KR101394871B1 - Outer packaging materials of reinforced composite and flame resistance for vacuum insulation panel, preparing method thereof and vacuum insulation panel containing that - Google Patents

Abstract

The present invention relates to an external package material for a vacuum insulation material, a vacuum insulation material pouch including the same and a vacuum insulation material using the same. More specifically, unlike a traditional vacuum insulation material vulnerable to an external impact, the external package material for a vacuum insulation material, the vacuum insulation material pouch including the same and the vacuum insulation material using the same are prevented from receiving damages caused by an external impacts when stored, used, and transferred.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite reinforced flame-retardant outer cover material for vacuum insulation, a method of manufacturing the same, and a vacuum insulation material containing the same,

The present invention relates to a composite reinforced flame retardant outer material for a vacuum insulation material, which is capable of preventing a conventional vacuum insulation material from being extremely poorly impacted by an external impact or the like and being prevented from being damaged during storage, use or movement, a method of manufacturing the same, and a vacuum insulation material will be.

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 difficult to handle because the density of the panel is as high as 200 to 300 kg / m ³ , and there is a risk that the material of the vacuum insulation material is sharply sharpened and there is a risk of welding failure of the joint portion of the outer packaging material Respectively. 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, in Japanese Patent No. 59-140046, high-density polyethylene and polypropylene are used in the film used for the heat-sealable layer in view of gas-ducting and heat resistance, which blocks the gas permeating along the periphery of the heat- 2000-108255 discloses a technique of using a film laminated with polyethylene having a different melting point in a heat-sealable layer in order to ensure airtightness even in the presence of foreign matter during thermal fusion. 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 .

In order to eliminate the adverse effect of the sealing portion, a technique of folding and sealing the sealing portion is disclosed in Patent Document 10-141583. 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, The deterioration of the heat insulation performance due to the bridge is minimized.

However, the vacuum insulation material made of such a sheath material is suitable for use in an environment where the use environment such as a refrigerator is not severe or an external impact is not applied, but it has been limited to use as a vacuum insulation material for construction. There is a problem that the outer material and / or the core material of the vacuum insulation material is broken by the external impact and the vacuum is destroyed when used for the construction. Therefore, there is a limitation in using the existing vacuum insulation material for construction, And the insulation effect is greatly reduced. In addition, although it is disclosed that the nonwoven fabric is stuck to the reinforcement for strength reinforcement in the publication No. 10-2011-0077859, since the nonwoven fabric layer is made of polypropylene and polyethylene terephthalate, it is difficult to expect a flame retardant effect.

The present inventors have made efforts and studies to prevent the vacuum insulation material from being broken by an external impact. As a result, the present inventors have found that the vacuum insulation material can be protected from the external impact by using the vacuum insulation material without increasing the weight of the vacuum insulation material, And developed a composite reinforced flame retardant outer covering for insulation. That is, the present invention provides a composite reinforced flame retardant outer material for vacuum insulation material, a method of manufacturing the same, and a vacuum insulation material manufactured using the same.

The present invention provides a composite reinforced flame retardant outer covering for vacuum insulation material, comprising: a heat fusion layer; Aluminum thin film layer; Nylon layer; A PET layer containing a layer of alumina vapor-deposited polyethylene terephthalate (VM-PET) or a layer of polyethylene phthalate (Alox-PET) vapor-deposited on silica; A low density polyethylene (LDPE) layer; And an impact protection layer.

As a preferred embodiment of the present invention, the composite reinforced flame retardant outer covering material of the present invention comprises a thermofusion layer in the outward direction inside the outer covering material; Aluminum thin film layer; Nylon layer; A PET layer; A low density polyethylene layer; And an impact protection layer laminated in this order.

As a preferred embodiment of the present invention, the composite reinforced flame retardant outer covering of the present invention comprises a heat-sealable layer and an aluminum thin film layer; An aluminum thin film layer and a nylon layer; A nylon layer and a PET layer; And a PET layer and a low density polyethylene layer; And an adhesive layer therebetween.

In another preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the impact protection layer includes a polyethylene layer, an anchor coating layer and a glass fiber layer, and the polyethylene layer is a linear low density polyethylene And an AC coating layer and a glass fiber layer are laminated on the other surface of the polyethylene layer.

According to another preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the AC coating layer of the impact protection layer is formed of an isocyanate-based AC coating agent and has a coating amount of 0.5 to 1.5 g / m ² can do.

In another preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the polyethylene layer of the impact protection layer has an average thickness of 10 to 20 탆, the AC coating layer has an average thickness of 0.5 to 1.5 탆, And the glass fiber layer has an average thickness of 30 to 200 mu m.

In another preferred embodiment of the present invention, the glass fiber layer may include at least one selected from the group consisting of E-glass, C-glass, and S-glass.

In another preferred embodiment of the present invention, the glass fiber layer comprises 50 to 60 wt% of SiO ₂ , 10 to 20 wt% of Al ₂ O ₃ , 8 to 10 wt% of B ₂ O ₃ , 1 to 2 wt% of MgO, Wherein the composition comprises 20 to 24 wt% of MaO, 0.1 to 1 wt% of Na ₂ O, 0.1 to 1 wt% of K ₂ O, 0.01 to 0.5 wt% of TiO _{2, and} 0.01 to 0.5 wt% of Fe ₂ O ₃ have.

In the composite reinforced flame retardant outer covering of the present invention, the heat-sealable layer may be made of a material selected from the group consisting of linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene ), Ethylene-acrylic acid (EAA), ethylene-methylacrylate (EMA), ethylene-methylmethacrylic acid (EMAA), ethylene-methylmethacrylate (EMMA) , An ionomer (Ionomer, IO), and ethylene-ethyl acrylate (EEA). The linear low density polyethylene may have a specific gravity of 0.92 or more.

Further, as a preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the linear low density polyethylene may be metallocene linear low density polyethylene (m-LLEPE).

Further, as a preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the PET layer has an average thickness of 8 to 20 μm.

Further, as a preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the nylon layer has an average thickness of 15 to 30 탆.

In one preferred embodiment of the present invention, in the composite reinforced flame retardant outer covering of the present invention, the aluminum thin film layer includes an aluminum deposited film or an aluminum foil, and the aluminum thin film layer has an average thickness of 6 to 9 탆 .

Further, as a preferred embodiment of the present invention, the composite reinforced flame-retardant outer covering material of the present invention may have a total thickness of 140 to 350 μm, and the above-mentioned vacuum insulation- .

Another aspect of the present invention relates to a method of manufacturing the composite reinforced flame retardant outer cover material for vacuum insulation materials of various embodiments as described above, which comprises a heat-fusion layer, an aluminum thin film layer, a nylon layer, a VM- And a linear low density polyethylene layer are successively laminated by dry lamination to produce a lamination base layer; And forming an impact protection layer on the lamination base material layer by extrusion lamination in which a polyethylene resin is coated between the glass fiber coated on one side with the laminating base material layer and the AC coating material, An outer covering material for a heat insulating material can be manufactured.

Another aspect of the present invention relates to a vacuum insulation material comprising: the composite reinforced flame retardant outer material as described above; And a heat insulating material containing at least one selected from glass fiber, polyurethane, polypropylene and polyester.

As a preferred embodiment of the present invention, the vacuum insulation material of the present invention may further include a getter material attached to or inserted into the heat insulation material.

The composite reinforced flame retardant outer cover material for vacuum insulators of the present invention is excellent in mechanical strength such as impact resistance and sealing strength and physical properties such as moisture and gas barrier property and is used to protect the inside insulation of vacuum insulation and to maintain the vacuum, And the outer shell material itself is excellent in the adiabatic effect. In addition to the thermal insulation effect by the inner insulation and the vacuum, the adiabatic material itself has an effect of further increasing the adiabatic effect. Particularly, And it is expected that it will be possible to substitute and use vacuum insulation material for existing construction.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a composite reinforced flame retardant outer covering material for a vacuum insulator of the present invention and a heat insulating material (or core material).
Figs. 2A and 2B are photographs taken on the outside and inside of the composite reinforced flame retardant outer cover material for vacuum insulator prepared in Example 1. Fig.
3 is a schematic view of a step of forming an adhesive layer by a dry lamination method according to one embodiment of the present invention.
4 is a schematic diagram of an extrusion lamination process in which an impact protection layer is formed on a laminating substrate (or substrate layer), according to one embodiment of the present invention.
5A and 5B are photographs of the flame retardance measurement results of Example 1 and Comparative Example 4 performed in Experimental Example 2. FIG.
6A and 6B are photographs of heat resistance measurement results of Example 1 and Comparative Example 4 performed in Experimental Example 2. FIG.

Hereinafter, the composite reinforced flame retardant outer covering for vacuum insulators of the present invention will be described in detail.

As shown in FIG. 1, the composite reinforced flame retardant outer covering material 200 for a vacuum insulator of the present invention comprises a heat-sealable layer 201; An aluminum thin film layer (Al thin film layer, 202); Nylon layer (NY layer, 203); A polyethylene terephthalate layer (PET layer) 204 containing a layer of polyethylene terephthalate (VM-PET) on which alumina is vapor-deposited or a layer of polyethylene terephthalate (Alox-PET) on which silica is vapor-deposited; A low-density polyethylene layer (LDPE layer) 205; And an impact-protective layer 250, wherein the heat-sealable layer in the outward direction inside the sheathing material; Aluminum thin film layer; Nylon layer; A PET layer; A linear low density polyethylene layer; And an impact protection layer laminated in this order.

The laminating base material 230 or the laminate base material layer (laminated layer) in the order of the heat-sealable layer -Al thin film layer -NY layer -PET layer -LDPE layer excluding the impact protection layer among the composite reinforced flame retardant foreign material for vacuum insulator of the present invention 230).

Specifically, each layer of the outer covering material for vacuum insulation material of the present invention includes a heat-sealable layer and an Al thin film layer; An Al thin film layer and an NY layer; NY layer and PET layer; And each layer of the PET layer and the LDPE layer can be adhered (or bonded) by a common method used in the related art. As shown schematically in FIG. 3, each layer can be adhered to each other using a dry lamination method It is preferable to produce a laminating base layer by bonding. The adhesive used for bonding each layer may be a general adhesive used in the related art, but it is preferable to use a polyester urethane adhesive in consideration of the characteristics of each layer.

The adhesive layer formed of the adhesive is preferably formed so as to have an average thickness of 2.5 to 5 占 퐉, preferably an average thickness of 3.5 to 4.5 占 퐉, and if it is less than 2.5 占 퐉, If it is more than 5.0 탆, it is disadvantageous from the viewpoint of thinning, and the adhesive is over-used, which is not economical.

The impact protection layer 250 constituting the composite reinforced flame retardant outer covering material for a vacuum insulator of the present invention comprises a polyethylene layer (PE layer) 206, an AC coating layer 207 and a glass fiber layer 208, The PE layer 206 is formed on one surface of a low density polyethylene (LDPE) layer 205, preferably on one side of a linear low density polyethylene (LLDPE) layer, and the AC coating layer and / A glass fiber layer may be laminated.

In the impact protection layer, the polyethylene (PE) layer serves to connect the glass fiber layer and the LDPE layer (or preferably, the LLDPE layer) to each other. In this case, the glass fiber layer and the VM- It is preferable to laminate an LDPE layer (or LLDPE layer) on the PET layer and form a PE layer because it is difficult to directly adhere the PET layer such as Alox-PET layer by the extrusion lamination method. The PE layer may be formed by coating (or injecting or inserting) a polyethylene resin between the AC coating layer (or adhesive layer) formed on one side of the glass fiber and the LDPE layer formed on the upper side of the laminating base layer have. There is no separate adhesive layer between the PE layer of the impact protection layer and the laminating base layer, and the PE layer and the laminate base layer are bonded directly to the LDPE layer to bond (or bond) the impact protection layer and the LDPE layer. The PE layer can directly adhere the LDPE layer and the glass fiber layer in which the A.C coating layer is formed by a PE resin through a T die having a high extrusion temperature as shown in FIG. 4 without a separate adhesive.

The average thickness of the PE layer (extruded PE layer) is preferably 5 to 40 占 퐉, more preferably 10 to 30 占 퐉, and further preferably 10 to 20 占 퐉. At this time, the average thickness of the PE layer is less than 10 占 퐉 There is a problem that the extrusion processability is difficult and the adhesive force is weak. If it is more than 40 탆, the thickness is too thick, which makes the thickness of the outer covering difficult to be formed.

A coating layer (or adhesive layer) is formed therebetween in order to adhere the PE layer of the impact protection layer and the glass fiber layer. The coating layer (or adhesive layer) is coated with an anchor coating agent in the manner schematically shown in FIG. The reason for introducing the AC coating layer is that the PE (polyethylene) resin used for the formation of the PE layer is different from the PE resin used for forming the PE layer, because the AC coating is applied on one side of the glass fiber layer, Since it is inactive, there is no polar group, and therefore adhesion to glass fiber may be deteriorated. Therefore, it is advantageous to introduce an AC coating layer and to induce molecular attraction between the surfaces of the substrates to be bonded (or bonded) The reason for introducing the AC coating layer is that the adhesion between the glass fiber layer and the LDPE layer and / or the PET layer is very poor, (Or bonding) the substrate layer and the impact protection layer.

If the average thickness of the AC coating layer (or adhesive layer) is less than 0.3 μm, it is preferable that the AC coating layer (or the adhesive layer) has an average thickness of 0.3 to 2.0 μm, preferably an average thickness of 0.5 to 1.5 μm. There may be a problem that a part of the glass fiber layer falls due to an external impact or the like because the adhesive force between the glass fiber layer and the glass fiber layer is decreased. When the average thickness exceeds 2.0 탆, the adhesive is excessively used, It is good.

The AC coating agent may be one or more AC coating agents selected from the group consisting of titanate, polyimine, butadiene, and isocyanate, and is preferably an isocyanate The use of an AC coating agent is advantageous in terms of adhesive strength, heat resistance, water resistance, boilability and oil resistance.

In the impact protection layer 250, the glass fiber layer 208 may be made of general glass fiber. Preferably, the glass fiber layer 208 may be made of glass containing at least one selected from the group consisting of E-glass, C-glass and S- Fiber, and more preferably E-glass fiber.

Further, the glass fiber layer is SiO ₂ 50 ~ 60 _{wt%, Al 2 O 3 10 ~} 20 _{wt%, B 2 O 3 8 ~} 10 wt%, MgO 1 ~ 2 weight%, MaO 20 ~ 24 wt%, Na ₂ O 0.1 ~ 1 wt%, K ₂ O 0.1 ~ 1 wt%, TiO ₂ 0.01 ~ 0.5 wt% of Fe ₂ O ₃ 0.01 ~ glass fiber containing 0.5 wt.%, preferably SiO ₂ 52 ~ 58% by weight _{, Al 2 O 3 10 ~ 18} % by weight, B ₂ O ₃ 8 ~ 9 wt%, MgO 1 ~ 2 weight%, MaO 20 ~ 23 wt%, Na ₂ O 0.5 ~ 1 wt%, K ₂ O 0.5 ~ 1 0.01 to 0.1% by weight of TiO _{2, and} 0.01 to 0.1% by weight of Fe ₂ O ₃ .

In addition, the glass fiber used in the glass fiber layer is not particularly limited in its woven form, but may be plain, twilled, satin, leno plain or imocked (mock leno or imitation leno) is preferably used.

The glass fiber layer preferably has an average thickness of 30 to 200 占 퐉, preferably an average thickness of 30 to 120 占 퐉. If the glass fiber layer is less than 30 占 퐉, there may be a problem that the strength is weakened. The flexibility of the outer covering material for vacuum insulation is deteriorated due to too thick, and workability and workability may be deteriorated. Therefore, it is preferable to have an average thickness within the above range.

In the composite reinforced flame retardant outer covering for vacuum insulators according to the present invention, the heat-sealable layer 201 is formed by sealing or inserting a heat insulating material (or a core material 100) (HDPE), polypropylene (PP), ethylene-acrylic acid (EAA), ethylene-methylene chloride (HDPE) Ethylene-methylacrylate (EMA), ethylene-methylmethacrylic acid (EMAA), ethylene methylmethacrylate (EMMA), ionomer (Ionomer IO) and ethylene ethyl acrylate , ethylene-ethylacrylate, and preferably at least one selected from the group consisting of LLDPE, LDPE and HDPE, more preferably LLDPE, More preferably, metallocene linear low-density polyethylene (m-LLDPE) among LLDPE is used in terms of heat-sealing composition, heat sealing strength, low brittleness and transparency. The LLDPE preferably has a specific gravity of 0.92 or more, and preferably has a specific gravity of 0.92 to 0.95.

The heat-sealable layer 201 preferably has an average thickness of 25 to 60 占 퐉, preferably 30 to 50 占 퐉. If the heat-sealable layer is less than 25 占 퐉, the heat sealable strength is weak and the problem of gas and moisture permeability And when it exceeds 60 탆, it is disadvantageous for thinning. Therefore, it is preferable that the thickness is within the above range.

The aluminum foil layer may be formed on one side of the heat-sealable layer. The aluminum foil layer may be formed of aluminum 8011, aluminum 8021, aluminum 8077, Aluminum 8000 series products such as Aluminum 8079 or Aluminum 1000 series products such as Aluminum 1050 and Aluminum 1235 and preferably Aluminum 8011, Aluminum 8021, Aluminum 8077, Aluminum 8079 and Aluminum 8021 of Sanya Aluminum Co., It is preferable to use pinholes and cracks.

The aluminum thin film layer is preferably formed to have an average thickness of 4.5 to 9 占 퐉, preferably an average thickness of 6 to 9 占 퐉, more preferably 6 to 7 占 퐉. At this time, if the aluminum thin film layer is less than 4.5 占 퐉 There may be a problem that the gas and moisture barrier properties are reduced due to the presence of a large number of pinholes. On the other hand, when the thickness exceeds 9 탆, the thermal conductivity may be high and the heat insulating effect may deteriorate. Therefore, it is preferable to form the aluminum thin film layer so as to have a thickness within the above range.

The nylon layer (NY layer 203) serves to impart gas barrier properties and flexibility, and the nylon layer includes at least one selected from NY11, NY6, NY66 and NY610 And the average thickness of the NY layer is preferably 15 to 30 탆, preferably 15 to 25 탆. When the average thickness of the nylon layer is less than 15 탆 There may be a problem of high air permeability. If it exceeds 30 탆, there may be a problem of thinning, so it is preferable to form the layer with an average thickness within the above range.

The polyethylene terephthalate layer (PET layer) 204 of the outer covering material for a vacuum insulator of the present invention has mechanical strength and water barrier properties and can be formed on one side of the NY layer 203. The PET layer may be formed of a polyethylene terephthalate (VM-PET) coated with alumina or a polyethylene terephthalate (Alox-PET) coated with silica, preferably a VM-PET Is advantageous in terms of flexibility and minimum crack occurrence. Among conventional vacuum insulation materials, PVDC-coated K-PET films are used for the cross section of the PET film, which is excellent in barrier properties such as oxygen permeability and moisture permeability and sealing ability. However, Or VM-PET.

The PET layer is preferably formed so as to have an average thickness of 8 to 20 占 퐉, preferably 10 to 12 占 퐉. If it is less than 8 占 퐉, the strength may be weak and the moisture permeability may be deteriorated. There is a problem in thinning, so it is preferable that the thickness is within the above range.

In the present invention, the low density polyethylene layer (LDPE layer) 205 of the outer covering material for a vacuum insulator of the present invention has a function of easily bonding the laminate layer and the glass fiber, and the low density polyethylene resin is preferably a low density polyethylene A polyethylene (LLDPE) resin may be formed on one surface of the PET layer after filming or sheeting. The low-density polyethylene layer has an average thickness of 20 to 40 탆, preferably 25 to 30 탆, which satisfies the adhesive property and is advantageous in cost.

It is preferable that the outer covering material of the vacuum insulation material of the present invention has a total thickness of 72 to 160 mu m, preferably 80 to 140 mu m, of the laminate base material layer 230 of the present invention, , The strength of the vacuum insulator pouch is weak, which may be detrimental to maintaining the vacuum state. If it exceeds 160 μm, the vacuum insulator pouch may be detrimental to thinning.

Further, the total thickness of the composite reinforced flame retardant outer cover material for vacuum insulation material including the laminate base material and the impact protection layer is preferably 140 to 350 μm, more preferably 150 to 300 μm. At this time, the total thickness of the outer cover material for vacuum insulation If the total thickness of the outer covering material for the vacuum insulation material is more than 350 μm, the mechanical properties are excellent, but the flexibility of the outer covering material for the vacuum insulation material falls and the folding operation It is preferable to produce the outer cover material for vacuum insulation material so that the average thickness within the above range is obtained.

A method for producing a composite reinforced flame retardant outer covering material for a vacuum insulator according to the present invention will now be described with reference to the accompanying drawings. A PET layer, and a low-density polyethylene (LDPE) layer in this order by dry lamination to produce a lamination substrate layer; And forming an impact protection layer on the lamination base material layer by extrusion lamination in which a polyethylene resin is coated between the laminated base material layer and the glass fiber coated on one side of the AC coating material, The outer covering material for a vacuum insulator of the present invention can be produced.

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 exemplified in Fig. Specifically, the first paper-feeding unit 1 supplies aluminum on a roll constituting a lower layer to be laminated. When passing through the coating roll 3 with the adhesive 2 and the press 4, A film and a nip roll (6) constituting the upper layer to be laminated, fed from the second paper feed unit (8), are passed through a dryer (5, dry chamber) 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, an Al thin film is provided in the first paper-feeding unit and a film constituting the heat-sealable layer is provided in the second paper-feeding unit to produce a film in which the heat-sealable layer-Al thin film layer in which these are stacked is formed. Next, the film of the heat-sealable layer-Al thin film layer is provided by the first paper-feeding unit, the NY film (or sheet) is provided by the second paper-feeding unit, Can be manufactured. This process is repeated to produce a laminate substrate (or substrate layer) in which a hot-melt adhesive layer-Al thin film layer -NY layer-PET layer-LDPE layer is laminated in order.

The outer covering material for vacuum insulation material of the present invention in which the impact protection layer and the lamination base material layer are laminated can be produced by an extrusion lamination method, and can be manufactured through a process as shown in the example shown in Fig. Specifically, when the glass fiber is fed from the paper feeding unit 21, the glass fiber passes through the press 23 and the AC coating unit 22, and the AC coating is applied to one side of the glass fiber, chamber. Next, the laminating base material supplied from the laminating base material supply unit 27 and the glass fiber coated with the AC coating material pass between the rubber roll 29 and the cooling roll 30, and an impact protection layer is formed on the top of the laminating base material. (Thermally fusible layer-AL thin film layer -NY layer-PET layer-LDPE layer) and a laminate layer (thermoplastic resin layer) are formed by coating (or supplying) the PE resin 26 between the AC coating layer of the glass fiber and the laminating base material through the extruder 25 The outer cover material for vacuum insulator of the present invention can be manufactured through the winding portion 31 after the impact protection layer (PE layer -AC coating layer-glass fiber layer) is laminated.

At this time, the coating of the polyethylene (PE) resin is preferably performed by extruding the polyethylene resin through an extruder at an extrusion temperature of 280 ° C. to 320 ° C., preferably 290 ° C. to 310 ° C., It is preferable to give a change within the extrusion temperature.

The above-described composite reinforced flame-retardant outer cover material for vacuum insulation material of the present invention can be used to produce a vacuum insulation material by inserting a heat insulation material (or a core material) into the outer material, and the vacuum insulation material can be produced using the same. In one embodiment, the vacuum insulator composite reinforced flame retardant outer sheath of various forms described above; And a getter material which can include at least one selected from the group consisting of glass fiber, polyurethane, polypropylene, and polyester, and a getter material attached to or inserted into the heat insulating material, .

The getter material mainly adsorbs residual gas molecules in the vacuum, forms a compound with the gas, and removes gas components flowing through the outer wall of the vacuum insulation material so as to maintain the heat insulation performance as a vacuum insulation material for a long period of time.

The vacuum insulation material of the present invention can be widely used not only as a vacuum insulation material for electronic appliances such as a refrigerator but also as a vacuum insulation material for construction.

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: Combined reinforced flame retardancy for vacuum insulation Outer material  And vacuum insulation

(1) Production of laminate substrate

1) An adhesive (Urethane adhesive) was applied to one surface of an aluminum foil (average thickness of 7 mu m, Sanyo Aluminum Co., Ltd., 8079 material) using a dry lamination method as shown in Fig. 3 and then a nylon film , AT-93) were laminated to prepare Film 1 (Al thin film layer -NY layer).

2) Next, VM-PET film (coron, CGR-31) having an average thickness of 12 탆 was laminated on the film 1 by using the same dry lamination method to prepare film 2 (Al thin film layer -NY layer-PET layer) .

3) Next, using the same dry lamination method, the film 2 was laminated with an average thickness 30 占 퐉 of a metallocene linear low density polyethylene (m-LLDPE) film (Korean prepack, M-PE film heat fusion layer) ) To prepare Film 3 (heat fusion layer-Al thin film layer -NY layer-PET layer).

4) Next, a linear low density polyethylene (LLDPE) film (Korean prepack, LDPE Film) having an average thickness of 30 占 퐉 was laminated on the film 3 using the same dry lamination method to form a laminate base material Layer-PET layer-low density polyethylene layer).

(2) Impact protective layer lamination

(E-glass, SiO ₂ 52.8% by weight, Al ₂ O ₃ 14% by weight, B ₂ O ₃ 8.3% by weight) having a mean thickness of 100 μm by using an extrusion lamination method as shown in FIG. %, MgO 1.5 wt.%, MaO 21.5% by weight, Na ₂ O 0.6% by weight, K ₂ O 0.7 wt%, TiO ₂ 0.3% by weight of Fe ₂ O ₃ 0.3% by weight) isocyanate AC coatings (曹達on one side of, T-160), followed by drying to form an AC coating layer. Then, as an extruder, a polyethylene resin was extruded with a T-die having an average temperature of 300 ° C to form an impact protection layer on the top of the laminating base material Thereby producing an outer covering material for vacuum insulation.

In the manufactured impact protection layer, the average thickness of the PE layer was 15 占 퐉, the AC coating layer had an average thickness of 1.2 占 퐉, and the glass fiber layer had an average thickness of 100 占 퐉.

2) The pouch-type composite heat-strengthening flame-retardant outer covering material was fabricated by stacking the heat-sealable layer of the outer fabric so as to face each other. FIG. 2 is a photograph showing the exterior and interior of the produced vacuum insulator composite reinforced flame retardant outer cover material.

Comparative Example  1 ~ Comparative Example  3

Except that a titanate-based AC coating, a polyimide-based AC coating and a butadiene-based AC coating were used instead of the isocyanate-based AC coating as an AC coating, respectively, in the same manner as in Example 1, And Comparative Example 1 to Comparative Example 3 were carried out, respectively.

Experimental Example  1: For vacuum insulation material Outer shell  Physical property measurement experiment

The adhesive strength, water resistance, boilability and heat resistance of the outer covering material for vacuum insulation material prepared in Example 1 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Adhesion О О О О Water resistance × × △ О Surname × × × О Heat resistance △ △ △ О ◯: Excellent, △: Normal, Ũ: Not good

As a result of the test results shown in Table 1, all of Comparative Examples 1 to 3 and Example 1 using the titanate-based AC coating agent, the polyimide-based AC coating agent and the butadiene-based AC coating agent were excellent in adhesion, It was confirmed that the water resistance, the releasability and the heat resistance were not good as compared with Example 1 using the isocyanate-based AC coating agent, and it was confirmed that the use of the isocyanate-based AC coating agent is advantageous in terms of physical properties.

Example  2 ~ Example  3

A pouch-type composite reinforced flame-retardant covering material for a vacuum insulator was prepared in the same manner as in Example 1, except that each layer had a thickness as shown in Table 2 below.

Example  4

A composite reinforced flame retardant outer covering material for a vacuum insulator in the form of a pouch was prepared in the same manner as in Example 1 except that 8021 material of Sana Aluminum was used in place of aluminum 8079 material as an aluminum thin film layer and VM- CGR-31) instead of Alox-PET film.

Example  5 ~ Example  6

(M-LLDPE, Korea Pre-Pack, M-PE Film) instead of a metallocene linear low-density polyethylene film as a heat-sealable layer in the same manner as in Example 1, Example 5 and Example 6 were respectively carried out using a polyethylene film (LLDPE film, Korea prepack, L-LDPE film) and a low density polyethylene film (LDPE film, Korea prepack, LDPE Film).

Comparative Example  4

A laminating substrate made of a heat-sealable layer-an Al thin film layer -NY layer-PET layer without an impact protection layer (polyethylene layer-AC coating layer-glass fiber layer) was prepared in the same manner as in Example 1 above Itself was made of an outer covering material for vacuum insulation.

Comparative Example  5 ~ Comparative Example  7

A composite reinforced flame-retardant covering material for a vacuum insulator in the form of a pouch was prepared in the same manner as in Example 1, except that each layer had a thickness as shown in Table 3 below.

division
(Unit: 占 퐉) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 ramie
Nate
The substrate layer The heat- 30 40 35 30 30 30 Al
Thin film layer 7 7 6 7 7 7 NY Floor 25 20 28 25 25 25 PET layer 12 15 12 12 12 12 LDPE layer 30 28 28 30 30 30 Shock
Protective layer PE layer 15 18 20 15 15 15 A.C coating layer 1.2 1.2 1.2 1.2 1.2 1.2 Glass fiber layer 100 90 140 100 100 100

division
(Unit: 占 퐉) Comparative Example
4 Comparative Example
5 Comparative Example
6 Comparative Example
7 ramie
Nate
The substrate layer The heat- 30 15 30 30 Al
Thin film layer 7 7 7 4.2 NY Floor 25 12 25 25 PET layer 12 12 12 12 LDPE layer 30 30 30 30 Shock
Protective layer PE layer - 15 8 15 A.C coating layer - 1.2 0.3 1.2 Glass fiber layer - 90 140 100

Experimental Example  2: Composite reinforced flame retardant for vacuum insulation Outer shell  Measurement of heat resistance and flame retardancy

The flame retardancy, heat resistance and flexibility of each of the outer cladding materials prepared in Example 1, Comparative Example 4, Comparative Example 6, and Comparative Example 7 were measured in the following manner, and the results are shown in Table 4 below. Further, the results of photographs measuring flame retardancy are shown in Fig. 5, and the results of photographs in which heat resistance is measured are shown in Fig. 6, respectively.

1) Flame retardancy: According to the UL 94 method, the outermost layer of the cladding material was contacted with a flame for 10 seconds to visually observe the combustion.

2) Heat resistance test method: The specimen was contacted with an electric heater (electric heater, spiral type) for 10 seconds, and the shrinkage phenomenon was visually observed (heater surface temperature: 300 ° C).

3) Evaluation of Flexibility and Foldability: The center portion was folded and reciprocated 10 times with a 2 kg roller, and then folded in the opposite direction and reciprocated 10 times. Then, the cracks and pinholes of the aluminum thin film layer were observed.

division Example  One Comparative Example  4 Comparative Example  6 Comparative Example  7 Flammability Good Burned Good Good Heat resistance Good Shrinkage occurs Good Good Flexibility and Foldability Good Al thin film layer cracks occur Separation between laminate substrate and impact protection layer occurred Al thin film layer cracks and pinholes occur

In the case of the composite reinforced flame-retardant outer covering for vacuum insulator of the present invention of Example 1, excellent results were obtained in terms of flame retardancy, heat resistance, flexibility, and foldability. Referring to FIG. 5A, only a slight soot It was confirmed that the flame retardancy was excellent. Further, as shown in FIG. 6A, it was confirmed that the shrinkage and the combustion did not occur, and the heat resistance was excellent.

However, in the case of Comparative Example 4 having no impact protection layer, as shown in FIG. 5B and FIG. 6B, flame retardancy was low and shrinkage occurred and heat resistance was not good.

Further, in the case of Comparative Example 6 in which the PE layer of the impact protection layer is less than 10 占 퐉 and the AC coating layer is formed to be not more than 0.5 占 퐉, the adhesion between the impact protection layer and the laminate base layer is weak, There is a problem that the folding property is deteriorated.

In the case of Comparative Example 7 in which the Al thin film layer was formed to have a thickness of less than 4.5 탆, the flame retardancy and heat resistance were good, but the Al thin film layer was too thin and cracks and pinholes were generated.

Experimental Example  3: Combined reinforced flame retardant for vacuum insulation Outer shell  Physical property measurement experiment

The oxygen permeability, the moisture permeability, the tensile strength and the tear strength of each of the vacuum insulation materials prepared in Examples 1 to 4 and Comparative Examples 4 to 5 were measured by the following methods, and the results are shown in Table 5 below.

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

(2) Water vapor permeability: Measured according to ASTM F-1249 method, using 3/33 equipment manufactured by 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 Oxygen permeability
(cc / m 3 · day) Moisture permeability
(g / m 2 · day) The tensile strength
(Kg / mm < 2 & Burst strength
(Kg / cm2) Example 1 0.046 0.0045 148 12 Example 2 0.044 0.0042 145 12 Example 3 0.045 0.0048 162 14 Example 4 0.045 0.0039 143 11 Example 5 0.046 0.0041 140 10 Example 6 0.044 0.0042 138 11 Comparative Example 4 0.042 0.0040 53 10 Comparative Example 5 0.063 0.0281 139 11

In Examples 1 to 6, not only the oxygen permeability was 0.05 or less and the moisture permeability was 0.005 or less, the tensile strength and the burst strength were also excellent.

In the case of Comparative Example 4 having no impact protection layer, the oxygen permeability was 0.05 or less and the moisture permeability was 0.005 or less, but the tensile strength was not very good as compared with Examples 1 to 4 of the present invention.

In Comparative Example 5 in which the heat-welded layer was less than 25 占 퐉 and the NY layer was less than 15 占 퐉, the tensile strength and the burst strength were excellent, but the oxygen permeability exceeded 0.05, 4 and Comparative Example 4, the moisture permeability was not so good because the heat-sealable layer was too thin to make the gas and moisture permeability weak, and the NY layer was thin and the durability was poor.

Experimental Example  3: Heat Seal Strength  Measurement experiment

The heat sealing strengths of the composite reinforced flame retardant outer cover materials for vacuum insulators prepared in Examples 1, 5 and 6 were measured using an Instron 4465 instrument according to ASTM D-882, and the results are shown in Table 6 Respectively.

division Example 1 Example 2 Example 3 Heat Seal Strength
(kg / 15 mm) 7.9 6.8 5.2

In all of the outer materials of Examples 1 to 3, the heat sealing strength was generally excellent at 5 kg / 15 mm or more, but Example 1 using m-LLDPE showed the best heat sealing strength.

The vacuum insulator made of the composite reinforced flame retardant outer material for vacuum insulator of the present invention is excellent in physical properties such as flame retardance, heat resistance, oxygen permeability, moisture permeability, tensile strength and burst strength, I was able to confirm that it was excellent. In particular, it has been confirmed that the vacuum insulation material of the present invention is highly suitable for use as a vacuum insulation material for construction, which is harsh for use or work environment.

1: first paper feed unit, 2: adhesive 3: coating roll
4: Press 5: Dryer 6: Nip roll
7: cooling roll 8: second paper feed unit 9: winding unit
21: paper feed unit 22: AC coating unit 23: press
24: dryer 25: extruder 26: PE resin
27: Lamina? Base feeder 28: back up roll
29: rubber roll 30: cooling roll 31:

Claims (17)

A heat fusion layer; Aluminum thin film layer; Nylon layer; A PET layer containing a polyethylene terephthalate (VM-PET) layer on which alumina is vapor-deposited or a polyethylene terephthalate (Alox-PET) layer on which silica is vapor-deposited; A low density polyethylene layer; And an impact protection layer,
A thermally fusible layer in the outer direction inside the outer covering material; Aluminum thin film layer; Nylon layer; A PET layer; A low density polyethylene layer; And an impact protection layer; Are stacked in this order,
Wherein the impact protection layer comprises a polyethylene layer, an anchor coating layer and a glass fiber layer,
Wherein the polyethylene layer is formed on one surface of the linear low density polyethylene layer and the AC coating layer and the glass fiber layer are laminated on the other surface of the linear low density polyethylene layer.
The heat sink according to claim 1, further comprising: a heat fusion layer and an aluminum thin film layer; An aluminum thin film layer and a nylon layer; A nylon layer and a PET layer; And an adhesive layer between each of the layers of the PET layer and the low-density polyethylene layer.
delete The composite reinforced flame retardant outer covering material for vacuum insulators according to claim 1, wherein the AC coating layer is formed of an isocyanate-based AC coating agent and has a coating amount of 0.5 to 1.5 g / m ² .
The vacuum insulator according to claim 1, wherein the polyethylene layer has an average thickness of 10 to 20 占 퐉, the AC coating layer has an average thickness of 0.5 to 1.5 占 퐉, and the glass fiber layer has an average thickness of 30 to 200 占 퐉. Outer material.
The composite reinforced flame-retardant outer covering as claimed in claim 1, wherein the glass fiber layer comprises at least one selected from the group consisting of E-glass, C-glass and S-glass.
The optical fiber according to claim 1, wherein the glass fiber layer comprises 50 to 60 wt% of SiO ₂ , 10 to 20 wt% of Al ₂ O ₃ , 8 to 10 wt% of B ₂ O ₃ , 1 to 2 wt% of MgO, 20 to 24 wt , 0.1 to 1 wt% of Na ₂ O, 0.1 to 1 wt% of K ₂ O, 0.01 to 0.05 wt% of TiO ₂ , and 0.01 to 0.5 wt% of Fe ₂ O _3. Outer material.
The heat-sealable layer according to claim 1, wherein the heat-sealable layer is made of a material selected from the group consisting of linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene acrylic acid (EAA), ethylene methyl acrylate The present invention relates to a composite reinforced flame retardant for vacuum insulation material, which comprises at least one selected from the group consisting of ethylene methacrylic acid (EMAA), ethylene methyl methacrylate (EMMA), ionomer (Ionomer, IO) and ethylene ethyl acrylate Outer material.
The composite reinforced flame-retardant outer covering according to claim 8, wherein said linear low density polyethylene is metallocene linear low density polyethylene (m-LLEPE).
The composite reinforced flame retardant outer covering material for vacuum insulators according to claim 1, wherein the PET layer has an average thickness of 8 to 20 占 퐉.
The composite reinforced flame retardant outer covering material for vacuum insulator according to claim 1, wherein the nylon layer has an average thickness of 15 to 30 占 퐉.
The composite reinforced flame retardant outer covering according to claim 1, wherein the aluminum thin film layer comprises an aluminum deposited film or an aluminum foil and has an average thickness of 6 to 9 占 퐉.
The composite reinforced flame-retardant outer covering for vacuum insulation material according to any one of claims 1 to 4, wherein the total thickness of the outer covering material is 140 to 350 占 퐉.
A composite reinforced flame retardant outer covering according to any one of claims 1 to 2 and 4 to 12; And
A heat insulating material comprising at least one selected from glass fiber, glass wool, polyurethane, polypropylene and polyester;
Wherein the vacuum insulator is a vacuum insulator.
The vacuum insulator according to claim 14, further comprising: a getter material adhered to or inserted into the heat insulating material.
15. The vacuum insulation material according to claim 14, wherein the vacuum insulation material is a vacuum insulation material for construction.
A step of laminating a thermally fusible layer, an aluminum thin film layer, a nylon layer, a VM-PET layer or a PET layer containing an Alox-PET layer, and a linear low density polyethylene layer by dry lamination in this order to produce a laminating base layer ;
Forming an impact protection layer on the lamination base material layer by extrusion lamination in which a polyethylene resin is coated between the laminated base material layer and the glass fiber coated on one side of the AC coating material;
Wherein the flame-retardant outer covering material is a flame-retardant flame retardant.

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