KR20160057287A - Gas Adsorbing Material, and Vacuum Insulation Material Including Same - Google Patents

Abstract

A gas adsorbing material capable of reducing the gas adsorption rate while maintaining the gas adsorption performance and enhancing the gas barrier property to the target gas, and a zeolite skeleton as the ZSM-5 type zeolite subjected to copper ion exchange as the vacuum insulating material using the gas adsorbing material And a sintered body of a compression-molded product comprising a gas-absorbing composition and a water-absorbing material, wherein the ratio of silica to alumina is 10 or more and 50 or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a gas adsorbing material and a vacuum insulating material using the gas adsorbing material,

The present invention relates to a gas adsorbing material and a vacuum insulator using the gas adsorbing material. Gas adsorbent materials are used in various fields such as vacuum maintenance, removal of trace gases in inert gas, and removal of gas in fluorescent lamps.

In recent years, energy conservation has been actively promoted, and vacuum insulation materials that exhibit excellent heat insulation effect in household appliances or equipment are required. As a vacuum insulator, it is known that a core material having microvoids such as glass wool or silica powder is covered with a casing material having gas barrier properties and the interior of the casing material is vacuum-sealed. Vacuum heat insulation materials are vacuum-sealed to vacuum insulation materials together with the core material to remove water vapor, oxygen, nitrogen, and other gases that invade into the vacuum insulation material in order to maintain its excellent heat insulation effect for a long period of time.

It is known that a chemical adsorption material which irremovably fixes and adsorbs moisture in an adsorbent material to an adsorbent is preferable for a vacuum insulator. Calcium oxide CaO is an example. However, with respect to oxygen and nitrogen in the air that permeates the exterior material of the vacuum insulation material, the moisture absorptive agent such as calcium oxide does not have the capability of adsorbing. Therefore, in order to maintain a reduced pressure state in a vacuum adiabatic environment, an adsorbent material for these gases is required.

A metal adsorbing material comprising barium getter or a ternary alloy of zirconium-vanadium-iron is known which exhibits adsorption ability against oxygen or nitrogen. However, since these metal adsorbing materials need to be activated at a high temperature of 400 DEG C or higher in a reduced-pressure environment, in a configuration in which a reduced-pressure environment is constructed by using an exterior material in which a plastic film and a metal foil are multilayered, external materials are melted and broken, The material can not be heated.

On the other hand, there is ZMS-5 type zeolite which is copper ion-exchanged as an adsorbent material for removing impurity gas such as nitrogen from the gas to be purified. For example, in Patent Document 1, ZMS- A vacuum insulator is known in which copper ions are introduced into form zeolite and heat treatment is performed to impart nitrogen adsorption activity.

However, since the water is always present in the insulating material of the vacuum insulating material, copper ion, which is a nitrogen active site, has a higher reactivity with water than nitrogen, so that it is oxidized by moisture to form copper hydroxide and becomes inert with respect to nitrogen have. Actually, according to this vacuum insulator, the maximum nitrogen adsorption amount at a pressure of 10 Pa is reported to be 0.238 mol / kg (5.33 cc-STP / g).

In order to solve this problem, Patent Document 2 discloses a vacuum insulation material in which the periphery of the copper ion-exchanged ZMS-5 type zeolite is covered with a water absorbing material to avoid the influence of moisture. However, the copper ion-exchanged ZMS-5 type zeolite having a ratio of silica to alumina of from 8 to 25 has a high adsorption rate to moisture, and if it is covered with an adsorbent under an inert gas, there is a risk of inactivation due to a trace amount of moisture in the inert gas.

Patent Document 3 discloses an adsorbent material characterized in that at least 84% or more of the copper sites of the copper ion-exchanged ZSM-5 type zeolite is a copper monovalent site having an oxygen-3 coordination number.

(Patent Document 1) Patent No. 3693626

(Patent Document 2) Patent No. 4734865

(Patent Document 3) Patent 4807552.

The adsorbent material of Patent Document 3 is capable of adsorbing and fixing gas species of a larger capacity than conventional adsorbent materials of the related art and is safe in handling without generating hydrogen gas and the like, but the rate of reaction with gas species is excessively large, The adsorption reaction proceeds rapidly.

In general, a vacuum insulator needs to vacuum-seal an adsorbent material in a metal container under an atmosphere in a manufacturing process, and the process of sealing while performing vacuum heating is complicated and energy-consuming. In particular, when the adsorbent material of Patent Document 3 is input, it is necessary to pay attention to the handling of the sealing material up to the introduction into the vacuum insulator due to the adsorption reaction rate, so there is a concern about the cost in production.

Therefore, in this embodiment, in order to solve the above-mentioned conventional problems, there is a need to provide a gas adsorbent material which improves the handling efficiency by lowering the adsorption rate and effectively utilizes the nitrogen adsorbing ability in the vacuum insulating material in order to reduce inactivation in vacuum- And a vacuum insulator using the gas adsorbing material.

One embodiment is a gas adsorption composition having a silica to alumina ratio in the zeolite framework of 10 to 50 as a copper ion-exchanged ZSM-5 type zeolite, And a sintered body of a compression-molded product including a water-absorbing material.

Another embodiment is a vacuum insulation material exhibiting an adiabatic effect by placing an internal environment in a reduced pressure state and placing it in a heat conduction region and is used in the internal environment under an environment in which it is necessary to reduce the target gas concentration, A gas adsorption composition comprising a zeolite of copper ion-exchanged ZSM-5 type, wherein the ratio of silica to alumina in the zeolite framework is 10 or more and 50 or less; and a water absorbing material for covering the gas adsorption composition There is provided a vacuum insulator comprising a gas adsorbent material obtained by vacuum sintering together with the gas adsorption composition in a state in which the water absorbing material is compression molded.

According to this embodiment, it is possible to provide a gas adsorbing material capable of increasing the gas barrier property to the target gas by reducing the gas adsorption rate while maintaining the gas adsorption performance, and a vacuum insulator using the gas adsorbing material.

1 is a schematic sectional view showing an example of a vacuum insulation material according to one embodiment.
Fig. 2 is an explanatory view showing the configuration of the gas adsorbent material shown in Fig. 1;
3 is an explanatory diagram showing another configuration of the gas adsorbent material.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In the present specification and drawings, constituent elements having substantially the same functional configuration are denoted by the same reference numerals, and redundant description will be omitted.

As a form of the gas adsorbing material according to the embodiment of the present invention, there is a nitrogen adsorbing material. And its application is not limited to a specific one. The nitrogen adsorbing material can be used for removing nitrogen gas in vacuum insulation.

It is known that a vacuum insulator is formed by covering a core material having microvoids such as glass wool or silica powder with a casing material having gas barrier properties and decompression-sealing the inside of the casing material. The vacuum insulator is used for refrigerator, freezer, Insulation materials for buildings, vending machines, refrigerated boxes, heaters, refrigerators and so on.

1 is a schematic sectional view showing an example of a vacuum insulator 1;

As shown in Fig. 1, the vacuum insulator 1 according to the embodiment of the present invention is formed by enclosing and sealing the core material 6 and the gas adsorbing material 7 between two external materials.

The periphery of the two sheathing materials 2 is formed into a bag-like shape as a whole by sealing (for example, heat sealing) the three sides by leaving the open end and attaching the core material 6 and the gas After the adsorbent material 7 is received, the inside pressure is lowered to seal (for example, heat seal) the opening. Reference numeral 8 denotes an abutted portion where the opening is sealed.

Hereinafter, each member of the vacuum insulator according to one embodiment will be described.

As the exterior material 2 according to one embodiment, any of conventional materials can be used as long as it has gas barrier property and can suppress invasion of gas. Normally, the exterior material is provided with barrier properties by laminating thermoplastic resin, metal foil or plastic film, and serves to isolate the core material with air or moisture.

1, the laminated film which can be used as the sheathing material 2 has a thermally fused layer (hot melt film) 5 as the innermost layer and a gas barrier layer (Film) 4 having a metal foil or a metal deposition layer, and an outermost layer having a surface protective layer (surface protective film) 3.

The thermally welded film 5 is a thermally welded layer of the outer material 2 that is solidified after being melted by heat and pressure, and serves to maintain the outer material 2 in a predetermined shape. In addition, it plays a role of suppressing the intrusion of gas or water vapor from the end of the sheathing material 2 into the vacuum insulator 1.

The thermal welding film 5 is not particularly limited as long as it can be adhered by a usual sealing method (for example, heat sealing). Examples of the material constituting the thermally welded film include polyolefins such as low density polyethylene, linear low density polyethylene, high density polyethylene and polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene- A thermoplastic resin such as an ethylene-acrylic acid ester copolymer and polyacrylonitrile, and the like. These materials may be used alone or in combination of two or more. The thermal welding film 5 may have a single layer or a laminate of two or more layers. In the latter case, each layer may have the same composition or may have a different composition.

The thickness of the heat-sealable film 5 is not particularly limited and may be the same as a known thickness. For example, the thickness of the heat-sealable film 5 may be 10 탆 to 100 탆. When it is thinner than 10 μm, there is a fear that sufficient adhesion strength can not be obtained when the sheet is sealed. If it is thicker than 100 μm, the workability such as flexibility may be deteriorated. On the other hand, when the thermally welded film has a laminate structure of two or more layers, the thickness of the thermally welded film means the total thickness. In this case, the thickness of each layer may be the same or different.

The gas barrier film is not particularly limited and may be a metal foil such as aluminum foil or copper foil or a metal foil such as aluminum or copper or a metal oxide such as alumina or silica to a polyethylene terephthalate film or an ethylene- One film or the like can be used.

The thickness of the gas barrier film is not particularly limited and may be the same as a known thickness.

The surface protective film (3) is not particularly limited, and the same materials as those usually used as the surface protective film of the exterior material can be used. Examples of the material constituting the surface protective film include polyamide (nylon) (PA) such as nylon-6 and nylon-66, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) Polyvinylidene chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene chloride (PVDC), polyvinylidene chloride (PVDC) (EVOH), polyvinyl alcohol resin (PVA), polycarbonate (PC), polyethersulfone (PES), polymethylmethacrylate (PMMA), polyacrylonitrile resin .

The thickness of the surface protective film 3 is not particularly limited and may be the same as a known thickness. For example, the thickness of the surface protective film 3 may be 10 탆 to 100 탆. If it is thinner than 10 탆, there is a fear that protection of the barrier layer is not sufficient. If it is thicker than 100 m, the workability such as flexibility may be deteriorated as in the case of the heat-sealable film. On the other hand, when the surface protective film 3 has a laminated structure of two or more layers, the thickness means the total thickness. In this case, the thickness of each layer may be the same or different.

Various known additives and stabilizers such as an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant and the like may be used for these films. On the other hand, the above materials may be used alone or in a mixture of two or more. The surface protective film may be a single layer or a laminate of two or more layers. In the latter case, each layer may have the same composition or may have a different composition.

The thickness of the exterior material 2 is not particularly limited. For example, from about 1 [mu] m to 100 [mu] m. If the sheathing material is as thin as described above, the heat bridge can be more effectively suppressed and prevented to improve the heat insulating performance, and also the gas barrier property and the workability are excellent.

According to another preferred embodiment, the sheathing material 2 made of a gas-barrier film is composed of at least two surfaces of a surface composed of a laminated film laminated with a metal foil and a surface composed of a laminate film not laminated with a metal foil, A surface of the laminate film on which the metal foil is not laminated is provided with a film layer made of an ethylene-vinyl alcohol copolymer resin composition in which aluminum is vapor-deposited at least on the inner layer side or a film layer made of a polyethylene terephthalate resin composition in which aluminum is vapor- You can have either one.

The exterior material 2 according to this embodiment may not be a laminate film as described above, and may be, for example, a metal container, a glass container, or a gas barrier container in which a resin and a metal are laminated. As such a plastic laminate film container, a container in which one kind or two or more kinds of films are laminated, such as polyvinylidene chloride, polyvinyl alcohol, polyester, polypropylene, polyamide, polyethylene, have.

As shown in Fig. 1, the core material 6 is disposed inside the exterior material. The core material usable in the present invention becomes the skeleton of the vacuum insulator and forms a vacuum space. Here, the material of the core material 6 is not particularly limited, and known materials can be used. For example, inorganic fibers such as glass wool, rock wool, alumina fibers, and metal fibers made of a metal having a low thermal conductivity; Synthetic fibers such as polyester, polyamide, acrylic, polyolefin and aramid; natural fibers such as cellulose, cotton, ramie, wool and silk produced from wood pulp; regenerated fibers such as rayon; and semi-synthetic fibers such as acetate Fiber and the like.

The core material may be used alone or in combination of two or more. Of these, for example, glass wool can be used. The core material made of these materials has high elasticity of the fiber itself, low thermal conductivity of the fiber itself, and further low industrial cost.

As shown in Fig. 2, the gas adsorbing material 7 shown in Fig. 1 is a hard case having a gas permeable opening, or a gas permeable film obtained by coating a copper ion exchange type zeolite 10 with a moisture adsorbing material 11 in a gas permeable film And a configuration in which a compression molded body is housed. One example of a gas permeable opening is an opening on the top of the hard case. The compression-molded body may be formed into a granular or pellet-like mass, and a plurality of these mass bodies may be dispersed in the core material.

The copper ion exchange type zeolite (10), which is the main material of the gas adsorbing material, is made of a porous crystalline aluminosilicate and a copper ion-exchanged ZSM-5 having a silica to alumina ratio (Si / Al) Type zeolite.

The copper ion exchange type zeolite (10) having a silica to alumina ratio of 10 or more to 50 or less in the zeolite framework according to the embodiment of the present invention will be described.

The ZSM-5 type zeolite used as a raw material for the copper ion exchange can be a commercially available material. However, when the silica to alumina ratio exceeds 50, the amount of copper ions exchanged decreases and the amount of trace impurities adsorbed decreases. On the other hand, ZSM-5 having a silica to alumina ratio of less than 5 is difficult to obtain.

The exchange rate of copper ions in the copper ion exchange type zeolite 10 is preferably at least 40% of the ion exchangeable amount of each zeolite. This is because the ion-exchanged copper ions are a specific adsorption factor of nitrogen and carbon monoxide. If the exchange rate of copper ions is too low, the specific adsorption performance is not manifested.

The method of ion-exchanging sodium contained in the ZSM-5 type zeolite with copper is not particularly limited, and a well-known method which has been conventionally performed can be employed. For example, sodium can be ion-exchanged to copper by immersing ZSM-5 type zeolite in an aqueous solution of a soluble salt of copper (nitrate, acetate, oxalate, hydrochloride, etc.). In this case, the amount of copper ion exchange can be adjusted to a desired amount by selecting the concentration of the copper salt, the immersion time, the immersion temperature, the number of immersion times, and the like.

After the ion exchange, cleaning is carried out by using water, and after drying, baking is carried out at a suitable temperature, whereby a usable state is obtained. The drying temperature at this time is suitably about 100 DEG C, and the firing temperature is 350 DEG C or higher, for example, 500 DEG C to 800 DEG C under a nitrogen gas atmosphere.

Since the specific adsorption performance of this adsorbent is considered to be expressed by the presence of monovalent copper ion, it is difficult to exhibit sufficient adsorption performance because the change from one side to the other side is insufficient at a firing temperature of less than 500 DEG C, The structure itself of zeolite may be destroyed.

The amount of copper ions contained in the copper ion-exchanged zeolite may be from 3.0 wt% to 6.4 wt%. The weight can be measured by any method, but can be measured by, for example, ICP emission analysis (induced charge emission spectrometry).

On the other hand, the ion exchange rate in this embodiment is obtained from the assumption that one copper ion exchanges with two sodium ions. In other words, at the time of ion exchange, copper ions are assumed to be present in two directions. Actually, since monovalent copper ions are also present, a conversion rate of 100% or more can be obtained as a calculated value, and when all the copper ions are present in one transverse state, the upper limit is reached, and the calculated ion exchange rate is 200% do.

By using the gas adsorbing material 7 including the copper ion exchange type zeolite 10, impurities existing in trace amounts in inert gas, oxygen, hydrogen, carbon dioxide, hydrocarbons and sulfur hexafluoride gas, It is possible to purify the gas by efficiently adsorbing and removing carbon monoxide, ammonia, nitrogen trifluoride, carbon dioxide, methane, hydrogen and oxygen, and the amount of impurities contained in the gas after purification is 1 ppm or less, % Or more.

The gas adsorbing material 7 according to this embodiment is characterized in that it is a compression sintered body obtained by vacuum-sintering a water-absorbing material 11 obtained by compression molding together with a copper ion exchange type zeolite 10. This compression sintered body has the effect of increasing the solid density of the calcium oxide layer forming the moisture adsorbing material 11, thereby deteriorating the permeability of nitrogen, that is, improving the gas barrier property. It was demonstrated that the adsorption rate of nitrogen can be reduced to 1/10 or less as compared with the conventional nitrogen adsorption powder (before vacuum sintering). Specifically, it is preferable that the solid density of the sintered body is adjusted such that the adsorption rate of the target gas is 0.005 cc / min or more and 0.1 cc / min or less.

When the adsorption rate of the target gas is less than 0.005 cc / min, the desired gas adsorbing ability can not be exhibited. When the target gas adsorbing rate is more than 0.1 cc / min, the gas adsorbing ability is sometimes inactivated early. For example, 0.008 cc / min or more and 0.05 cc / min or less, for example, 0.01 cc / min or more and 0.02 cc / min or less.

Aluminum in the formed body of copper ion-exchanged ZSM-5 type zeolite is dehydrated by vacuum heating at a rate of 15% or more while nitrogen adsorption rate is reduced and nitrogen that has remained in the vacuum insulating material or continuously passed through the exterior material is sufficiently It also proved that it can adsorb.

The term "dealumination" as used herein refers to a phenomenon in which the ratio of silica to alumina before firing is reduced by Al (alumina) due to vacuum heating to increase the silica to alumina ratio. In the present invention, it is known in the present invention that the structure destabilization due to de-aluminaization of ZSM-5 zeolite is attributed to the adsorption of copper on the surface of copper The adsorption of nitrogen is caused in association with the content of nitrogen.

On the other hand, the "vacuum sintering" in Examples and Comparative Examples described below means sintering treatment at 550 to 650 ° C. for 3 hours or more at a pressure of 10 Pa to 2 Pa or less by using an oil diffusion pump. The adsorption rate was measured according to the method of ASTM F798-97.

Example

≪ Example 1 >

Exchanged ZSM-5 (manufactured by Tosoh Corporation) having a silica to alumina ratio of 20.3 and a copper loading of 3.12 wt% was locally applied to a part of a water adsorbent having a BET specific surface area of 3 m ² / g and a secondary particle diameter of 100 μm (For example, in the form of a dry-coated tablet), or both of them are mixed, compression molded at 120 kgf / cm ² , and vacuum sintered to produce a compact having a solid density of 1.4 g / cm ³ did.

The nitrogen adsorption rate was measured to be 0.02 cc / min.

The degree of dealumination after firing was 15.8%.

≪ Example 2 >

Ion exchanged ZSM-5 (product of Sud - Chemie ) having a ratio of silica to alumina of 47.4 was ion-exchanged with a copper nitrate solution, and copper ion-exchanged ZSM-5 having a copper loading of 2.95 wt% was vacuum-dried at room temperature. Then, the dried copper ion-exchanged ZSM-5 was localized to a part of a moisture adsorbent having a BET specific surface area of 10 m ² / g and a secondary particle diameter of 100 μm, compression molded at 100 kgf / cm ² , And sintered to obtain a molded body having a solid density of 1.2 g / cm ³ .

The nitrogen adsorption rate was 0.02 cc / min.

The degree of dealumination after firing was 17.8%.

≪ Example 3 >

Ion exchanged ZSM-5 (product of Tosoh Corporation) having a silica to alumina ratio of 11.5 is ion-exchanged with a copper acetate solution, and copper ion-exchanged ZSM-5 having a copper loading amount of 5.8 wt% is vacuum-dried at room temperature. Subsequently, the dried copper ion-exchanged ZSM-5 was compression molded at 290 kgf / cm ² and vacuum sintered to produce a molded body having a solid density of 2.0 g / cm ³ .

As a result of measuring the nitrogen adsorption ability, the nitrogen adsorption rate was 0.010 cc / min.

The degree of dealumination after firing was 36.0%.

<Example 4>

Ion exchanged ZSM-5 (product of Tosoh Corporation) having a silica to alumina ratio of 11.5 is ion-exchanged with a copper acetate solution, and copper ion-exchanged ZSM-5 having a copper loading amount of 6.4 wt% is vacuum-dried at room temperature. Subsequently, the dried copper ion-exchanged ZSM-5 was compression molded at 140 kgf / cm ² and vacuum sintered to produce a molded body having a solid density of 1.5 g / cm ³ .

As a result of measuring the nitrogen adsorption capacity, the nitrogen adsorption rate was 0.020 cc / min.

The degree of dealumination after firing was 58.6%.

&Lt; Comparative Example 1 &

Exchanged ZSM-5 (manufactured by Tosoh Corporation) having a silica to alumina ratio of 20.3 and a copper loading of 3.12 wt% and a moisture adsorbent were mixed, and the mixture was vacuum-heated at 600 캜.

The nitrogen adsorption rate was measured to be 0.21 cc / min.

&Lt; Comparative Example 2 &

Exchanged ZSM-5 (product of Sud - Chemie ) having a ratio of silica to alumina of 47.4 is ion-exchanged with a copper nitrate solution, and copper ion-exchanged ZSM-5 having a copper loading amount of 2.95 wt% is vacuum-dried at room temperature. Then, the dried copper ion-exchanged ZSM-5 was mixed with the moisture adsorbent, and the surrounding was covered and vacuum-heated to 600 ° C. As a result of measuring the nitrogen adsorption rate, the nitrogen adsorption rate was 0.22 cc / min.

&Lt; Comparative Example 3 &

Ion exchanged ZSM-5 (product of Tosoh Corporation) having a silica to alumina ratio of 11.5 was ion-exchanged with a copper acetate solution, and copper ion-exchanged ZSM-5 having a copper loading amount of 5.8 wt% was vacuum-dried at room temperature. Then, the dried copper ion-exchanged ZSM-5 was hopped with a moisture adsorbent, covered with a vacuum, and heated at 600 캜 under vacuum.

As a result of measuring the nitrogen adsorption ability, the nitrogen adsorption rate was 0.14 cc / min.

&Lt; Comparative Example 4 &

Ion exchanged ZSM-5 (manufactured by Tosoh Corporation) having a silica to alumina ratio of 11.5 was ion-exchanged with a copper acetate solution, and copper ion-exchanged ZSM-5 having a copper loading of 6.4 wt% was vacuum-dried at room temperature. Then, the dried copper ion-exchanged ZSM-5 was mixed with the moisture adsorbent, and the surrounding was covered and vacuum-heated to 600 ° C.

As a result of measuring the nitrogen adsorption ability, the nitrogen adsorption rate was 0.21 cc / min.

Item Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 Example 4 Comparative Example 4 Nitrogen adsorption
speed
cc-STP / min 0.02 0.21 0.02 0.22 0.01 0.14 0.02 0.21 Compressive strength
Kgf / cm ² 120 - 100 - 290 - 140 - Solid density g / cm ³ 1.4 0.7 1.2 0.7 2.0 0.7 1.5 0.7 Copper loading weight% 3.12 3.12 2.95 2.95 5.8 5.8 6.4 6.4 Thall aluminum ratio% 15.8 - 17.8 - 36.0 - 58.6 -

It can be seen from Table 1 that Examples 1 to 4 in which the copper ion-exchanged ZSM-5 was vacuum-sintered while being covered with the moisture adsorbent and compression-molded in the gas adsorbing material had a nitrogen adsorption rate of 10 minutes Lt; RTI ID = 0.0 &gt; 1 &lt; / RTI &gt;

&Lt; Example 5 >

The copper ion-exchanged ZSM-5 (manufactured by Tosoh Corporation) having a silica to alumina ratio of 20.3 and a copper loading of 3.12 wt% was laid under the water-impermeable metal container 21 as shown in Fig. 3, Coated with a moisture adsorbent 11, compression molded at 120 kgf / cm ² , and then vacuum sintered to obtain a molded article having a solid density of 1.4 g / cm ³ as a gas adsorbing material 20.

This adsorbent material was inserted together with an exterior material having gas barrier properties and glass fiber, and vacuum-sealed to prepare a vacuum insulation material.

The thermal conductivity was measured and found to be 2.29 mW / mK.

&Lt; Comparative Example 5 &

A copper ion-exchanged ZSM-5 (product of Tosoh Corporation) having a silica to alumina ratio of 20.3 and a copper loading of 3.12 wt% was covered with a moisture adsorbent and inserted into a metal container and vacuum sintered without compression to produce an adsorbent material.

This adsorbent material was inserted together with a glass fiber and an exterior material having gas barrier properties, and vacuum sealed to prepare a vacuum insulation material.

The thermal conductivity was measured and found to be 2.77 mW / mK.

&Lt; Example 6 >

The gas adsorbent material produced in Example 1 was inserted together with a casing material having a gas barrier property and glass fiber and vacuum sealed to prepare a vacuum insulation material.

The thermal conductivity was measured and found to be 2.07 mW / mK.

Thereafter, an environmental test was conducted at 30 占 폚 and a humidity of 95% for one month, and the thermal conductivity was 2.22 mW / mK.

&Lt; Comparative Example 6 >

The gas adsorbing material produced in Comparative Example 1 was inserted together with a glass fiber and an exterior material having gas barrier properties and vacuum sealed to prepare a vacuum insulating material.

The thermal conductivity was measured and found to be 2.01 mW / mK.

Thereafter, an environmental test was conducted for 1 month at 30 캜 and a humidity of 95%. As a result, the thermal conductivity was 4.07 mW / mK.

In Comparative Example 5, the nitrogen adsorption ability of copper ion-exchanged ZSM-5 was reduced because the periphery was covered with a moisture adsorbent without being subjected to compression molding.

In Comparative Example 6, the initial thermal conductivity was almost the same as in Example 5, but there was a large difference in the environmental test results. This is an effect that the gas barrier property is improved by increasing the solid density of the gas adsorbent material by vacuum sintering in the compression molding state of Example 6.

It is possible to provide a reliable solution to the fact that the gas adsorbing material for vacuum insulator according to this embodiment functions as a nitrogen adsorbent among the vacuum insulators and maintains a desired degree of vacuum in the insulator.

1: Vacuum insulation
2: Exterior material
6: Core material
7: Gas adsorbent material
10: Copper ion exchange type zeolite
11: Moisture absorbing material

Claims (7)

As a gas adsorbing material having adsorption ability to a target gas,
Wherein the zeolite skeleton is a copper ion-exchanged ZSM-5 type zeolite having a ratio of silica to alumina of 10 or more and 50 or less, and a sintered body of a compression-molded material including a water-absorbing material. The gas-absorbing material according to claim 1, wherein the ZSM-5 type zeolite has a copper ion content of not less than 3 wt% and not more than 6.4 wt%. The gas adsorbent material according to any one of claims 1 to 3, wherein the water absorption material and the dealumination ratio after vacuum sintering the gas adsorption composition are 15% or more. The gas adsorbent material according to any one of claims 1 to 3, wherein the solid body of the molded article obtained by vacuum sintering the gas absorbing composition and the water absorbing material together is 1.2 g / cm ³ or more and 2.0 g / cm ³ or less. The gas adsorbing material according to claim 4, wherein the water absorbing material has a BET specific surface area of 10 m ² / g or less and a secondary particle diameter of 100 μm or less. 5. The gas adsorbent material according to claim 4, wherein the solid density of the sintered body is adjusted such that the adsorption rate of the target gas is 0.005 cc / min or more and 0.1 cc / min or less. A vacuum insulation material exhibiting an adiabatic effect by placing the internal environment in a reduced pressure state and placing it in a heat conduction region,
Wherein the internal environment includes a gas adsorbing material capable of adsorbing a target gas,
Wherein the gas adsorbent material is a copper ion-exchanged ZSM-5 type zeolite, wherein the zeolite skeleton has a silica to alumina ratio of 10 or more to 50 or less, and a sintered compact of a compression-molded material containing a water-absorbing material.

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