure is formed between the outer cylinder and the inner cylinder, and this vacuum heat insulating container has an advantageous effect of stably improving the vacuum heat insulating performance thereof. Therefore, the present invention can be widely applied to vacuum vessels such as vacuum heat insulating vessels, and is useful.
Description of the reference numerals
1 container (vacuum heat insulation container)
2 inner cylinder
2a side part
2b bottom
2c bottle neck
2d bottle shoulder
3 outer cylinder
3a side part
3b bottom
3c bottle neck
3d bottle shoulder
4. 5 coating film
6 bottle cap
10 tectorial membrane structure
14 coating liquid
Hollow part of S1
Inside S2
Claims (9)
1. A film for a vacuum container, characterized in that:
the vacuum vessel includes: a bottomed cylindrical outer tube, a bottomed cylindrical inner tube disposed inside the outer tube, and the coating film,
a hollow portion decompressed compared with atmospheric pressure is formed between an outer surface of the inner cylinder and an inner surface of the outer cylinder, the inner cylinder and the outer cylinder are joined to seal the hollow portion,
the coating film is formed on at least one of the inner surface of the outer cylinder and the outer surface of the inner cylinder in the hollow portion,
the coating contains copper ion-exchanged ZSM-5 zeolite as a gas adsorbent.
2. A coating film for a vacuum vessel according to claim 1, wherein:
the covering film has a foamed structure.
3. The film for a vacuum vessel according to claim 1 or 2, wherein:
the particle diameter of the copper ion-exchanged ZSM-5 zeolite is set to a value of 300 μm or less.
4. The coating film for a vacuum vessel according to any one of claims 1 to 3, wherein:
the coating film contains an inorganic binder.
5. The film for a vacuum vessel according to claim 4, wherein:
the weight of the inorganic binder in the coating film is set to a value in a range of more than 0 wt% and not more than 20 wt% of the weight of the coating film.
6. The coating film for a vacuum vessel according to any one of claims 1 to 5, wherein:
the nitrogen adsorption amount of the gas adsorbent is set to a value of 10ml/g or more at normal temperature and pressure.
7. A coating liquid characterized by comprising:
a coating film according to any one of claims 1 to 6, which contains at least the gas adsorbent and a binder and is applied to form the coating film.
8. The coating liquid according to claim 7, characterized in that:
also contains a thermal decomposition type foaming agent.
9. A vacuum insulated container characterized by:
the coating film according to any one of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-011577 | 2018-01-26 | ||
| JP2018011577 | 2018-01-26 | ||
| PCT/JP2019/001166 WO2019146471A1 (en) | 2018-01-26 | 2019-01-17 | Coating film, coating liquid for vacuum container, and vacuum insulation container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111629979A true CN111629979A (en) | 2020-09-04 |
Family
ID=67395640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980009185.3A Pending CN111629979A (en) | 2018-01-26 | 2019-01-17 | Coating film for vacuum container, coating liquid, and vacuum heat-insulating container |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2019146471A1 (en) |
| CN (1) | CN111629979A (en) |
| WO (1) | WO2019146471A1 (en) |
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| JP2008050020A (en) * | 2006-08-23 | 2008-03-06 | Matsushita Electric Ind Co Ltd | Synthetic resin insulating container |
| JP6411457B2 (en) * | 2013-03-29 | 2018-10-24 | トキタエ エルエルシー | Temperature controlled storage system |
| JP2015105806A (en) * | 2013-12-02 | 2015-06-08 | 三菱電機株式会社 | Vacuum heat insulation box |
| JP2015169372A (en) * | 2014-03-06 | 2015-09-28 | 大日本印刷株式会社 | Heat insulation container, and method of manufacturing heat insulation container |
| JP6726842B2 (en) * | 2014-05-22 | 2020-07-22 | パナソニックＩｐマネジメント株式会社 | Insulation |
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2019
- 2019-01-17 WO PCT/JP2019/001166 patent/WO2019146471A1/en active Application Filing
- 2019-01-17 CN CN201980009185.3A patent/CN111629979A/en active Pending
- 2019-01-17 JP JP2019567016A patent/JPWO2019146471A1/en active Pending
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| JPH01317413A (en) * | 1988-06-20 | 1989-12-22 | Kawasaki Steel Corp | Vacuum heat insulating double vessel and manufacture |
| JPH06113963A (en) * | 1992-10-06 | 1994-04-26 | Nippon Sanso Kk | Vacuum heat-insulating container made of synthetic resin and manufacture thereof |
| JPH07148078A (en) * | 1993-11-25 | 1995-06-13 | Nippon Sanso Kk | Vacuum heat insulating vessel made of synthetic resin and its manufacture |
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| JP2010259967A (en) * | 2009-04-30 | 2010-11-18 | Panasonic Corp | Device for adsorbing gas |
| US20130160652A1 (en) * | 2010-09-09 | 2013-06-27 | Panasonic Corporation | Sheet-shaped gas adsorbent and insulating body using same |
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| WO2014174837A1 (en) * | 2013-04-23 | 2014-10-30 | パナソニックＩｐマネジメント株式会社 | Insulator including gas adsorbing material |
| JP2016152878A (en) * | 2015-02-20 | 2016-08-25 | タイガー魔法瓶株式会社 | Vacuum double container |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019146471A1 (en) | 2021-03-04 |
| WO2019146471A1 (en) | 2019-08-01 |
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