KR101944162B1 - Outer packaging materials having high temperature resistance for vacuum insulation panel, Vacuum insulation panel using the same, and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a shell material for a vacuum insulation panel, a vacuum insulation panel using the same, and a method for manufacturing the same, and more specifically, by introducing a specific material, And a vacuum insulated panel using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum insulated panel.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a high-temperature vacuum insulation panel for a high-temperature vacuum insulation panel, a high-temperature vacuum insulation panel using the same,

The present invention relates to a cover material for a vacuum thermal insulation panel which can be used in products such as a heater, a heat seat sheet and the like but has a small thickness, a vacuum insulation panel using the same, and a method for manufacturing the same.

In general, glass wool (or glass fiber or the like) is used as an inner core member used for a vacuum insulation material, and a metal material such as a stainless steel thin plate is used as a sheath material. Such a metal material does not substantially transmit gas, There is an advantage that the insulation performance is not deteriorated. However, such a vacuum insulation material is not easy to handle because the density of the panel is about 200 kg / m ³ to 300 kg / m ³ , and there is a risk that it has a risk factor due to the sharpness of the joint portion of the vacuum insulation material. A problem has occurred. Even if the inside is a vacuum, it is difficult to expect the desired heat insulating performance because the heat conduction through a metal material such as stainless steel, which is a sheath material, is high.

To solve this problem, a laminate sheathing material for a vacuum insulator has been developed. In order to maintain the degree of vacuum in the laminate sheathing material, the laminate sheathing material is protected against external impact, pinholes, tears, cracks, A moisture barrier function for preventing water and gas from permeating from the outside, and a heat-sealing function for putting a core material in a sheathing material and sealingly sealing it are required, and a plurality of films A laminating film laminated thereon was developed.

For example, high-density polyethylene and polypropylene are used in the film used for the heat-sealable layer in view of gas-barrier property and heat resistance, which gas permeates along the periphery of the heat-sealed portion. In addition, Discloses a technique using a film in which polyethylene having a different melting point is laminated on a heat-sealable layer in order to ensure airtightness. In addition, the vacuum insulation material seals the skin material through thermal fusion and inserts the core material, so that the sealing material is formed only at the edges of the vacuum insulation material including the slightly larger structure. However, since the sealing portion has no adiabatic effect, not only the effective heat insulating area is reduced but also the flow of the heat bridge or the foam insulating material is inhibited when the vacuum insulating material is applied to the heat insulating wall of a refrigerator or the like .

Therefore, in order to eliminate the adverse effect of the sealing portion, there is known a technique of folding and fixing the sealing portion. This is because the sealing portion of the vacuum insulating material attached to the inner surface of the heat insulating wall is folded to the other side to deteriorate the heat insulating performance according to the heat bridge of the sealing portion To a minimum.

However, the vacuum insulation material made of such a sheath material is integrated with the adhesive between the layers due to the characteristics of the multi-layered sheathing material. However, since the conventional adhesive has poor heat resistance, the adhesive layer and each layer formed thereon can not withstand a high temperature of 150 ° C or higher, There is a problem that the vacuum state can not be maintained, and there is a problem that the surface of the shell material is deformed due to thermal shock, shrinkage or the like.

Korean Registered Patent No. 10-0359738 (October 23, 2002)

Accordingly, the present inventors have made efforts and studies to produce a vacuum insulation panel excellent in economic efficiency, productivity and heat insulation, and having excellent high temperature heat resistance. As a result, it has been found that, while maintaining the vacuum insulation degree, And developed a cover material for this excellent vacuum insulation panel. That is, the present invention provides a casing material for a high-temperature vacuum insulation panel, a vacuum insulation panel manufactured using the same, and a method of manufacturing the same.

In order to solve the above problems, a shell material for a high-temperature vacuum insulation panel of the present invention comprises a heat-sealable layer; A first railway fault layer; Gas-moisture barrier layer; And a second heat shielding layer laminated in order from the inside to the outside.

In one preferred embodiment of the present invention, a high heat-resistant adhesive layer may be disposed between the heat-sealable layer and the first heat-shielding layer, between the first heat-shielding layer and the gas-moisture barrier layer, and between the gas- .

As a preferred embodiment of the present invention, the high heat-resistant adhesive layer may be comprised of a urethane two-component adhesive.

In one preferred embodiment of the present invention, the urethane two-pack type adhesive comprises a hard segment and a soft segment at a molar ratio of 1: 1.1 to 1.4, and a urethane having a weight average molecular weight of 30,000 to 40,000 g / mol It may be a two-pack type adhesive.

In one preferred embodiment of the present invention, the urethane two-component adhesive may have an NCO molar ratio of 0.88 to 0.92 with respect to 1 mole of the main (-OH).

In one preferred embodiment of the present invention, the heat-sealable layer may include a film containing at least one selected from a casting polypropylene (CPP) film and a high density polyethylene (HDPE) film.

As a preferred embodiment of the present invention, the first and second heat shielding layers of the cover material for a hot vacuum insulated panel of the present invention may independently comprise a polyimide (PI) film or a polyethylene naphthalate (PEN) film .

As a preferred embodiment of the present invention, both the first heat shielding layer and the second heat shielding layer of the cover material for the hot vacuum insulated panel may include a polyimide film or a polyethylene naphthalate film.

In a preferred embodiment of the present invention, the first heat shield layer of the cover material for the hot vacuum insulated panel comprises a polyethylene naphthalate film, and the second heat shield layer may comprise a polyimide film.

In one preferred embodiment of the present invention, the gas-water barrier layer of the jacket material for a hot vacuum adiabatic panel may comprise a polyethylene terephthalate film deposited with aluminum foil or aluminum (Al).

As a preferred embodiment of the present invention, in the casing material for a high-temperature vacuum insulation panel, the heat-sealable layer has an average thickness of 35 mu m to 70 mu m, the first heat fault layer has a thickness of 6 mu m to 15 mu m, Mu m to 25 mu m, and the second heat fault layer may be 10 mu m to 30 mu m.

In one preferred embodiment of the present invention, the high heat-resistant adhesive layer may have an average thickness of 2 탆 to 5 탆.

In one preferred embodiment of the present invention, the overall thickness of the cover material for a high-temperature vacuum insulation panel may be 70 μm to 150 μm.

As a preferred embodiment of the present invention, the casing material for a high-temperature vacuum insulation panel of the present invention has a heat shrinkage in the MD (machine direction) of 1% or less and a heat shrinkage in the TD (transverse direction) 0.8% or less.

As a preferred embodiment of the present invention, the outer cover material for a high-temperature vacuum insulation panel of the present invention has a thermal conductivity ranging from 0.1500 to 0.2850 W / mK in the MD direction and from 16.000 to 18.000 W in the TD direction when measured based on the thermal conductivity measurement method (KS L 9016) / mk.

As a preferred embodiment of the present invention, the shell material for a high-temperature vacuum insulation panel of the present invention may have a moisture absorption rate of 0.1 to 0.8%.

As a preferred embodiment of the present invention, the shell material for a high-temperature vacuum insulation panel of the present invention may have a gas permeability of 0.10 cc / m < 2 > day or less when measured according to ASTM D3985.

As a preferred embodiment of the present invention, the shell material for a high-temperature vacuum insulation panel of the present invention may have a water vapor permeability (ASTM F1249) of 0.05 g / m 2 · day or less when measured according to ASTM F1249.

Another object of the present invention is to provide a high-temperature vacuum insulation panel using the cover material for vacuum insulation panels of various forms described above, And a jacket material for vacuum insulation panels for vacuum packing the core material.

In a preferred embodiment of the present invention, the core material may further include a getter material attached to or inserted into the core material.

As a preferred embodiment of the present invention, the high-temperature vacuum thermal insulation panel of the present invention may further include a foam formed on the outer surface of the casing.

In a preferred embodiment of the present invention, the joint portion between the shell and the foam may be heat sealed and chemically bonded, so that the shell and the foam may be integrated.

In a preferred embodiment of the present invention, the foam may be a polystyrene or polyurethane foam.

As a preferred embodiment of the present invention, the high-temperature vacuum insulation panel of the present invention may have a total thickness of 10 mm to 50 mm.

As a preferred embodiment of the present invention, the high temperature vacuum thermal insulation panel of the present invention may have a heat conduction ratio of 0.25 W / m < 2 > K or less when the overall thickness of the panel is 20 mm when measured according to KS F2278.

As a preferred embodiment of the present invention, the high temperature vacuum thermal insulation panel of the present invention may have a thermal conductivity of 0.0045 W / mK or less when the overall thickness of the panel is 20 mm when measured according to the method of KS L 9016.

Another object of the present invention is to provide a method of manufacturing a hot vacuum insulated panel as described above, wherein a hot-melt adhesive layer, a first adhesive layer, a gas-moisture barrier layer and a second adhesive layer are laminated by dry lamination A first step of producing a laminated shell material; And a step of vacuum-packing the core material with the encapsulation material to produce a vacuum insulation material.

As a preferred embodiment of the present invention, a method for manufacturing a high-temperature vacuum thermal insulation panel according to the present invention comprises the steps of placing a vacuum insulation material in which a core material is vacuum-packed with a sheathing material in a mold, applying and foaming a foaming agent to form a foam; .

As a preferred embodiment of the present invention, the laminate of the first stage can be produced by laminating by dry lamination.

As a preferred embodiment of the present invention, the two-stage packing can be performed in a vacuum chamber at a vacuum of 0.005 to 0.05 Torr.

The cover material for a high-temperature vacuum insulation panel of the present invention is excellent in the effects of maintaining the vacuum degree, insulation, water / gas barrier, etc., which are basic physical properties to be provided by the outer cover material for vacuum insulation material, It can be applied to electric / electronic products, automobile electronic sensors, heat seat sheets as well as materials, containers for storage and transportation, refrigeration equipment, and heat insulation equipment.

1 is a schematic cross-sectional view of a shell material for a high-temperature vacuum insulation panel of the present invention
2 is a schematic cross-sectional view of the high temperature vacuum insulation panel of the present invention.
Figure 3 is a schematic view of a section of a hot vacuum insulation panel of the invention with foam on the outside.
4 is a schematic view of a step of forming an adhesive layer and laminating a film by a dry lamination method according to a preferred embodiment of the present invention.
5 is a photograph of a high-temperature vacuum insulation panel manufactured using the cloister material of Example 1. Fig.
6 is a photograph of the vacuum insulation panel produced in Comparative Production Example 1. Fig.
7A and 7B are photographs taken after completion of the vacuum insulation panel test of Comparative Production Example 1 and Comparative Production Example 2 in Experimental Example 5, respectively.

Hereinafter, the envelope material (hereinafter referred to as "envelope material") for a high-temperature vacuum insulation panel of the present invention will be described in detail.

The envelope material 100 of the present invention comprises a heat-sealable layer 1 as shown in a schematic sectional view in Fig. 1; A first train fault layer (2); A gas-moisture barrier layer 3; And a second heat fault layer (4) are stacked in order from the inside to the outside.

The covering material is integrated between the heat-sealable layer and the first heat-insulating layer, between the first heat-shielding layer, the gas barrier-water barrier layer and the gas barrier-moisture barrier layer and the second heat barrier layer by means of the high heat- Can be.

In the sheathing material of the present invention, the heat-sealable layer 10 serves to seal or fix the gasket and the moisture to prevent penetration of the core material (or the heat insulating material 100) inside the sheath material 100, The heat-sealable layer may be a film containing at least one selected from CPP (casting polypropylene film) and HDPE, and preferably a CPP film having a melting point of 155 ° C or higher may be used.

The heat-sealable layer 1 preferably has an average thickness of 35 to 70 m, preferably 40 to 60 m, and if the heat-sealable layer is less than 35 m, the heat seal strength is weak and the gas and moisture permeability If the thickness exceeds 65 μm, there may be a problem of thinning, and if heat transfer due to the thickness is not sufficient at the heat sealing site for heat sealing at the time of dispensing, the adhesive strength is decreased due to insufficient melting of the heat sealing layer There may be a problem of weakening, so it is necessary to set the temperature of the heater bar which applies heat to be high and there is a problem that the production speed should be lowered.

In the case of the outer cover material for a vacuum insulation panel of the present invention, the first thermal insulation layer (2) has a function of preventing barrier (moisture permeation and dumping), protecting the gas-moisture barrier layer, , A polyimide (PI) film or a polyethylene naphthalate (PEN) film, preferably a PI film. In this case, the PEN film may be a general PEN film of the related art. Preferably, the BEN film is made of 2,6-Dimethyl Naphthalene Dicarboxylate (NDC) and EG (Ethylene Glycol G) through an ester interchange, And then synthesized through a condensation reaction. The PEN film has a melting point of about 10 higher than that of PET (polyethylene terephthalate) film (266) and has a glass transition point of 113, which is higher than 68 of PET due to the presence of a large naphthalene ring. It is characterized by excellent chemical resistance, hydrolysis resistance, electrical insulation, excellent mechanical strength, gas barrier and radiation resistance.

The PI film may be a conventional PI film used in the art. For example, a PI film prepared by polymerizing and imidizing PMDA (Pyromellitic dianhydride) and ODA (oxy-dianiline) may be used .

The average thickness of the first thermal insulation layer is 6 탆 to 15 탆, preferably 8 탆 to 14 탆, and more preferably 9 탆 to 13 탆. If the average thickness of the first thermal insulation layer is less than 6 탆, There may be a problem that the gas barrier property is lowered and a crack is generated at the corner of the gas-moisture barrier layer when the core material is packed. When the thickness is more than 15 탆, it is disadvantageous in terms of thinning of the outer cover material. good.

The gas-moisture barrier layer (3) serves to block gas and prevent external moisture from flowing into the core material. The aluminum foil or aluminum (Al ) May be a single layer structure composed of a deposited polyethylene terephthalate film or a multilayer structure composed of a plurality of stacked layers.

The average thickness of the gas-water barrier layer is preferably 4.5 to 25 μm, more preferably 6 to 20 μm, and if it is less than 4.5 μm, there may be a problem of high pitting and moisture permeability due to a large number of pin holes If it exceeds 25 mu m, it is disadvantageous to reduce the thickness of the outer cover material. Particularly, when aluminum foil is used as the gas-moisture barrier layer, it is preferable to use an aluminum foil having an average thickness of 4.5 탆 to 10 탆, preferably an average thickness of 6 탆 to 8 탆. When a polyethylene terephthalate film in which aluminum (Al) is deposited as a gas-moisture barrier layer is used, it is preferable to use an aluminum foil having an average thickness of 12 탆 to 25 탆, preferably an average thickness of 14 탆 to 20 탆.

The second thermal barrier layer (4) of the present invention has a function of preventing moisture permeation and permeability as well as preventing shrinkage due to heat at high temperature and mechanical strength to prevent breakage and cracking during handling. A polyimide (PI) film or a polyethylene naphthalate (PEN) film, preferably a PI film can be used. The PI film and the PEN film to be used are the same as those described above in the first heat fault layer.

The average thickness of the second thermal barrier layer is 10 to 30 탆, preferably 10 to 25 탆, more preferably 12 to 15 탆. If the average thickness of the second thermal barrier layer is less than 10 탆, There may be a problem of cracking and breakage in handling due to deterioration, and when it exceeds 30 탆, it is disadvantageous from the viewpoint of thinning of the outer cover material.

In the case of the casing material for a vacuum insulation panel of the present invention, the heat-resistant adhesive layer 5 is not a general flexible package adhesive but a heat-resistant adhesive. When a general adhesive is used, delamination It is preferable to use a specific high heat resistant adhesive. The high heat-resistant adhesive layer formed between the respective layers is formed of an adhesive of the same or different component and may be a general adhesive used in the related art. However, considering the characteristics of each layer, ) Urethane adhesives and polyether urethane adhesives, it is preferable to use a polyester-based urethane two-component adhesive.

The polyester-based urethane two-pack type adhesive has an NCO molar ratio of 0.88 to 0.92 based on 1 mol of the main chain (-OH), a weight average molecular weight of 30,000 to 40,000 g / mol, preferably a weight average molecular weight of 32,000 to 40,000 g / mol, And preferably 34,000 to 40,000 g / mol. The urethane two-component adhesive may have a hard segment and a soft segment in a molar ratio of 1: 1.1 to 1.4, preferably 1: 1.25 to 1.40. At this time, the hard segment If the soft segment exceeds 1.40 molar ratio, the hard segment may be relatively small and the heat resistance may be deteriorated. If the soft segment is less than 1.1 molar, the flexibility of the high heat resistant adhesive layer may be too low to cause the folding property to deteriorate. It is preferable to use a hard segment having a soft segment molar ratio. Herein, the hard segment refers to a crystalline portion composed of benzene ring, urethane bond, urea bond, etc., and the soft segment means an amorphous portion having a single bond.

The polyester-based urethane two-pack type adhesive preferably comprises a polyester polyol, a chain extender, TDI and a solvent, preferably 45 to 48 wt% of a polyester polyol, 2 to 5 wt% of a chain extender, 5 to 8 wt By weight and 40 to 48% by weight of a solvent.

The high heat-resistant adhesive layer formed between the respective layers may be formed to have the same thickness or different average thicknesses, and the high heat-resistant adhesive layer formed between the layers may have a thickness of 2 to 5 μm, preferably an average thickness of 2 Mu m to 4 mu m. If the thickness is less than 2 mu m, there is a problem that the adhesive strength between the layers is too weak. If the thickness is more than 5 mu m, it is disadvantageous in terms of thinning and the adhesive is overused.

The total thickness of the envelope for a vacuum insulation panel of the present invention is preferably 70 to 150 μm, more preferably 80 to 125 μm. If the total thickness of the envelope is less than 70 μm, Since each layer must be relatively thin, one layer may fail to function properly, and mechanical properties may be reduced, which may be vulnerable to external impact. If the total thickness of the jacket material exceeds 150 mu m, it is disadvantageous to flake-form the jacket material and the flexibility of the jacket material deteriorates and the fold workability and workability may be deteriorated.

The shell material of the present invention may have an oxygen permeability of 0.1 cc / m 3 · day or less, preferably 0.05 to 0.09 cc / m 3 day, and more preferably 0.01 to 0.05 cc / m 3 · day.

The cover material for a vacuum insulation panel of the present invention may have a moisture permeability of 0.05 g / m ² · day or less, preferably 0.02 to 0.04 g / m ² · day, more preferably 0.015 to 0.035 g / m ² · day have.

The jacket for a vacuum insulation panel of the present invention may have a tensile strength of 10.0 kgf / 15 mm or more, preferably 10.5 to 13.5 kgf / 15 mm, and more preferably 11.0 to 13.0 kgf / 15 mm.

The cover material for a vacuum insulation panel of the present invention may have a tear strength of 10.5 kgf / cm2 or more, preferably 10.7 to 14.5 kg / cm2, and more preferably 11.0 to 13.5 kg / cm2.

In addition, the sheathing material of the present invention has a heat shrinkage in the MD (machine direction) of 1% or less, preferably 0.010 to 0.075% when heated at 150 占 폚 for 30 minutes, a heat shrinkage ratio in TD (transverse direction) And may be preferably 0.001 to 0.055%

The shell material of the present invention may have a water absorption rate of 0.1 to 0.8%, preferably 0.15 to 0.70%.

In addition, the sheath material of the present invention may have a thermal conductivity of 0.1500 to 0.2850 W / mK, preferably 0.1500 to 0.2650 W / mK, more preferably 0.1600 to 0.2600 W in the MD direction when measured according to KS L 9016 / mK. The thermal conductivity in the TD direction may be 16,000 to 18,000 W / mK, preferably 16.200 to 17,800 W / mK, and more preferably 16,500 to 17,500 W / mK.

The shell material of the present invention may have a gas permeability (gas barrier property) of 0.1 cc / m < 2 > day or less when measured according to ASTM D3985, and preferably 0.005 to 0.05 cc / m &

The cover material of the present invention may have a moisture barrier property of 0.05 g / m 2 · day or less, preferably 0.005 to 0.045 g / m 2 · day, more preferably 0.005 to 0.040 g / m 2 · day, as measured according to ASTM F1249. M 2 · day.

Hereinafter, a method for manufacturing a high-temperature vacuum insulation panel using the envelope material for a vacuum insulation panel as described above will be described.

The vacuum adiabatic panel of the present invention comprises a first step of laminating a heat-sealable layer, a first thermal insulation layer, a gas-moisture barrier layer and a second thermal insulation layer, And a step of vacuum-packing the core material with the encapsulation material to produce a vacuum insulation material.

Further, the method may further include applying a foaming agent to the outer surface of the vacuum insulating material and foaming the foaming agent to form a foam, and the foaming agent is suitable for use as a vacuum insulation material for construction when forming a foaming agent.

In the first step, the specific types and thicknesses of the heat-sealable layer, the first thermal insulation layer, the gas-moisture barrier layer and the second thermal insulation layer are the same as those described above. The layers may be bonded (or bonded) by a common method used in the related art. For example, a dry lamination method may be used to bond each layer with an adhesive.

Each layer of the laminating base layer can be formed by laminating by a dry lamination method, and can be manufactured through a process as schematically shown in Fig. Specifically, the first paper feed unit 12 supplies a film on a roll constituting a lower layer to be laminated. When the film passes through the space between the coating roll 3 and the press 4 with the adhesive 14 applied thereto, A film and a nip roll 6 constituting an upper layer to be laminated and supplied from the second paper feed unit 8 are passed through a dryer 5 and then a glue is applied to one side of the film supplied from the first paper feed unit, A lower layer and an upper layer are laminated and a film in which a lower layer and an upper layer are finally laminated in the winding section 9 via a cooling roll 7 can be obtained. That is, the PI film or the PEN film may be provided in the first paper-feeding unit, and the aluminum film may be provided in the second paper-feeding unit to produce the film 1 having the first thermal barrier layer-> gas-moisture barrier layer laminated thereon. Next, the film 1 is provided by the first paper-feeding unit, the PI film or the PEN film is provided by the second paper-feeding unit, and the first heat-insulating layer-> the gas- moisture barrier layer-> the second heat- Film 2 can be produced. Then, the film 2 is provided by the first paper-feeding unit and the CPP film is provided by the second paper-feeding unit to form a sheathing material (laminate material) in which the heat-sealable layer-> the first heat shield-> the gas- ) Can be produced.

Also, the two-stage packing can be carried out by packing the core material with the envelope material prepared in Step 2 in a vacuum chamber at a vacuum pressure of 0.005 to 0.05 Torr, preferably 0.005 to 0.02 Torr. The vacuum packed insulation panel is shown in Fig.

In addition, as described above, in the case of application as a thermal insulation material for building, it is also possible to form a foam by blowing a foaming agent into a mold by vacuum-insulating the core material into a mold. At this time, depending on the foaming temperature, The shell material and the foam can be integrated through chemical bonding.

In addition, it is possible to manufacture a vacuum insulation panel of a desired shape and size by controlling the shape of the mold.

The foaming agent may include one kind or two kinds selected from polystyrene or polyurethane. The polystyrene may be EPS (expandable polystyrene). The EPS is prepared by suspension polymerization of PS (polystyrene) resin. Suspension polymerization produces pellets having a size of narrow egg white. And / or pentane gas into a granular polymer. When steam is sprayed on expanded polystyrene, it is foamed and swollen into round granules. The granules are put into a mold, and once again steam is swollen, And it forms a foamed body.

When polyol and isocyanate are mixed with each other, the polyurethane is cured by a crosslinking reaction which is entangled with each other. The polyurethane is applied to a sheathing material for foaming, and then a foaming gas such as a chlorofluorocarbon gas is introduced into the polyurethane curing reaction .

The foam preferably has an average thickness of 15 mm to 40 mm, preferably about 18 mm to 30 mm. When the thickness of the foam is less than 15 mm, If it exceeds 40 mm, the vacuum insulating panel becomes too thick and the flexibility becomes poor, so that it is preferable to form the foam with the thickness within the above range.

The vacuum insulation panel of the present invention manufactured by the above-described method comprises: a core material; And a cover material for the vacuum insulation panel for vacuum packing the core material; And the core material may further include a getter material attached to or inserted into the core material. At this time, the getter material mainly adsorbs residual gas molecules in the vacuum, forms a compound with the gas, and removes gas components flowing through the vacuum insulation material to maintain the heat insulation performance as a vacuum insulation material for a long period of time will be.

Further, it may further comprise a foam formed on the outer surface of the shell material.

The vacuum insulation panel of the present invention may have a total thickness of 10 mm to 50 mm, preferably 10 mm to 40 mm, and when the total thickness of the vacuum insulation panel is 20 mm, , The heat conduction ratio may be 0.25 W / m < 2 > K or less, preferably 0.05 to 0.25 W / m < 2 > K, more preferably 0.12 to 0.25 W /

As a preferred embodiment of the present invention, the high-temperature vacuum thermal insulation panel of the present invention has a thermal conductivity of 0.0045 W / mK or less when the total thickness is 20 mm when measured based on the thermal conductivity measurement method (KS L 9016) May be 0.0040 W / mK or less. When the high-temperature vacuum thermal insulation panel of the present invention can not withstand high temperatures and cracks (breakage) of the casing material occur, there may be a problem that the thermal conductivity rapidly increases to 0.0180 W / mK or more due to air inflow.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Example ]

Example  1: For vacuum insulation panels Envelope  Produce

1) A polyester urethane two-component adhesive was applied to one surface of a PI film (manufacturer: SKCKOLON, average thickness 12 占 퐉) using a dry lamination method as shown in Fig. 5 and then an aluminum film having an average thickness of 7 占 퐉 (First heat shield layer - > high heat resistant adhesive layer- > gas-moisture barrier layer). At this time, the thickness of the high heat-resistant adhesive layer was 3.3 m.

2) Next, using the same dry lamination method, the same polyester urethane two-part type adhesive as described above was applied to one side of the film 1, and then a PI film (manufacturer: SKCKOLONPI, average thickness 12 탆) A first heat shield layer -> a high heat resistant adhesive layer -> a gas - moisture barrier layer -> a high heat resistant adhesive layer -> a second heat shield layer). At this time, the thickness of the high heat-resistant adhesive layer was 3.5 탆.

3) Next, using the same dry lamination method, the same polyester urethane two-part type adhesive as described above was applied to one side of the film 1, and then a casting polypropylene (CPP) film (manufactured by PILMAX, trade name HU, Thickness: 50 占 퐉) was stacked to form a heat-sealable layer (CPP) -> high heat-resistant adhesive layer -> first heat shield layer (PI) -> high heat resistant adhesive layer -> gas- (Al) -> high heat-resistant adhesive layer-> second thermal barrier layer (PI). At this time, the thickness of the high heat-resistant adhesive layer was 3.5 占 퐉.

The polyester urethane two-component type adhesive used for forming the high heat-resistant adhesive layer of each layer had an NCO molar ratio of about 0.90, a weight average molecular weight of 36,200 to 36,300 g / mol, and a hard segment ( hard segment and soft segment are 1: 1.32 mole ratio.

Example  2 ~ Example  3

The second thermal barrier layer was formed as a PEN film in Example 2, and the first thermal barrier layer was formed as a PEN film in the same manner as in Example 1, as shown in Table 1 below.

At this time, the PEN film is a polymer film synthesized through BHEN formation by NDE (2,6-Dimethyl Naphthalene Dicarboxylate) and EG (Ester Interchange) followed by condensation reaction.

Example  4 ~ Example  8

Examples 4 to 8 were carried out in the same manner as in Example 1 except that the thickness of each layer was changed as shown in the following Table 1 to prepare outer cover materials.

Comparative Example  One

1) On one surface of an ethylene vinyl alcohol copolymer film (VM-EVOH, trade name: VM-XL, manufacturer: Kurary, average thickness 12 占 퐉) coated with aluminum by vapor deposition using a dry lamination method as shown in Fig. 5, (VM-EVOH) to the adhesive layer (VM-EVOH) was obtained by laminating a PET film (VM-PET, manufacturer: - > moisture barrier layer (VM-PET)]. The average thickness of the adhesive layer was 3.5 mu m.

2) Next, using the same dry lamination method, a polyester-based urethane two-pack type adhesive was applied to the surface of the film 1, and then a polyethylene (PE) film having an average thickness of 50 탆 (trade name: ) Were laminated to produce a laminate (film) in which a laminate (heat-sealable layer-> adhesive layer-> gas barrier layer-> adhesive layer-> moisture barrier layer) was laminated. At this time, the average thickness of the adhesive layer was 3.2 占 퐉.

3) Next, a polyester-based urethane two-pack type adhesive was applied to one side of the ethylene vinyl alcohol copolymer film of the film 1 using the same dry lamination method, and then a nylon film (NY, trade name: RT92, (Heat-sealable layer- > adhesive layer-> gas barrier layer-> adhesive layer-> water barrier layer-> heat shield layer) was laminated. At this time, the average thickness of the adhesive layer was 3.2 占 퐉.

At this time, the polyester-based urethane two-pack type adhesive used in Example 1 was used.

Comparative Example  2

The polyester urethane two-pack type adhesive used for forming the adhesive layer of each layer had an NCO molar ratio of about 0.80 to 1 mol of the main (-OH) , A weight average molecular weight of 27,500 to 27,600 g / mol, and a hard segment and a soft segment in a molar ratio of 1: 0.95.

Comparative Examples 3 to 6

A sheathing material was prepared in the same manner as in Example 1 except that the sheathing material was prepared by varying the thicknesses of the first heat shielding layer, the gas-moisture barrier layer or the second heat shielding layer as shown in Table 2, Respectively.

division
(Unit: 占 퐉) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 The heat- CPP 50 50 50 50 40 55 50 50 PE - - - - - - - - The high heat resistant adhesive layer 3.5 3.5 3.5 2.8 2.6 2.5 3.0 3.5 First train fault PI 12 12 - 10 8 11 12 - PEN - - 12 - - - - 12 The high heat resistant adhesive layer 3.3 3.4 3.3 2.5 2.4 2.5 3.3 3.3 Gas-moisture barrier layer Al film 7 7 7 8 8 7 - - VM-PET - - - - - - 25 25 The high heat resistant adhesive layer 3.5 3.5 3.5 2.6 2.5 2.5 3.5 3.5 Second train fault PI 12 - - 13 14 11 12 - PEN - 12 12 - - - - 12

division
(Unit: 占 퐉) Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Comparative Example
6 The heat- CPP - 50 50 50 50 50 PE 50 - - - - - Heat-resistant adhesive layer 3.5 2.5 2.5 2.5 2.5 2.5 First train fault PI - 12 4 12 12 - PEN - - - - - - VM-EVOH 12 - - - - 12 The high heat resistant adhesive layer 3.2 2.4 2.5 2.5 2.5 2.5 Gas-moisture barrier layer Al film - 7 7 4 7 - VM-PET 25 - - - - 25 The high heat resistant adhesive layer 2.5 2.5 2.5 2.6 2.5 2.5 Second train fault PI - 12 12 12 8 12 PEN - - - - - - NY 15 - - - - -

Experimental Example  One : Envelope  Experiment 1

The oxygen permeability, the moisture permeability, the tensile strength, and the burst strength of each of the shell materials prepared in Examples 1 to 8 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Table 3 below.

(1) Gas permeability: Measured according to ASTM D-3985 method, using 2/21 equipment of MOCON.

(2) Moisture permeability: Measured according to ASTM F-1249 method, using 3/33 equipment of MOCON.

(3) Tensile strength: Measured according to ASTM D-882 method, using Instron 4465 instrument.

(4) Rupture strength: Measured according to ASTM D-3786 method, and measured using an EL device manufactured by TOYOSEIKI.

division Gas permeability
(cc / m 3 · day) Moisture permeability
(g / m ² · day) The tensile strength
(Kg / mm < 2 & Burst strength
(Kg / cm2) Example 1 0.091 0.030 14.5 12.0 Example 2 0.093 0.029 13.2 11.3 Example 3 0.095 0.023 12.1 10.1 Example 4 0.091 0.027 14.5 12.0 Example 5 0.100 0.027 14.3 11.9 Example 6 0.092 0.033 14.2 11.9 Example 7 0.091 0.031 14.3 13.5 Example 8 0.092 0.029 14.4 13.6 Comparative Example 1 0.110 0.700 14.2 13.4 Comparative Example 2 0.096 0.055 15.1 13.0 Comparative Example 3 0.154 0.067 13.3 10.8 Comparative Example 4 0.112 0.060 13.5 11.2 Comparative Example 5 0.154 0.078 14.3 11.9 Comparative Example 6 0.092 0.039 14.3 12.0

The results of the tests of the above Table 3 show that both Examples and Comparative Examples have excellent tensile strength and breaking strength as a whole. Particularly, the molar ratio of the soft segment of the polyester urethane two-component adhesive constituting the adhesive layer is In the case of Comparative Example 2 using a low value, the tensile strength was very excellent.

In Examples 1 to 8, low gas permeability of less than 0.10 cc / m 2 · day and low moisture permeability of less than 0.05 g / m 2 · day were exhibited.

On the contrary, Comparative Example 1 in which CPP was not used as the heat-sealable layer, Comparative Example 3 in which the thickness of the first heat shield layer was less than 6 탆, Comparative Example 4 in which the thickness of the gas- In the case of Comparative Example 5 in which the thickness was less than 10 占 퐉, the moisture and gas barrier properties were poor compared with the Examples, and the gas permeability and moisture permeability were relatively high.

Experimental Example  2 : Envelope  Experiment 2

The heat shrinkages of the cover materials prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were measured and the results are shown in Table 4 below.

In this case, the heat shrinkage was measured by measuring the length in the MD (machine direction) and the TD (transverse direction) before and after the oven was put in the oven at 150 ° C. for 30 minutes. In addition, the thermal conductivities in the MD and TD directions were measured based on the thermal conductivity measurement method (KS L 9016), and the results are shown in Table 4.

division Heat shrinkage Thermal conductivity MD direction
Heat shrinkage (%) TD direction
Heat shrinkage (%) Horizontal thermal conductivity (W / mk) Vertical thermal conductivity (W / mk) Example 1 0.040% 0.010% 17.25 0.2531 Example 2 0.041% 0.013% 17.26 0.2531 Example 3 0.063% 0.041% 17.26 0.2531 Example 4 0.045% 0.017% 17.95 0.2597 Example 5 0.041% 0.012% 17.95 0.2596 Example 6 0.046% 0.015% 17.26 0.2532 Example 7 0.041% 0.013% 2.34 0.2231 Example 8 0.045% 0.019% 2.25 0.2251 Comparative Example 1 1.500% 0.710% 2.51 0.2510 Comparative Example 2 0.078% 0.069% 17.27 0.2532 Comparative Example 3 0.043% 0.015% 17.30 0.2535 Comparative Example 4 0.041% 0.013% 17.07 0.2532 Comparative Example 5 0.040% 0.016% 17.24 0.2525 Comparative Example 6 0.083% 0.037% 2.32 0.2524

As a result of the test results in Table 4, it was confirmed that the heat shrinkage rate in the MD direction and / or the TD direction was too high in Comparative Example 1 and Comparative Example 6.

Manufacturing example  1: Manufacture of vacuum insulation panel

After the two heat-sealable layers of Example 1 were stacked so as to face each other, they were produced in the form of pouches at the cord M / C.

Next, the core material on which the getter material was placed was placed in the pouch-shaped casing material, and then the vacuum insulation panel manufactured by vacuum packaging was manufactured. A photograph of the vacuum thermal insulation panel is shown in FIG.

Manufacturing example  2 ~ Manufacturing example  8 and Comparative Manufacturing Example  One, Comparative Manufacturing Example  6

Vacuum insulation panels were manufactured in the same manner as in Production Example 1 except that the outer cover materials of Examples 1 to 8 and Comparative Example 6 were respectively used instead of the outer cover material of Example 1 to prepare vacuum insulation panels as shown in Table 5 . The thickness of the vacuum insulation panels is 20 mm.

division Sheath material Production Example 1 Example 1 Production Example 2 Example 2 Production Example 3 Example 3 Production Example 4 Example 4 Production Example 5 Example 5 Production Example 6 Example 6 Production Example 7 Example 7 Production Example 8 Example 8 Comparative Preparation Example 1 Comparative Example 1 Comparative Production Example 2 Comparative Example 6

A photograph of the vacuum insulation panel manufactured in Comparative Production Example 1 is shown in Fig.

Experimental Example  3: Long term stability test of vacuum insulation panel Heat conduction rate  Measure

(1) High-temperature long-term stability evaluation

The vacuum insulation panels prepared in Production Example 1, Comparative Production Example 1 and Comparative Production Example 6 were placed in an oven and left at 150 ° C for 3 months. After that, the vacuum insulation panel was taken out to remove cracks, delamination, And the suture strength was lowered. The photographs after the tests of Comparative Production Example 1 and Comparative Production Example 6 were shown in Figs. 7a and 7b, respectively.

(2) Heat conduction rate  evaluation

In addition, the heat conduction ratio of the vacuum insulating panel was measured based on the KS F2278 thermal conductivity measurement method, and the results are shown in Table 6 below. The heat conduction rate was measured by vacuum packing the vacuum insulation panels to produce vacuum insulation panels. The vacuum insulation panels were placed in an oven, left at 150 ° C for 3 months, taken out,

division Before oven injection
(W / m < 2 > k) After the oven injection
(W / m < 2 > k) Production Example 1 0.250 0.270 Production Example 2 0.252 0.271 Production Example 3 0.255 0.271 Production Example 4 0.257 0.279 Production Example 5 0.258 0.281 Production Example 6 0.250 0.270 Production Example 7 0.249 0.271 Production Example 8 0.249 0.273 Comparative Preparation Example 1 0.253 0.752 Comparative Production Example 2 0.251 0.705

7A and 7B, it can be confirmed that there is a problem that cracks are generated in the casing material in the case of the vacuum insulation panel manufactured from the exterior materials of Comparative Production Example 1 and Comparative Production Example 2.

As shown in Table 6, in the case of Production Examples 1 to 8, the increase in the heat conduction ratio before and after the folding operation is small, whereas in Comparative Production Example 1 and Comparative Production Example 2, the heat conduction rate increases by about 2.5 to 3 times , Which is considered to be the result of vacuum annealing due to cracking during long-term storage at high temperatures

It can be seen from the above Examples and Experimental Examples that the shell material for a high-temperature vacuum insulation panel of the present invention has excellent long-term stability at a high temperature and a temperature of 150 ° C or more, and is excellent in mechanical properties and heat insulation properties while being thin. It has been confirmed that it is possible to provide a heat insulating panel for a variety of uses such as electric and electronic parts and a seat for a seat, which operates under a high temperature, using the covering material of the present invention.

Experimental Example  4: Workability test in manufacturing vacuum insulation panel

The workability in the manufacture of the vacuum insulation panel was evaluated using the vacuum insulation panel envelope materials prepared in Production Examples 1 to 8 and Comparative Production Example 2.

It is a work of folding sealing part of the side during panel work and fixing it with tape. If folding or flexibility of vacuum insulation material is good, work is easy. If folding property is bad, workability is poor.

As a result of comparison, the jacket of Production Examples 1 to 8 was excellent in foldability, but the jacket of Comparative Example 2 had insufficient flexibility and had difficulty in folding work.

1: thermal fusion layer 2: first heat fault layer 3: gas-moisture barrier layer
4: second heat fault layer 5: high heat-resistant adhesive layer
100: shell material 200: core material 300: foam
400: vacuum insulation panel

Claims (17)

delete delete delete delete delete delete A heat fusion layer having an average thickness of 35 mu m to 70 mu m; A first heat shielding layer having an average thickness of 6 탆 to 15 탆; A gas-moisture barrier layer having an average thickness of 4.5 탆 to 10 탆; And a second thermal barrier layer having an average thickness of 10 mu m to 30 mu m;
Heat-resistant adhesive layer having an average thickness of 2 탆 to 4 탆 between the heat-sealable layer and the first thermal insulation layer, between the first thermal insulation layer and the gas-moisture barrier layer, and between the gas-moisture barrier layer and the second thermal insulation layer,
Wherein the heat-sealable layer comprises a cast polypropylene (CPP) film,
The first thermal barrier layer comprises a polyimide film and the second thermal barrier layer comprises a polyimide film or a polyethylene naphthalate film
Wherein the gas-water barrier layer comprises an aluminum foil (Foil)
Wherein the high heat-resistant adhesive layer has an NCO molar ratio of 0.88 to 0.92 with respect to 1 mole of the main chain (-OH), and the high heat-resistant adhesive layer has a hard segment and a soft segment at a molar ratio of 1: 1.25 to 1.4 , And is formed of a urethane two-pack type adhesive having a weight average molecular weight of 32,000 to 40,000 g / mol,
The cover material for a high-temperature vacuum insulation panel has a total thickness of 70 to 125 占 퐉,
The heat shrinkage ratio in the MD (machine direction) is 0.1% to 0.46% and the heat shrinkage ratio in the TD (transverse direction) is 0.001 to 0.055% when heated at 150 占 폚 for 30 minutes,
Wherein the outer cover material for the hot vacuum insulated panel has a thermal conductivity of 0.1500 to 0.2850 W / mK in the MD direction and 16.000 to 18.000 W / mk in the TD direction when measured according to KS L 9016.
delete delete delete 8. The article of claim 7, wherein the jacket material for the hot vacuum insulation panel
When measured according to ASTM D3985, the gas permeability is 0.10 cc / m < 2 > day or less,
Wherein the moisture permeability (ASTM F1249) is 0.05 g / m < 2 > day or less when measured according to ASTM F1249.
A core material containing at least one selected from glass fibers and glass wool; And
And a jacket material according to claim 7 for vacuum packing the core material.
13. The method according to claim 12, further comprising a foam formed on the outer surface of the outer shell,
Wherein the cover material and the foam are integrated with each other.
13. The hot vacuum insulation panel of claim 12, wherein the core material further comprises a getter material attached to or inserted into the core material.
14. A high-temperature vacuum insulation panel according to claim 13, characterized in that the foam is a polystyrene foam or a polyurethane foam.
A first step of laminating a heat-sealable layer, a first heat-shielding layer, a gas-moisture barrier layer and a second heat-shielding layer by dry lamination to produce a sheathing material as a laminate; And
And a second step of vacuum-packing the core material with the sheath material to produce a vacuum insulation material,
A high heat-resistant adhesive layer is provided between the heat-sealable layer and the first thermal insulation layer, between the first thermal insulation layer and the gas-moisture barrier layer, and between the gas-moisture barrier layer and the second thermal insulation layer,
Wherein the heat-sealable layer comprises a cast polypropylene (CPP) film,
The first thermal barrier layer comprises a polyimide film and the second thermal barrier layer comprises a polyimide film or a polyethylene naphthalate film
Wherein the gas-water barrier layer comprises an aluminum foil (Foil)
Wherein the high heat-resistant adhesive layer has an NCO molar ratio of 0.88 to 0.92 with respect to 1 mole of the main chain (-OH), and the high heat-resistant adhesive layer has a hard segment and a soft segment at a molar ratio of 1: 1.25 to 1.4 , And is formed of a urethane two-pack type adhesive having a weight average molecular weight of 32,000 to 40,000 g / mol,
Wherein the thermal insulation layer has an average thickness of 35 mu m to 70 mu m and the first thermal insulation layer has an average thickness of 6 mu m to 15 mu m and the gas- Wherein the barrier layer has an average thickness of 4.5 占 퐉 to 10 占 퐉, the second thermal barrier layer has an average thickness of 10 占 퐉 to 30 占 퐉, and the average thickness of the high heat-resistant adhesive layer is 2 占 퐉 to 4 占 퐉. Way.
17. The method of claim 16,
Further comprising the step of applying a foaming agent and foaming the foaming agent to form a foam after inserting the vacuum insulating material vacuum-packed with the core material into the mold, into the mold.

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