KR101369525B1 - Getter having gas adsorbent coated by water adsorbent and manufactiring method thereof - Google Patents

Abstract

The present invention relates to a getter material, comprising a gas adsorbent and a moisture adsorbent covering the surface of the gas adsorbent, and having a structure of enclosing a gas adsorbent having a high activity with the moisture adsorbent, thereby providing moisture and A getter material is provided which provides the effect of preventing the surface of the gas adsorbent from changing inactive during the manufacturing process while removing the gas.

Description

GETTER HAVING GAS ADSORBENT COATED BY WATER ADSORBENT AND MANUFACTIRING METHOD THEREOF}

The present invention relates to a getter material and a method for manufacturing the same, and more particularly, to have a structure that surrounds the gas adsorbent with a moisture adsorbent, thereby providing a getter material that can prevent deterioration of the gas adsorbent during the manufacturing process. It is.

As a countermeasure against global warming, energy saving of household electrical appliances, equipment, and the like is an important problem, and one of the solutions is the use of a vacuum insulator, which is a high-performance insulating material.

The vacuum insulation material includes a core material and an outer cover material covering the core material. The vacuum insulating material is a heat insulating material that significantly reduces the thermal conductivity of the gas by reducing the inside of the outer cover material to a state in which it is close to vacuum.

However, since the core material of the vacuum insulation material is generally a porous body having a fine gap, the surface area is large and the hygroscopicity is high, so that the moisture adhering to the surface remains. The internal pressure is increased, and eventually there is a problem that the desired insulation performance is not obtained.

On the other hand, in the related art, a number of proposals have been made to apply a moisture adsorbent inside the vacuum insulator to remove moisture adhering to the core surface.

However, the getter material composed of only moisture adsorbents has been effective in adsorbing moisture, but is insufficient in removing the gas remaining inside the vacuum insulation material and the gas penetrating the outer skin material from the outside in the long term. There was a problem that the internal pressure of the is deteriorated due to the increase in insulation performance.

On the other hand, it is currently considered to apply a gas adsorbent having high activity to adsorb gas.

However, since the gas adsorbent has a very high activity, the surface of the gas adsorbent easily reacts with oxygen and nitrogen present in the atmosphere in the manufacturing process, that is, at atmospheric pressure and room temperature, and thus the surface becomes inert, and thus does not function properly as a gas adsorbent. There was this.

The present invention is to provide a getter material having an effect of covering the gas adsorbent having high activity with a moisture adsorbent, thereby preventing the surface of the gas adsorbent from becoming inactive during the manufacturing process.

In addition, the present invention provides a method for producing a getter material that can prevent the surface of the gas adsorbent from changing inactive during the manufacturing process while reducing the manufacturing cost by going through the process of physically mixing and stirring the gas adsorbent and the moisture adsorbent. will be.

The getter material according to the embodiment of the present invention for achieving the above object comprises a gas adsorbent and a moisture adsorbent covering the surface of the gas adsorbent, characterized in that to prevent deterioration of the gas adsorbent during the manufacturing process.

Preferably, the getter material further includes a packaging material for packing the gas adsorbent and the moisture adsorbent.

Method for producing a getter material according to an embodiment of the present invention for achieving the above another object is to supply a gas adsorbent and a water adsorbent to the chamber, and the gas adsorbent and the water adsorbent supplied in the chamber physically in the range above the active temperature And mixing and stirring.

According to another aspect of the present invention, there is provided a method of manufacturing a getter material, the method comprising: supplying a gas adsorbent and a water adsorbent to a chamber, and physically mixing and stirring the gas adsorbent and the water adsorbent supplied in the chamber within an active temperature range. And heat-treating the gas adsorbent and the water adsorbent in the range of the active temperature or more.

The getter material according to the present invention has a structure in which a gas adsorbent having a high activity is wrapped with a moisture adsorbent, thereby preventing the surface of the gas adsorbent from becoming inactive during the manufacturing process while removing water and gas present in the vacuum insulator. to provide.

In addition, the method of manufacturing a getter material according to the present invention physically mixes and stirs a gas adsorbent and a water adsorbent to produce a getter material wrapped with a gas adsorbent with a water adsorbent, thereby providing an effect of significantly reducing the manufacturing cost.

1 is a cross-sectional view of a vacuum insulating material including a getter material according to an embodiment of the present invention,
2 is an enlarged cross-sectional view of a getter material according to an embodiment of the present invention;
3 is a cross-sectional view of a vacuum insulating material including a getter material according to another embodiment of the present invention;
4 is a view schematically showing a manufacturing process of a getter material according to the present invention.

Hereinafter, a getter material of the present invention and a manufacturing method thereof will be described with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to achieve them, will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

In the drawings, it is to be noted that the sizes of the constituent elements of the invention are exaggerated for clarity of description, and when it is described that any constituent element is present inside or connected to another constituent element, The element may be installed in contact with the other element, may be installed at a predetermined distance from the element, and may be provided with a third element for fixing or connecting the element to the other element, The description of the means may be omitted.

1 is a cross-sectional view of a vacuum insulating material including a getter material according to an embodiment of the present invention, Figure 2 is an enlarged cross-sectional view of the getter material according to an embodiment of the present invention.

1 and 2, the getter material 130 according to the present invention is sealed under reduced pressure by the shell material 120 together with the core material 110, and includes a gas adsorbent 131 and a moisture adsorbent 133. .

The gas adsorbent 131 adsorbs the gas inside the vacuum insulator 100. The gas adsorbent 131 adsorbs unnecessary gas components remaining in the process of manufacturing the vacuum insulation material 100, and in the long term, adsorbs gas components that penetrate the outer shell material 120 to penetrate the inside of the vacuum insulation material 100. To prevent the pressure from rising.

The gas adsorbent 131 may include a nanoporous material. By including the nanoporous material, the gas adsorbent 131 expands the contact area with the remaining gas, thereby increasing the activity of the remaining gas. The nanoporous material means a material having nano-sized pores, and examples of specific materials include zeolite, activated carbon, alumina, and the like.

Further, the gas adsorbent 131 is formed of Ta, Metal / metal oxides such as Cb, Zr, Th, Mg, Ba, Ti, Al, Nb, Fe, Li, Pb, Pt, Au and the like may be further included and used as the active point.

The moisture adsorbent 133 is disposed to surround the surface of the gas adsorbent 131.

Through the moisture adsorbent 133 disposed to surround the surface of the gas adsorbent 131, the surface of the gas adsorbent 131 is temporarily blocked to prevent deactivation in the manufacturing process, thereby preventing the gas in the completed vacuum insulation material 100. The adsorbent 131 can adsorb the remaining gas.

The moisture adsorbent 133 has a lower activity than the gas adsorbent 131. By covering the gas adsorbent 131 with the moisture adsorbent 133, the surface of the gas adsorbent 131 may be temporarily blocked to prevent the surface of the gas adsorbent 131 from being inactive in the manufacturing process of the vacuum insulation material 100. .

The water absorbent 133 may use an organic / inorganic material compound such as calcium oxide, calcium chloride, magnesium oxide, silica gel, or the like.

The moisture adsorbent 133 absorbs moisture adhered to the surface of the core material 110. By absorbing the moisture, the remaining moisture is vaporized to prevent the internal pressure of the vacuum insulator 100 from increasing, and thus, the desired heat insulating performance can be obtained together with the gas adsorbent 131.

3 is a cross-sectional view of a vacuum insulating material including a getter material according to another embodiment of the present invention.

Referring to FIG. 3, the getter material 130 according to the present invention may further include a packing material 135 for packing the gas adsorbent 131 and the moisture adsorbent 133.

By further including the packaging material 135, the core material 110 may be protected even when a material having a sharp fracture surface is used as the moisture adsorbent 133 in the process of inserting the getter material 130 into the core material 110. It is possible to prevent the pin hole and the like from being generated in the ash 120.

The packaging material 135 may include a polyethylene film or a polypropylene film. By including a polyethylene film or a polypropylene film, the gas adsorbent and the moisture adsorbent may be packed through the fusion process after packaging the moisture adsorbent 133.

In addition, the packaging material 135 may further include a nonwoven layer as an inner skin layer. Since the nonwoven fabric has a uniform small hole and excellent sticking resistance, damage to the packaging material 135 can be prevented even if the moisture absorbent 133 has a sharp fracture surface. In addition, in terms of breathability, it can be easily controlled by changing the lamination, thickness, and hole size of the nonwoven fabric.

4 is a view schematically showing a manufacturing process of a getter material according to the present invention. Referring to Figure 4, looks at with respect to the manufacturing method of the getter material 130 according to the present invention.

First, as shown in FIG. 4A, the gas adsorbent 131 and the moisture adsorbent 133 are supplied to the chamber 10.

Nanoporous materials may be used as the gas adsorbent 131 supplied to the chamber 10. Examples of the nanoporous materials include zeolite, activated carbon, alumina, and the like. Further, the gas adsorbent 131 is formed of Ta, Metal / metal oxides such as Cb, Zr, Th, Mg, Ba, Ti, Al, Nb, Fe, Li, Pb, Pt, Au, and the like may be further included and used as the active point.

As the water adsorbent 133 supplied to the chamber 10, a material having lower activity than that of the gas adsorbent 131 may be used. For example, an organic / inorganic material compound such as calcium oxide, calcium chloride, magnesium oxide, silica gel, or the like may be used. Can be used.

Next, as shown in FIG. 4B, the gas adsorbent 131 and the moisture adsorbent 133 supplied into the chamber 10 are physically mixed and stirred.

By physically mixing and stirring the gas adsorbent 131 and the moisture adsorbent 133, the surface of the gas adsorbent 131 is surrounded by the moisture adsorbent 133.

By covering the surface of the gas adsorbent 131 with the moisture adsorbent 133, the reactivity with the atmosphere is temporarily suppressed, thereby increasing the time for which the gas adsorbent 131 is inactivated during the manufacturing process.

The temperature during the mixing and stirring process may be divided into a range above the active temperature of the gas adsorbent 131 and the moisture adsorbent 133 and a range below the active temperature.

When mixing and stirring in the range of the active temperature of the gas adsorbent 131 and the moisture adsorbent 133 or more, it is possible to obtain the activated getter material 130 without additional heat treatment.

In the range of the active temperature or more of the gas adsorbent 131 and the moisture adsorbent 133, the active temperature means an active temperature of a larger temperature between the active temperature of the gas adsorbent 131 and the active temperature of the moisture adsorbent 133. For example, when zeolite is used as the gas adsorbent and calcium oxide is used as the water adsorbent, the zeolite's active temperature is 400 ° C and the calcium oxide's active temperature is 200 ° C. It means the range of ℃ or more.

As another example, when zeolite and iron oxide are used as the gas adsorbent and calcium oxide is used as the water adsorbent, the zeolite has an active temperature of 400 ° C., an iron oxide of 575 ° C., and an active temperature of calcium oxide is 200 ° C. The range above the active temperature of the adsorbent and the moisture adsorbent means the range above 575 ° C.

In this case, the getter material 130 may further include packing through the organic / inorganic film in a state filled with a vacuum chamber or an inert gas.

When mixing and stirring in the range below the active temperature of the gas adsorbent 131 and the moisture adsorbent 133, it can be manufactured and used as a product without the vacuum packaging as described above.

Here, in the range below the active temperature of the gas adsorbent 131 and the moisture adsorbent 133, the active temperature means the active temperature of the smaller of the active temperature of the gas adsorbent 131 and the active temperature of the moisture adsorbent 133.

For example, when zeolite is used as the gas adsorbent and calcium oxide is used as the water adsorbent, the zeolite's active temperature is 400 ° C. and the calcium oxide's active temperature is 200 ° C., which is therefore less than the active temperature of the gas adsorbent and the moisture adsorbent. Means a range of less than 200 ° C.

As another example, when zeolite and iron oxide are used as the gas adsorbent, and calcium chloride is used as the moisture adsorbent, the zeolite and iron oxide have an active temperature of 400 ° C., an iron oxide of 575 ° C., and an calcium chloride active temperature of 120 ° C. The range below the active temperature of the water absorbent means the range below 120 ° C.

At this time, since the gas adsorbent 131 and the moisture adsorbent 133 are not in an activated state, the gas adsorbent 131 and the moisture adsorbent 133 may be preferably further heat-treated at a range higher than the active temperature.

Example

In order to manufacture the getter material according to the present invention, the gas adsorbent of the zeolite component and the water adsorbent of the calcium oxide component are injected into the chamber, and then mixed and stirred at 450 ° C., which is the range of the active temperature or more, to wrap the gas adsorbent with the moisture adsorbent. I could get getter material.

Such a getter material was inserted into the core material which is the glass wool laminated body which laminated | stacked two layers of glass wool in which the glass fiber of diameter 1-10um was condensed. Thereafter, the core material and the getter material were wrapped in an outer shell material and sealed under reduced pressure. The outer shell material is LLDPE, which is a polyethylene resin of about 50 μm as a heat-sealing layer, an aluminum foil layer of about 6 μm as the gas barrier layer 24, a nylon film of about 25 μm as the first protective layer 26, and a second protective layer 28. About 12 μm of polyvinylidene chloride (PVDC) coated polyethylene terephthalate film (K-PET) was used.

After heat-treating the vacuum insulator for 30 days at 90 ° C., the thermal conductivity was measured by a thermal conductivity measuring device “HC 0074-200 (Eco)”. As a result, the thermal conductivity of the vacuum insulator was measured to be 0.0035 Kcal / mhr ° C.

Comparative Example  One

As Comparative Example 1, the water adsorbent of the calcium oxide component and the gas adsorbent of the zeolite component were inserted together into the core material in powder form without undergoing a separate process, and then sealed under reduced pressure with an outer shell material. Here, the core material and the shell material used the same core material and shell material as the above embodiment.

After heat-treating the vacuum insulator for 30 days at 90 ° C., the thermal conductivity was measured by a thermal conductivity meter “HC 0074-200 (Eco)”, and the thermal conductivity of the vacuum insulator was measured to be 0.0045 Kcal / mhr ° C.

Comparative Example  2

As Comparative Example 2, the water adsorbent of the calcium oxide component was activated by heating at a temperature of 250 ° C., which is equal to or higher than the active temperature, and then a getter material was inserted into the core material and sealed under reduced pressure with an outer shell material. The same core and sheath were used.

After heat-treating the vacuum insulator for 30 days at 90 ° C., the thermal conductivity was measured by a thermal conductivity meter “HC 0074-200 (Eco)”. As a result, the thermal conductivity of the vacuum insulator was measured to be 0.0054 Kcal / mhr ° C.

Example Comparative Example 1 Comparative Example 2 Thermal conductivity
(Kcal / mhr ℃) 0.0035 0.0045 0.0054

As can be seen in Table 1 above,

When the water adsorbent and the gas adsorbent are respectively inserted in powder form without a separate process as in Comparative Example 1, since the activity of the gas adsorbent is large, the surface of the gas adsorbent is changed to an inactive state in the manufacturing process so that the gas in the vacuum insulating material is completed. The performance as an adsorbent will not be exhibited. As a result, the thermal conductivity was not satisfactory as described above.

In addition, when only the moisture adsorbent is used as in Comparative Example 2, the moisture adsorbed on the surface of the core material can be absorbed, but the gas remaining in the vacuum heat insulating material cannot be removed, so that the internal pressure of the vacuum heat insulating material increases, and thus the thermal conductivity is increased. The result was not satisfactory.

On the other hand, in the case of using the getter material wrapped with the gas adsorbent as the moisture adsorbent according to the present invention, since the surface of the gas adsorbent is temporarily blocked from being inactivated in the manufacturing process, the thermal conductivity is lowered, so that the desired thermal insulation effect can be obtained as the vacuum insulation material. .

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is to be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: chamber
100: Vacuum insulation
110: heartwood
120:
130: getter material
131: gas adsorbent
133: moisture adsorbent
135: packaging material

Claims (9)

Gas adsorbents; And
A moisture adsorbent covering the surface of the gas adsorbent; to prevent deterioration of the gas adsorbent during the manufacturing process,
The gas adsorbent comprises a nanoporous material and a metal or metal oxide.
delete delete The method of claim 1,
The moisture adsorbent is a getter material, characterized in that it comprises at least one of CaO, CaCl ₂ , MgO, silica gel.
The method of claim 1,
The getter material further comprises a packaging material for packing the gas adsorbent and the moisture adsorbent.
6. The method of claim 5,
The packaging material is a getter material, characterized in that it comprises a polyethylene film or a polypropylene film.
The method according to claim 6,
The packaging material is a getter material, characterized in that it further comprises a nonwoven layer as an inner skin layer.
Supplying a gas adsorbent and a moisture adsorbent to the chamber; And
And physically mixing and agitating the gas adsorbent and the moisture adsorbent supplied in the chamber at an active temperature or higher to cover the gas adsorbent with the moisture adsorbent.
The gas adsorbent comprises a nanoporous material, and a metal or metal oxide manufacturing method of the getter material
Supplying a gas adsorbent and a moisture adsorbent to the chamber;
Wrapping the gas adsorbent with the moisture adsorbent by physically mixing and stirring the gas adsorbent and the moisture adsorbent supplied into the chamber within an active temperature range; And
A heat treatment in a range of at least an active temperature of the gas adsorbent and the moisture adsorbent;
The gas adsorbent comprises a nanoporous material, and a metal or metal oxide manufacturing method of the getter material

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