KR101722570B1

KR101722570B1 - The reinforced complex outer package of strength and flame resistance for vacuum insulation panel, method for manufacturing thereof and Vacuum insulation panel comprising the same

Info

Publication number: KR101722570B1
Application number: KR1020150124092A
Authority: KR
Inventors: 정석재; 최성진; 서창기; 박경태
Original assignee: 삼아알미늄(주)
Priority date: 2015-09-02
Filing date: 2015-09-02
Publication date: 2017-04-11
Also published as: KR20170027459A

Abstract

The present invention relates to a composite reinforced flame retardant outer covering material for vacuum insulation material, a method for producing the same, and a vacuum insulation material containing the same. More particularly, the present invention relates to an outer cover material for vacuum insulation material which is excellent in gas barrier property, moisture barrier property and heat shielding property To a method for manufacturing a composite reinforced flame retardant outer material for vacuum insulation material, and a vacuum insulation material containing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a composite reinforced flame retardant outer covering for vacuum insulation, a method for manufacturing the same, and a vacuum insulation panel including the same,

In general, glass wool (or glass fiber or the like) is used as an inner core material used for a vacuum insulation material, and a metal material such as a stainless steel thin plate is used as an outer covering material. Such a metal material does not substantially transmit gas, There is an advantage that the insulation performance is not deteriorated.

However, these vacuum insulation materials are difficult to handle due to their heavy panel density of about 200 kg / ㎥ to 300 kg / ㎥, and there is a risk that they have sharpness at the junction of the vacuum insulation material, Respectively. In addition, even if the inside is a vacuum, a metallic material such as stainless steel, which is an outer covering material, is a thermally conductive material, and thermal bridging phenomenon in which heat is conducted from the outside to the inside or from the inside to the outside through the insulating material is remarkable, It was difficult to expect.

To overcome such a problem, a laminate outer cover material for a vacuum insulation material has been developed. In order to maintain the degree of vacuum in the laminate outer cover material, protection for preventing occurrence of pinholes, tears, It is necessary to provide a heat insulating function capable of preventing thermal crosslinking, which is a basic function that a heat insulating material must have in addition to moisture permeation and gas barrier properties for preventing moisture from permeating from the outside, and furthermore, Studies have been actively conducted on an outer cover material having an adhesive function capable of sealing and maintaining a vacuum state. Korean Patent Laid-Open Publication No. 2014-0080737 discloses a core material sealed with such a vacuum insulation material and a vacuum insulation material using the core material have.

In recent years, a barrier material having a metal layer formed on a film has been provided on the outer cover material in order to significantly improve physical properties of heat insulation and gas / moisture barrier, and furthermore, outer cover materials having a plurality of such barrier materials have been developed . More specifically, FIG. 1 is a cross-sectional view of a conventional outer covering material for vacuum insulators. Three barrier materials 510, 520, and 530 including metal layers 511, 521, and 531 are formed on a sealing portion 550 for adhesion between outer covering materials And an adhesive layer 540 for bonding the barrier materials between the barrier materials.

1, an adhesive layer 540c is formed on one side of the third barrier material 530, a second barrier material 520 is laminated on the adhesive layer 540c, The adhesive layer 540b and the first barrier material 510 are laminated on the exposed one side of the barrier layer 520. When a plurality of barrier materials are provided, the process of forming and laminating the adhesive is repeated according to the barrier material, There is a very bad problem.

In general, the adhesive layer is designed to have a function of moisture permeation blocking through polyolefin-based components such as urethane-based components or polyethylene that exhibits hydrophobicity as a component of the adhesive layer. The urethane-based component and the polyolefin- The cracks and the pinholes are accelerated and the durability of the vacuum insulation material is greatly lowered. In addition, the urethane-based or polyolefin-based adhesive components not only cause a crack in the metal layer provided in the barrier material but also have poor adhesive force, resulting in frequent separation between the barrier materials, accelerating the inflow of moisture / gas into the separated gap, There is a problem in that the desired properties can not be completely attained and the use period of the heat insulating material is shortened.

In particular, according to the cross-sectional shape of a conventional vacuum insulator, it is inevitably necessary to have the bending portion A generated by sealing the core material inside the outer covering material 500 as shown in FIG. 2, Cracks are more likely to occur in the barrier material of the curved portion and generation of cracks makes it impossible to keep the inside of the vacuum insulation material in a vacuum state, thereby causing a problem of remarkably lowering the desired physical properties, reducing the function and shortening the cycle time .

On the other hand, there is a problem in that, even when the gas barrier property of the outer covering material is increased and the thermal conductivity is lowered, the outer covering material itself is weak against external impacts (external force, heat, fire) and is easily damaged during manufacture or use and the vacuum degree can not be maintained.

Accordingly, the adhesive force between a plurality of barrier materials is improved in order to improve the gas / water barrier property and thermal conductivity property required for the outer material, and even if the barrier material includes a plurality of barrier materials, flexibility of the outer material can be ensured, The development of the outer shell material which is remarkably superior in the basic properties such as heat insulation and moisture / gas shutoff which should be provided as the outer shell material of the vacuum insulation material while the damage of the outer shell material is prevented by the external force applied during the manufacturing process and / or product use of the product, It is urgent to develop a process capable of producing ash with higher productivity.

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above problems and it is an object of the present invention to firstly solve the problems of the prior art by improving the productivity by shortening the laminating process of the barrier laminating process And to provide a method for manufacturing a composite reinforced flame retardant outer covering material for a vacuum insulator.

A second problem to be solved by the present invention is to provide a vacuum insulation material which is excellent in the effects of insulation, moisture / gas shutoff, and the like, which are excellent in flexibility and durability, And the physical damage to the outer covering material is minimized during the manufacturing process of the vacuum insulation material and / or during use of the product, and a vacuum insulation material containing the same.

In order to solve the above-described first problem, the present invention provides a method of manufacturing a semiconductor device, comprising the steps of: (1) forming a first barrier material on both surfaces of a first substrate layer by vapor-coating an aluminum layer, Preparing a third barrier material on one side of the third substrate layer, the third barrier material being deposited and coated with an aluminum layer; (2) A second barrier material and a third barrier material are disposed on the upper and lower portions of the first barrier material so that the aluminum layers face each other, and a resin layer is interposed between the barrier materials facing each other to improve adhesion and flexibility between the barrier materials Extrusion lamination of a first barrier material to a third barrier material, and forming a thermal fusion layer below the third barrier material to produce a laminate; And (3) forming an impact protection layer including a glass fiber layer on the upper side of the laminated body. The present invention also provides a method for manufacturing a composite reinforced flame retardant outer covering material for vacuum insulation material.

According to a preferred embodiment of the present invention, the first base layer, the second base layer and the third base layer each independently include at least one of a polyester-based component, a polyamide-based component and a vinyl alcohol-based component .

According to another preferred embodiment of the present invention, the first base layer is a polyamide-based component or a vinyl alcohol-based component, and the second base layer and the third base layer may be polyester-based components.

According to another preferred embodiment of the present invention, the resin layer may include at least one of a copolymer and an ionomer including ethylene and at least one of acrylate and methacrylate as a monomer, Preferably, the resin layer may comprise a copolymer comprising ethylene, acrylate and methacrylate as monomers.

According to another preferred embodiment of the present invention, the optical density (OD) of the aluminum layer of the first barrier material may be 2.5 to 3.5.

According to another preferred embodiment of the present invention, 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) (EMA), ethylene methacrylic acid (EMAA), ethylene methyl methacrylate (EMMA), ionomer (Ionomer, IO) and ethylene ethyl acrylate (EEA).

According to another preferred embodiment of the present invention, the step (2) includes the steps of: preparing a laminate such that a linear low density polyethylene layer is further formed on the second barrier material; and the step (3) An impact protection layer may be formed on the laminate by extrusion lamination such that the polyethylene resin layer is interposed between the upper portion of the layer and the glass fiber layer coated on one side of the AC coating agent.

According to another preferred embodiment of the present invention, the AC coating layer may be formed on one side of the glass fiber layer with a coating amount of 0.5 to 1.5 g / m 2 of an isocyanate-based AC coating agent.

According to another preferred embodiment of the present invention, the linear low density polyethylene may be metallocene linear low density polyethylene (m-LLEPE).

According to 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.

According to another preferred embodiment of the present invention, the glass fiber layer comprises 50 to 60% by weight of SiO ₂ , 10 to 20% by weight of Al ₂ O ₃ , 8 to 10% by weight of B ₂ O ₃ , 1 to 2% by weight of MgO, 20 to 24% by weight of MaO, 0.1 to 1% by weight of Na ₂ O, 0.1 to 1% by weight of K ₂ O, 0.01 to 0.05% by weight of TiO ₂ , 0.01 to 0.5% by weight of Fe ₂ O ₃ .

According to another preferred embodiment of the present invention, the optical density (OD) of the aluminum layer of each of the second barrier material and the third barrier material is independently from 3.0 to 5.5, and the resin layer comprises ethylene, acrylate and methacrylate as monomers , &Lt; / RTI >

According to another aspect of the present invention, there is provided a plasma display panel comprising a plurality of barrier members including a first barrier, a second barrier and a third barrier, Wherein the second barrier material and the third barrier material each comprise an aluminum layer deposited and coated on one side of a second substrate layer and a third substrate layer, A barrier layer interposed between the second barrier layer and the third barrier layer so that the aluminum layer faces each other and including a resin layer between the respective barrier layers to improve adhesion and flexibility of the barrier layers; A heat-sealable layer formed on the lower portion of the barrier layer; And a shock-absorbing layer including a glass fiber layer formed on the barrier layer.

According to a preferred embodiment of the present invention, the barrier material has an average thickness of 8 to 30 탆, and the resin layer may have an average thickness of 8 to 30 탆.

According to another preferred embodiment of the present invention, the outer covering material may have a total thickness of 140 mu m to 360 mu m.

According to another preferred embodiment of the present invention, the optical density (OD) of the aluminum layer of each of the second barrier material and the third barrier material is independently 3.0 to 5.5, and the resin layer contains ethylene, acrylate and methacrylate And may include copolymers that are included as monomers.

According to another preferred embodiment of the present invention, the heat-sealable layer is formed on the lower portion of the third barrier material, and further the linear low-density polyethylene layer is interposed between the second barrier material and the shock- Layer, an anchor coating layer and a glass fiber layer, and the polyethylene layer of the impact protection layer may be formed to face the linear low density polyethylene layer.

According to another preferred embodiment of the present invention, the polyethylene layer has an average thickness of 10 탆 to 20 탆, the AC coating layer has an average thickness of 0.5 탆 to 1.5 탆, and the glass fiber layer has an average thickness of 30 탆 to 200 탆 have.

According to another preferred embodiment of the present invention, the composite reinforced flame-retardant outer covering material may be formed by bonding a second barrier material, which is the uppermost layer of the barrier layer, and a glass fiber layer of the impact protection layer, with an adhesive layer interposed therebetween.

According to another aspect of the present invention, there is provided an outer cover material for a vacuum insulator according to the present invention. And a core material encapsulated by the outer covering material and containing at least one selected from glass fiber, glass wool, polyurethane, polypropylene, and polyester.

According to a preferred embodiment of the present invention, a getter material included in the vacuum insulating material may be further included.

According to another preferred embodiment of the present invention, the vacuum insulator may be used for building materials, containers for storage and transportation, and refrigeration appliances.

Hereinafter, terms used in the present invention will be defined.

The term "formed on one surface" or "formed on a layer" of the specific layer as used in the present invention means that the layer formed directly opposite to the specific layer or indirectly formed after one or more other layers are inserted For example, in the case of "B layer formed on one surface of the A layer", the A layer and the B layer face each other, or a third C layer is formed on the A layer, and then a B layer is formed on the C layer .

It is also to be understood that in the description of the embodiments according to the present invention, each layer, region, and structure is referred to as being "on", "upper", "upper", "under" The terms "on", "upper", "upper", "under", "lower", "lower" And the relative positional relationship between them.

As used herein, the term "copolymer" means a polymer prepared from two or more monomers, and "monomer" means a monomer constituting a copolymer. In the present specification, the term "acrylate" refers collectively to acrylic acid compounds such as acrylic acid esters and acrylic acid salts.

The term "film" used in the present invention is a general term including a thin film, and is a concept including all what is commonly called a sheet and a wrap.

The outer covering material for vacuum insulation material according to the present invention can remarkably improve the productivity by shortening the lapping process of the barrier materials and further shortening the laminating process of the impact protection layer, and the outer covering material to be manufactured is a base material Which is excellent in the effects of maintaining the degree of vacuum, insulation, water / gas shutoff, etc., and is also excellent in flexibility, durability, impact resistance, heat resistance and flame retardancy, It has the advantage of minimizing physical damage and maintaining excellent physical properties for a long period of time. As it exhibits excellent physical properties, it can be widely used where various insulation materials such as building materials, containers for storage and transportation, refrigeration equipment, .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a conventional outer covering for vacuum insulators.
2 is a sectional view of a conventional vacuum insulator.
3 is a schematic view showing an extrusion lamination process of barrier materials included in a preferred embodiment of the present invention.
4 is a schematic view showing an extrusion lamination process of barrier materials included in another preferred embodiment of the present invention.
5 is a schematic view showing a dry lamination process according to a preferred embodiment of the present invention.
6 is a schematic view showing an extrusion lamination process for an outer wrapper according to a preferred embodiment of the present invention.
7 is a cross-sectional view of an outer covering according to a preferred embodiment of the present invention.
8 is a cross-sectional view of an outer covering according to another preferred embodiment of the present invention.
FIG. 9A is a photograph of a core and a getter included in a preferred embodiment of the present invention, FIG. 9B is a photograph of a comparative example of the present invention manufactured by inserting a core and a getter in a state without an impact protection layer, FIG. 9C is a photograph of a vacuum insulation material manufactured by inserting a core material and a getter according to FIG. 9A into an outer covering material having an impact protection layer formed thereon and vacuum-packing the same. FIG.
10A and 10B are photographs of evaluation results of the flame retardancy of a vacuum insulator according to a preferred embodiment of the present invention. FIG. 10C is a photograph of the evaluation result of the flame retardancy of the vacuum insulator (Comparative Example 3) according to the comparative example of the present invention. FIG.
FIG. 11A is a photograph of heat resistance evaluation results of a vacuum insulator according to a preferred embodiment of the present invention, and FIG. 11B is a photograph of heat resistance evaluation results of a vacuum insulator (Comparative Example 3) according to a comparative example of the present invention.

Hereinafter, the present invention will be described in more detail.

As described above, in the case of manufacturing a conventional outer covering material for vacuum insulator, when a plurality of barrier materials are provided, a plurality of batches are required to be repeatedly formed in order to form an adhesive form and a laminating process. In addition, a polyolefin-based component such as polyethylene or urethane-based component exhibiting hydrophobicity is usually used as an adhesive for bonding the barrier material. Such an adhesive component significantly reduces the flexibility of the outer cover material, especially the flexibility of the barrier material, Cracks, pinholes, and the like of the vacuum insulation material, thereby greatly reducing the durability of the vacuum insulation material. In addition, since the adhesive force of the adhesive components to the metal layer provided in the barrier material is not good, separation phenomenon frequently occurs between the barrier materials, and the intended properties such as accelerating the inflow of water / gas into the separated gap, And the use period of the heat insulating material is shortened. Particularly, the outer covering material for vacuum insulation has inevitably a curved portion according to the sectional shape of a conventional vacuum insulation material. However, when the flexibility of the outer covering material is lowered, the occurrence of cracks in the barrier material of the curved portion is further increased to keep the inside of the vacuum insulation material in a vacuum state , There is a problem of remarkable deterioration of the desired physical properties, loss of function and shortening of the use period. Furthermore, conventional outer covering materials have poor impact resistance, heat resistance, and flame retardancy, which limits their use in extreme external environments.

(1) a first barrier material on both sides of the first base material layer, a second barrier material having an aluminum layer deposited on one side of the second base material layer, and an aluminum layer Preparing a third barrier material that is vapor-deposited; (2) A second barrier material and a third barrier material are disposed on the upper and lower portions of the first barrier material so that the aluminum layers face each other, and a resin layer is interposed between the barrier materials facing each other to improve adhesion and flexibility between the barrier materials Extrusion lamination of a first barrier material to a third barrier material, and forming a thermal fusion layer below the third barrier material to produce a laminate; And (3) a step of forming an impact protection layer including a glass fiber layer on the upper side of the laminate. The present invention provides a method for manufacturing a composite reinforced flame retardant outer material for vacuum insulators.

As a result, the outer cover material for vacuum insulation according to the present invention can remarkably improve the productivity by shortening the laminating process of the barrier materials and further shortening the laminating process of the impact protection layer, and the outer cover material to be manufactured must be equipped with the outer cover material for vacuum insulation It is very effective in maintaining the basic properties of vacuum degree, insulation, water / gas shutoff, etc., and is also excellent in flexibility, durability, impact resistance, heat resistance and flame retardancy, Various physical damages are minimized, and excellent physical properties can be maintained for a long period of time.

First, in step (1) according to the present invention, a first barrier material having an aluminum layer deposited on both surfaces of a first base material layer, a second barrier material having an aluminum layer deposited and coated on one surface of the second base material layer, And a third barrier material on which an aluminum layer is deposited and coated on one side of the first barrier material.

The present invention is a barrier material comprising a double-sided barrier material in which an aluminum layer is formed on both surfaces of a substrate layer and a barrier material in which an aluminum layer is formed only on one surface of the substrate layer, And a second barrier material and a third barrier material having an aluminum layer deposited and coated on only one side of the base material layer.

As described above with reference to FIG. 1, an outer covering material having a plurality of barrier members has been developed in the past. However, in the conventional outer covering material, a cross-sectional barrier material having a metal layer formed on only one side of the base layer as shown in Fig. 1 has been used. In order to manifest the desired level of adhesion between the barrier materials by laminating a plurality of cross- It was required to be a component capable of excellently exhibiting physical properties on the layer. 1, an adhesive layer 540b is formed between the first barrier material 510 and the second barrier material 520. One surface of the adhesive layer 540b is formed on the base layer 512 of the first barrier material 510 And the other surface faces the metal layer 521 of the second barrier material 520. [ Therefore, in order to secure the adhesive force between the first barrier material 510 and the second barrier material 520, the adhesive component forming the adhesive layer 540b must exhibit good adhesion to both the metal layer and the base layer, There should be compatibility between the components of each of the metal layer or adhesive component / substrate layer.

However, in general, an adhesive component having compatibility with both the polymer resin component forming the substrate layer and the metal component of the metal layer is very difficult to exist in terms of material, and in order to solve this problem, physical compatibility, There is a problem that a process of forming an illuminance for improving adhesion or performing a separate surface treatment is further required. Also, the outer covering material as shown in FIG. 1 has a problem that the process is remarkably prolonged as the adhesive layer is formed on one barrier material and the number of barrier materials for laminating the other barrier material is repeated.

When the inventors of the present invention conducted research to solve this problem, when at least one of the plurality of barrier materials is provided with a double-sided barrier material having metal layers formed on both surfaces of the base layer, one surface of the barrier material facing the adhesive layer In this case, when an adhesive component compatible only with the metal layer is used, excellent adhesion can be exhibited. Even if the same number of barrier materials are provided, the number of metal layers provided on the outer covering material It is possible to improve the physical properties and to adhere a plurality of barrier materials in one process as in the manufacturing process according to FIG. 3 described below, thereby remarkably shortening the process. .

Each of the first to third barrier materials according to the present invention includes a substrate layer and an aluminum layer deposited on one or both surfaces of the substrate layer.

First, the base layer may be in the form of a flat sheet or film, and its shape may be polygonal, circular, oval, etc., and the specific shape / shape is not particularly limited in the present invention. The material of the base layer may preferably include at least one of a polyester-based component, a polyamide-based component, and a vinyl alcohol-based component.

The polyester-based component may be used without limitation in the case of a polyester-based component used as a substrate layer in the art, and examples thereof include polyethyleneterephthalate (PET), polybutylene terephthalate (PBT), and poly (PTT), an aromatic polycarboxylic acid such as terephthalate, and a diol component such as ethylene glycol as main components, and a modified poly (arylene ether) copolymer including other aliphatic polycarboxylic acids, sulfonic acid metal salts, Ester component. However, polyethylene terephthalate is preferable considering heat resistance, unit cost and hydrophobicity. The polyamide-based component may be nylon 6, nylon 66, nylon 12 or the like, but is preferably nylon 6 in consideration of heat resistance. Further, the vinyl alcohol-based component may contain at least one of ethylene vinyl alcohol copolymer and ethylene vinyl alcohol copolymer and polyvinyl alcohol, which may be very advantageous in gas barrier property and adhesion.

The constituent components of the first to third base layers included in each of the first to third barrier materials may be the same as either one of the constituents or the constituents of the base layer included in each of the respective barrier materials may be all different , Or only the base layer component of one of the barrier materials may be different from the base layer composition of the other barrier material. According to a preferred embodiment of the present invention, one of the first base layer, the second base layer and the third base layer includes a polyester-based component and the other base layer contains a polyamide-based component and a vinyl alcohol And more preferably the first base layer may be nylon, ethylene vinyl alcohol copolymer or polyvinyl alcohol, and the second base layer and the third base layer may be at least one of polyethylene terephthalate Through which the moisture barrier properties of the polyethylene terephthalate layer which can be in direct contact with the atmosphere can be enhanced and the gas barrier property can be further improved through the first base layer so that the outer covering material can simultaneously exhibit moisture and gas barrier properties There is an advantage.

If the material of the second base material layer of the second barrier material and / or the third base material layer of the third barrier material is made of nylon, ethylene vinyl alcohol copolymer or polyvinyl alcohol component in order to improve the gas barrier property of the outer covering material, nylon, ethylene The vinyl alcohol copolymer or the polyvinyl alcohol may be relatively weak to moisture compared to polyethylene terephthalate. Therefore, when it comes into direct contact with the atmosphere, there arises a problem of deterioration of the adhesive force due to invasion, peeling of the barrier material and deterioration of durability, There is a problem in that it is impossible to achieve even improvement of the gas barrier agent eventually due to the remarkable increase of gas inflow into the peeled gap.

Next, the aluminum layer vapor-coated on the base layer functions to shut off the gas / moisture flowing from the outside. In the case of the barrier material in which the aluminum layer is laminated on the base layer in the form of a thin film or the base material is covered with the aluminum foil, thermal bridging heat is generated on the base material layer, Is significantly higher than that in the case of vapor-deposited coating, there is a problem that the heat insulating performance is deteriorated.

In addition, the optical density (OD) of the aluminum layer included in the first barrier material of the aluminum layer deposited on the base layer may be 2.5 to 3.5, and more preferably, the optical density may be 3.0 to 3.5.

If the optical density of the aluminum layer of the first barrier is less than 2.5, the desired gas / moisture barrier properties may not be achievable, and if it exceeds 3.5, the first barrier will be too thick to allow the OD to become too large as the aluminum layer is deposited on both sides There is a problem such as cracks and reduced flexibility, and there is a problem that gas / moisture barrier properties may be lowered at the same time when cracks occur.

In addition, any one of the layers of the second barrier material and the third barrier material may have an optical density of 3.0 to 5.5, preferably 3.5 to 5.0, thereby improving gas / water barrier properties The desired physical properties can be expressed more remarkably. If the optical density of the second barrier material and / or the third barrier material aluminum layer is less than 3.0, physical properties such as gas barrier property and moisture permeability may be significantly deteriorated. If the optical density exceeds 5.5, cracks tend to occur in the aluminum layer, Is significantly lowered, cracks in the bent portion are increased, and moisture barrier property and gas barrier property are lowered.

In addition, the optical density of the aluminum layer included in the first to third barrier materials may be the same or different depending on the purpose, at least two barrier materials.

Next, in step (2) according to the present invention, a second barrier material and a third barrier material are disposed on the upper and lower portions of the first barrier material so that the aluminum layers face each other, and adhesion between the barrier materials and flexibility The first barrier material to the third barrier material is subjected to extrusion lamination.

First, as for the structural arrangement of the first to third barrier members, a second barrier member is disposed on the first barrier member, which is a double-sided barrier member, and a third barrier member is disposed under the first barrier member. It is preferable that the aluminum layer of the second barrier material and the third barrier material are disposed so as to face the aluminum layer of the first barrier material so that the material of one of the barrier materials becomes the same (aluminum layer).

3 is a schematic view illustrating a manufacturing process according to a preferred embodiment of the present invention. Referring to FIG. 3, a first barrier material 111 is supplied through a first supply roller 110, and a second barrier material The third barrier material 131 is supplied through the third supply roller 130 and the aluminum layer of the second barrier material 121 and the third barrier material 131 to be supplied is supplied to the first barrier material 111 As shown in Fig. A resin layer 143 extruded from the extruders 141 and 142 is interposed between the first barrier material 111 and the third barrier material 131 to be fed and extruded and laminated via the rubber roll 150 and the cooling roll 151, And can be wound on the mounting portion 160.

4 is a schematic view of a manufacturing process according to another preferred embodiment of the present invention. Referring to FIG. 4, a first barrier 111 and a second supply roller 120 ', which are supplied through a first supply roller 110' The supplied second barrier material 121 'is extruded through the first resin 144 extruded from the first extruder 141', and the extruded first barrier material 111 'and the second barrier material 121' The second resin 145 is extruded from the second extruder 142 'after the third barrier 131' supplied through the first barrier 111 'and the third feed roller 130' Can be wound around the winding part 160 'after being extruded by interposing the first barrier material 111' and the third barrier material 131 'therebetween.

Hereinafter, step (2) will be described in detail with reference to the process of FIG.

The resin layer 143 serves to bond each of the first to third barrier materials 111, 121, and 131, and has flexibility that does not break or break even when subjected to a bending external force exerted on the laminated body Lt; / RTI >

The resin layer 143 may be used without limitation as long as it is compatible with the vapor-deposited aluminum layer. Preferably, the resin layer 143 is a copolymer or an ionomer containing ethylene, acrylate or methacrylate as a monomer, More preferably, the acrylate includes at least one of an acrylate ester monomer and an alkyl acrylate ester monomer, and the methacrylate may be any one of a methacrylate ester monomer and an alkyl methacrylate ester monomer Or more. Non-limiting examples of such monomers include monomers containing carboxyl groups such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid, maleic anhydride or itaconic anhydride (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl Hydroxyl group-containing monomers such as 8-hydroxyoctyl, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl or (4-hydroxymethylcyclohexyl) -methylacrylate, styrene sulfonic acid (Meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate or (meth) One reel to the sulfonic acid group-containing monomer, or 2-hydroxyethyl acrylate, such as oxy-naphthalene sulfonic acid may include phosphoric acid group-containing monomers such as phosphate. In addition, the rubber-based monomer may include monomers such as butadiene, styrene, and acrylonitrile.

In the case of the copolymer comprising ethylene and acrylate or methacrylate as a monomer, the ethylene content is preferably 70 to 95% by weight, and the content of acrylate or methacrylate is preferably 5 to 30% by weight, It is more preferable that the content is 80 to 95 mol% and the acrylate or methacrylate content is 5 to 20 mol%. The ethylene content in the copolymer is an important factor for improving the mechanical properties such as flexibility and the acrylate or methacrylate content particularly contributes to enhance the gas barrier property and can satisfy the content range between the two monomers It is possible to induce a synergistic effect that exerts more excellent adhesiveness to the aluminum layer through it. If the content of ethylene and acrylate or methacrylate is not satisfied, the adhesive strength and flexibility are deteriorated and the interfacial peeling between the barrier material and the resin layer frequently occurs, and the resin layer is broken, , Water or gas is accelerated by cracks or peeled gaps, and there may be a fatal problem of loss of function or loss of function as an outer shell material. As a preferred example of the copolymer, a copolymer of ethylene-ethyl acrylate (EEA), an ethylene-methyl acrylate (EMA) copolymer, a copolymer of ethylene-n-butyl acrylate (EnBA) (EAA), a copolymer of ethylene-methacrylic acid (EMAA), a terpolymer of ethylene-methacrylic acid-acrylic acid and an ionomer (Ionomer), more preferably at least one selected from the group consisting of Copolymers of ethylene-methacrylic acid (EMAA) and terpolymers of ethylene-methacrylic acid-acrylic acid can be used, more preferably copolymers of low temperature extruded ethylene-methacrylic acid (EMAA) Methacrylic acid-acrylic acid terpolymers may be used. As a result, it is possible to simultaneously obtain effects such as adhesion and flexibility with an improved aluminum layer and effects such as gas barrier properties, and to prevent cracks from occurring in the metal vapor deposition film included in the barrier material at high temperature conditions when the resin layer is melt- There is an advantage of improving durability. The low-temperature extrusion type ethylene-methacrylic acid (EMAA) copolymer and the ethylene-methacrylic acid-acrylic acid terpolymer may have a melting point of 100 ° C or less, more preferably 75 to 100 ° C, More preferably, the melting index (MI) may be 20 g / 10 min or more, and still more preferably 30 to 45 g / 10 min. If the melt index is less than 20 g / 10 min, a high temperature operation of 280 ° C or higher is required, which may cause cracking of the metal thin film layer. If the melt index exceeds 45 g / 10 min, EMAA) and an ethylene-methacrylic acid-acrylic acid terpolymer are extrusion-coated, the problem of defective products may be caused due to a serious neck-in phenomenon in which both side portions shrink greatly inward.

Next, a step of forming an adhesive layer on the lower part of the third barrier material and forming a thermal fusion layer on the lower part of the adhesive layer is performed.

The thermally fusing layer serves to fix the sealing or heat insulating material so that gas and moisture are not penetrated in the state that the heat insulating material (or core material, 300 of FIG. 8) is inserted into the inside of the outer covering material. The heat sealing layer is made of a linear low density polyethylene (LLDPE ), Low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene acrylic acid (EAA), ethylene methyl acrylate (EMA), ethylene methacrylic acid (EMAA, ethylene-methylmethacrylic acid, ethylene-methylmethacrylate (EMMA), ionomer and ethylene-ethylacrylate (EEA) may be used, and preferably LLDPE , LDPE and HDPE, and more preferably LLDPE, and even more preferably among LLDPE, metallocene linear low density poly Alkylene (m-LLDPE) is good in terms of heat sealing properties, heat seal strength, low brittleness, transparency for use. 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 may be formed on either the upper portion of the second barrier material or the lower portion of the third barrier material, that is, the upper or lower surface of the barrier layer including the extrusion-laminated barrier materials. In this case, have. The adhesive layer is formed through an adhesive known in the art. Preferably, it is preferable to use a polyester urethane adhesive which is advantageous in interlayer properties of each layer and in blocking moisture introduced into the end face of the outer covering. Since the adhesive layer can be formed by a method known in the art, the adhesive layer is not particularly limited in the present invention.

Next, in step (3) according to the present invention, an impact protection layer including a glass fiber layer is formed on the laminate.

The glass fiber layer 208 may be made of general glass fibers, but preferably glass fibers containing at least one selected from the group consisting of E-glass, C-glass, and S- It is better to use glass fiberglass.

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.

According to a first preferred embodiment of the present invention, the glass fiber layer may be laminated with the laminate via an adhesive layer which may be formed on the top of the laminate (on top of the second barrier material 250). The adhesive layer may be formed through an adhesive known in the art, preferably using a polyester urethane adhesive, and more preferably formed through an adhesive composition without a supporting substrate such as a double-sided tape, which is preferable in terms of thinness . The thickness of the adhesive layer may be designed differently according to the purpose and is not particularly limited in the present invention, but it may preferably be formed to an average thickness of 1 to 6 탆. 5 is a schematic view of a manufacturing process according to a preferred embodiment of the present invention. The first supply unit 1 supplies the laminate manufactured through FIG. 3 (or FIG. 4), and the adhesive 2 (For example, the upper surface of the second base layer of the second barrier material) supplied from the first supply portion 1 when the coating is passed between the coated roll 3 and the press 4, 5, a dry chamber), and then laminated in a nip roll 6 and an impact protection layer including a glass fiber layer supplied from a second supply part 8, (9) can be finally obtained.

Meanwhile, according to a second preferred embodiment of the present invention, an AC coating layer is formed on at least one side of the glass fiber layer, and then the glass fiber layer and the laminate are extrusion-laminated by a polyethylene extrusion resin. At this time, preferably, the laminated body is formed between the upper part of the linear low density polyethylene layer formed on the upper part of the laminate (opposite to the side on which the heat fusion layer is formed), for example, the upper part of the second barrier material and the AC coating layer formed on one surface of the glass fiber layer A polyethylene extrusion resin may be supplied to extrusion laminate the laminate and the impact protection layer at the same time.

Such a manufacturing process has an advantage of achieving a further improved productivity of outer shell material by allowing the continuous laminate produced in one process to continuously manufacture the outer shell material through the impact protection layer and the laminate in one process . Further, excellent adhesion performance between the laminate and the impact protective layer is exhibited.

6 is a schematic view of a manufacturing process according to a preferred embodiment of the present invention. When a glass fiber layer is supplied from the first supply part 21, glass fibers pass through the press 23 and the AC coating part 22 The AC coating is applied to one side of the glass fiber layer, and is passed through a dry chamber (24). Next, the laminate further including the linear low density polyethylene layer supplied from the second supply section 27 and the glass fiber layer coated with the AC coating agent are passed between the rubber roll 29 and the cooling roll 30, The PE resin 26 is coated (or supplied) between the AC coating layer formed on one side of the glass fiber and the linear low density polyethylene layer of the laminate through the extruder 25. [ At this time, it is preferable to coat the polyethylene (PE) resin by extruding the polyethylene resin through an extruder at an extrusion temperature of 280 to 320 ° C, preferably 290 to 310 ° C, and the extrusion temperature may vary depending on the type of the polyethylene resin It is good to change within. Since the outer covering material is manufactured by the extrusion lamination method and then the winding portion 31 is wound up, the outer covering material can be manufactured by one continuous process which is extremely shortened, which is advantageous for remarkably excellent productivity and facility simplification.

In addition, excellent adhesion performance is exhibited through such a manufacturing process and layer construction.

Specifically, the impact protection layer is a matrix in which the glass fiber layer plays a key role in its function. For example, the polyethylene terephthalate layer, which is a base layer of a glass fiber layer and a barrier material, is not good in compatibility with each other. Is very unfavorable. In addition, even if the process is shortened by bonding the laminate and the impact protection layer to the polyethylene resin, the melt-extruded polyethylene resin is not compatible with the base material layer of the barrier material and the glass fiber layer, There is a problem in adhesiveness and there is a problem that the impact protection layer is easily peeled off from the laminate when it is interposed so as to face directly between the impact protection layers.

Therefore, it is preferable that the laminate further includes a low-density polyethylene layer excellent in compatibility with the melt-extruded polyethylene resin, more preferably a linear low-density polyethylene layer to improve the compatibility between the melt- extruded polyethylene layer and the laminate, An AC coating layer is disposed on one side of the glass fiber layer in order to improve the compatibility of the glass fiber layer. Thus, the excellent adhesion performance of the outer layer material extruded and laminated through the high compatibility between the AC coating layer and the melt extruded polyethylene layer can be exhibited.

The A.C coating layer is inactive and can exhibit a very good adhesion property between a polyethylene resin having no polar group and glass fiber by causing a molecular attraction force between the surface of the substrate and the AC coating layer to improve adhesion performance.

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-based AC coating agent. Is advantageous in terms of adhesive strength, heat resistance, water resistance, cold resistance and oil resistance.

As described above, the outer covering material manufactured through the above-described manufacturing method includes a plurality of barrier materials including a first barrier material, a second barrier material, and a third barrier material, and the first barrier material includes an aluminum layer deposited on both surfaces of the first base material layer Wherein the second barrier material and the third barrier material comprise an aluminum layer deposited and coated on one side of a second substrate layer and a third substrate layer, respectively, wherein the first barrier material comprises an aluminum layer vapor- A barrier layer interposed between the second barrier layer and the third barrier layer to face each other and including a resin layer between the respective barrier layers to improve adhesion and flexibility of the barrier layers; A heat-sealable layer formed on the lower portion of the barrier layer; And an impact protection layer comprising a glass fiber layer formed on the upper portion of the barrier layer.

7 is a cross-sectional view of the outer envelope according to the first preferred embodiment of the present invention. In the outer envelope according to the first embodiment of the present invention, the aluminum layer 232 is formed on the heat- The first barrier material 240 and the second barrier material 250 are laminated in this order and the adhesive layer 260 is interposed between the heat-sealing layer 210 and the third barrier material 230 Resin layers 221 and 222 are interposed between the first to third barrier materials 230 and 240 and the resin layers 221 and 222 are disposed between the barrier layers 232 and 242 and 243 / 252, and a glass fiber layer 291, which is an impact protection layer, is formed directly on the second base layer 251 of the second barrier material 250 of the laminate via an adhesive layer 261 Lt; / RTI >

8 is a cross-sectional view of a cushioning material according to a second preferred embodiment of the present invention in which an aluminum layer 232 is formed on the heat-sealable layer 210 by a cross-sectional shape The first barrier material 240 and the second barrier material 250 are stacked in this order and the adhesive layer 260 is interposed between the heat-sealable layer 210 and the third barrier material 230. The third barrier material 230, the double-sided first barrier material 240, And resin layers 221 and 222 are interposed between the first to third barrier materials 230 and 240 and the resin layers 221 and 222 are sandwiched between the barrier layers 232 and 242 And a linear low density polyethylene layer 270 is further laminated on the second base layer 251 of the second barrier material 250 via an adhesive layer 261 to form a laminate . The laminate includes a polyethylene layer 280, an AC coating layer 281 and a glass fiber layer 290 sequentially on the linear low density polyethylene layer 270.

On the other hand, the constituent elements constituting the outer covering material are the same as those in the above-described manufacturing method, and the description thereof will be omitted.

The heat-sealable layer 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 there is a possibility of gas and moisture permeability If it exceeds 60 탆, there may be a problem of thinning, and if the heat transfer due to the thickness is insufficient at the heat sealing site for heat sealing at the time of dispensing, the adhesive strength may become weak due to insufficient melting of the heat sealing layer Therefore, 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.

The adhesive layers 260 and 261 formed of the adhesive are preferably formed to have an average thickness of 2.5 μm to 5 μm, preferably an average thickness of 3.0 μm to 4.5 μm. If the thickness is less than 2.5 μm, If it is more than 5 탆, it is disadvantageous from the viewpoint of thinning, and the adhesive is over-used, resulting in poor economical efficiency.

The thicknesses of the first to third barrier members 230, 240, and 250 are set so that the average thickness is 8 占 퐉 to 30 占 퐉, preferably 10 占 퐉 to 26 占 퐉, more preferably 12 占 퐉 If the thickness is more than 30 mu m, there may be a problem in thinning. Therefore, it is preferable that the thickness is within the above range. The thicknesses of the first to third barrier materials may be the same or at least different from each other, and may be designed differently according to the purpose, and thus are not particularly limited in the present invention. The aluminum layer included in the barrier material may have an average thickness of 0.05 to 1 占 퐉, more preferably 0.1 to 0.7 占 퐉, still more preferably 0.2 to 0.5 占 퐉, The deposited aluminum layer is more advantageous in achieving the desired physical properties than when the aluminum laminated or rolled thin film such as aluminum foil alone is included in the outer cover material.

The resin layers 221 and 222 may be formed to have an average thickness of preferably 8 to 30 μm, more preferably 10 to 20 μm. If the thickness of the resin layer is less than 8 μm, There may be a problem that the bonding strength is lowered and cracks are generated at the time of folding, and when the thickness exceeds 30 탆, the inflow of water / gas into the resin layer exposed at one end of the covering material accelerates, There may be a problem of going back to thinning and a problem of an increase in cost. The thickness of the resin layer 222 formed between the resin layer 221 formed between the first barrier material 240 and the third barrier material 230 and the first barrier material 240 / And the material that becomes the material may be the same or different.

The linear low density polyethylene layer 270 preferably has an average thickness of 10 to 50 占 퐉, preferably 20 to 30 占 퐉. If the thickness is less than 10 占 퐉, there may be an adhesive force problem. If the thickness is more than 50 占 퐉, , And can have cost increasing issues.

The average thickness of the PE layer (extruded PE layer) 280 is preferably 5 to 40 占 퐉, more preferably 10 to 30 占 퐉, and still more preferably 10 to 20 占 퐉. At this time, If it is less than 10 mu m, extrusion processability may be difficult and adhesion may be weak. If the thickness is more than 40 mu m, the thickness is too thick and it is difficult to make the outer layer thinner.

The average thickness of the AC coating layer (or the adhesive layer 281) is preferably 0.3 to 2.0 占 퐉, more preferably 0.5 to 1.5 占 퐉, and the average thickness of the AC coating layer (adhesive layer) The adhesive strength between the PE layer and the glass fiber layer may deteriorate and a part of the glass fiber layer may fall due to an external impact or the like. If the average thickness exceeds 2.0 탆, the adhesive is excessively used, .

The glass fiber layer 290 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, Mu] m, it is too thick and the flexibility of the outer covering material for vacuum insulation decreases, and workability and workability may be deteriorated, so that it is preferable to have an average thickness within the above range.

It is preferable that the thickness of the covering material formed by laminating the above components is 140 mu m to 360 mu m, preferably 150 mu m to 310 mu m. When the thickness is less than 140 mu m, the strength of the vacuum insulation pouch is weak , And it may be disadvantageous to maintain the vacuum state. If it exceeds 400 mu m, it may be disadvantageous for thinning.

On the other hand, the present invention relates to a vacuum insulator comprising at least one member selected from the group consisting of glass fiber, glass wool, polyurethane, polypropylene and polyester, which is encapsulated with the outer cladding material and the outer cladding material according to the present invention, .

Each component of the core material may include a core material component known in the art other than one selected from glass fiber, glass wool, polyurethane, polypropylene, and polyester. When one or more of the above listed components are included, May be a content of a core material well known in the art, and its shape may also be a shape of a known core material, so that the present invention is not particularly limited thereto.

The getter material may further include a getter material mainly for adsorbing residual gas molecules in the vacuum, forming a gas and a compound thereof, and removing the gas components flowing through the vacuum insulation material, It is possible to perform a function of maintaining the heat insulation performance as a vacuum insulation material.

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.

&Lt; Example 1 >

1. Preparation of laminate

First, a cross-sectional barrier material (trade name: CORON, trade name: CGP-21) having an average thickness of 12 占 퐉 and an aluminum layer having an optical density of 3.3 deposited on only one side of the base material layer of PET material with an optical density of 4.0 is made of PET A double-sided barrier material having an average thickness of 12 占 퐉 deposited on both surfaces of the substrate layer was prepared. The prepared double-faced barrier material is fed to the first barrier material 111 shown in Fig. 3, the barrier material is fed to the second barrier material 121 and the third barrier material 131, and fed to the extruders 141 and 142 at 230 ° C Extruding a terpolymer resin of ethylene-methacrylic acid-acrylic acid (Dupont, Nucrel AN4211-5C (MI 32, melting point 94 ° C)) at a temperature of -10 ° C. to obtain a first barrier material / second barrier material and a first barrier material / And the barrier layer was extrusion-laminated. At this time, the thickness of the extruded resin layer was 15 占 퐉. An adhesive (Urethane adhesive) was applied as an adhesive layer to the lower surface of the third barrier material of the extruded laminated barrier layer and a 50 탆 average thickness metallocene linear low density polyethylene (m-LLDPE) film (manufactured by Korea Pre-pack, trade name: M-PE Film) was laminated as a heat-sealable layer, and the average thickness of the lower surface adhesive layer of the third barrier material was 3.3 탆. A specific method of laminating the heat-sealable layer on the lower surface of the third barrier material was carried out continuously through the same process as shown in Fig. 5, and an adhesive agent was applied to the lower part of the wound extruded first barrier material to the third barrier material (2), and extruded and laminated with a metallocene linear low-density polyethylene (m-LLDPE) film (8).

Then, an adhesive (Urethane adhesive) was applied to the upper surface of the second barrier material among the extruded laminated materials and an average thickness of 30 mu m metallocene linear low density polyethylene (m-LLDPE) film (manufactured by Korea Prepack, The average thickness of the adhesive layer sandwiched between the film laminated on the second barrier material and the second barrier material was 3.3 mu m. On the other hand, a specific method of laminating a linear low density polyethylene (m-LLDPE) film on the upper surface of the second barrier material was continuously performed through the same process as shown in FIG. 5, (M-LLDPE) film 8 to prepare a laminate through extrusion lamination. The laminate was extruded so that the adhesive 2 adhered to the upper part of the second barrier material of the laminate.

2. Manufacture of outer covering material by extrusion lamination of laminate and impact protection layer

Glass woven fabric (E-glass, SiO ₂ 52.8% by weight, Al ₂ O ₃ 14% by weight, B ₂ O ₃ 8.3% by weight, MgO 1.5% by weight An isocyanate-based AC coating agent (Soda, T-160) was applied on one surface of a substrate (a substrate made of Al ₂ O 3, 0.1 wt%, MaO 21.5 wt%, Na ₂ O 0.6 wt%, K ₂ O 0.7 wt%, TiO ₂ 0.3 wt% and Fe ₂ O ₃ 0.3 wt% Followed by drying to form an AC coating layer. Thereafter, a polyethylene resin was extruded with a T-die having an average temperature of 300 to obtain an outer cover material for a vacuum insulation material having a polyethylene resin interposed between the top of the linear low density polyethylene layer of the laminate and the AC coating layer of the impact protection layer . In the manufactured impact protection layer, the average thickness of the polyethylene 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. The coating amount of the AC coating layer was 1.16 g / m ² .

&Lt; Examples 2 to 9 &

The optical density of the aluminum layer of the barrier material and the kind of the base layer of the barrier material were changed as shown in Table 1 or Table 2 to produce an outer material as shown in Table 1 or 2 below .

&Lt; Comparative Example 1 &

Except that a barrier material having a mean thickness of 25 占 퐉 was used as a first barrier material in place of the first barrier material, which is a double-sided barrier material, in the same manner as in Example 1, ) Were laminated by a dry lamination method to prepare an outer covering material as shown in Table 1 below. At this time, the average thickness of the adhesive layer interposed between the barrier materials was 3.9 mu m.

&Lt; Comparative Example 2 &

Except that the adhesive layer was replaced with the resin layer component of Example 1 instead of the urethane adhesive between the barrier materials to prepare an outer covering material as shown in Table 2 below.

The following materials were evaluated for the outer covering materials prepared through Examples 1 to 7 and Comparative Examples 1 and 2, and are shown in Table 1 and Table 2. [

(1) Oxygen permeability

Measured according to ASTM D-3985 method, using 2/21 equipment from MOCON.

(2) Water vapor permeability

Measurement was made according to ASTM F-1249 method, using 3/33 equipment of MOCON.

(3) Durability evaluation

The center part of the outer cloth was folded and then reciprocated 10 times by a roller of 2 kg. The aluminum layer was folded in the opposite direction and reciprocated ten times. The aluminum layer was observed with a light microscope to find cracks, pinholes and folding- And pinholes. In the case of the resin layer, it was observed by an optical microscope whether interface peeling between the barrier material and the resin layer, cracking of the resin layer, or cracking occurred. 0 for no abnormal findings, and 1 to 5 for greater severity.

(4) Productivity (%)

The amount of the outer covering material produced per hour was measured and shown. At this time, the amount of the outer cladding material produced in Comparative Example 1 was 100% relative to the amount of outer cladding material produced per hour.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Outer material The first barrier material type Double-sided type Double-sided type Double-sided type Double-sided type Double-sided type Double-sided type Aluminum layer optical density 3.3 2.3 3.6 3.3 3.3 3.3 The substrate layer PET PET PET EVOH NY PVOH The second barrier material Aluminum layer optical density 4.0 4.0 4.0 4.0 4.0 4.0 The substrate layer PET PET PET PET PET PET The third barrier material Aluminum layer optical density 4.0 4.0 4.0 4.0 4.0 4.0 The substrate layer PET PET PET PET PET PET Resin layer Material / Thickness (㎛) A ¹⁾ /
15 A /
15 A /
15 A /
15 A /
15 A /
15 Oxygen permeability (cc / m 3 · day) 0.0425 0.0531 0.0411 0.0420 0.0421 0.0410 Water vapor permeability (g / m ^{2 ·} day) 0.0041 0.0051 0.0040 0.0048 0.0050 0.0049 durability Aluminum layer 0 0 2 0 0 0 Resin layer 0 0 One 0 0 0 productivity(%) 150 150 150 150 150 150 1) A: Ethylene-methacrylic acid-acrylate terpolymer

Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Outer material The first barrier material type Double-sided type Double-sided type Double-sided type Section type Section type Aluminum layer optical density 3.3 2.5 3.3 3.3 3.3 The substrate layer PET PET PET PET PET The second barrier material Aluminum layer optical density 4.0 2.5 4.0 4.0 4.0 The substrate layer PET PET PET PET PET The third barrier material Aluminum layer optical density 4.0 2.5 4.0 4.0 4.0 The substrate layer PVOH PET PET PET PET Resin layer Material / Thickness (㎛) A ¹⁾ / 15 A / 15 Urethane adhesive / 3.9 Urethane adhesive / 3.9 A / 15 Oxygen permeability (cc / m 3 · day) 0.0412 0.0582 0.0433 0.0611 0.0641 Water vapor permeability (g / m ^{2 ·} day) 0.0063 0.0057 0.0042 0.0052 0.0059 durability Aluminum layer 0 3 5 4 0 Resin layer 0 0 5
(fracture) 5
(Peeling) 4
(Peeling) productivity(%) 150 150 150 100 100 1) A: Ethylene-methacrylic acid-acrylate terpolymer

Specifically, as can be seen from Tables 1 and 2,

In the case of Example 3 in which the optical density of the aluminum layer of the first barrier material exceeds 3.5, the oxygen permeability and the moisture permeability were somewhat superior to those of Example 1, but the durability of the aluminum layer and the durability of the resin layer were remarkably lowered.

In addition, in the case of Example 2 in which the OD value of the first barrier agent is smaller than that of Example 1, it can be confirmed that the physical properties were significantly lowered in the oxygen permeability and the moisture permeability.

Further, it can be confirmed that the moisture permeability of Example 7, in which the base material of the third barrier material is PVOH, is significantly higher than that of Example 1.

It can also be seen that the oxygen permeability of the outer cover material according to Example 8 using the barrier material whose optical density of the second barrier material and the third barrier material aluminum layer is lower than that of Example 1 is remarkably decreased.

In Example 9 in which the resin layer was changed to a urethane adhesive instead of EMAA, it was confirmed that the durability of the aluminum layer and the resin layer was remarkably decreased.

On the other hand, in Comparative Example 1, the base material of which the both sides of the resin layer were not the same, that is, one side of the resin layer faced the aluminum layer and the other side of the resin layer was not significantly durable as facing the base layer. It was confirmed that the physical properties were significantly deteriorated in oxygen permeability and water vapor permeability.

In Comparative Example 2, when the kind of the resin layer was changed to a terpolymer of ethylene-methacrylic acid-acrylic acid, as in Comparative Example 1, the material of the layer facing the both surfaces of the resin layer was different, Can not be solved. However, it can be confirmed that no problem such as breakage of the aluminum layer occurred.

In Comparative Example 1 and Comparative Example 2, lamination processes were sequentially required for each of the first barrier material, the second barrier material, the third barrier material, and the heat-sealable layer, so that a total of three lamination processes were required. The barrier material, the second barrier material and the third barrier material are laminated by only one lamination process, and then the production speed is 1.5 times faster as the laminate process of the heat-sealable layer is performed.

&Lt; Examples 10 to 13 >

(Ethylene-methacrylic acid (EMAA) copolymer and ethylene-methacrylic acid-acrylic acid terpolymer used as a resin layer were prepared in the same manner as in Example 1, The outer shell material as shown in Table 3 was produced. The properties of the outer cladding material thus prepared were evaluated in accordance with the physical properties of Experimental Example 1 and the presence or absence of Neck In in Experimental Example 2 as shown below.

It was visually observed whether a necking phenomenon occurred in the manufactured outer covering material. When the above phenomenon did not occur, 0 was shown as 1 to 5 as the degree of the phenomenon was increased.

Example 1 Example 10 Example 11 Example 12 Example 13 Outer material Resin layer ingredient A ¹⁾ EMAA EMAA EMAA EAA Melting point (g / 10 min, ASTM D1238) 32 25 6.5 60 10.0 Melting point (캜) 94 92 104 91 97 Manufacturer / Product Name Dupont / Nucrel 4211-5C Dupont /
Nucrel
925 Dupont /
Nucrel
0609 Dupont /
Nucrel
960 Dupont /
Nucrel 3990L Coating temperature
(° C) 230 230 280 210 270 Oxygen permeability (cc / m 3 · day) 0.0425 0.0427 0.0610 0.0415 0.07 Water vapor permeability (g / m ^{2 ·} day) 0.0041 0.0049 0.0057 0.0042 0.007 durability Aluminum layer 0 2 3 0 4 Resin layer 0 One One One 3 Presence or absence of neck phenomenon 0 0 0 5 0 1) terpolymers of ethylene-methacrylic acid-acrylate

Specifically, as shown in Table 3,

It can be confirmed that the durability of the aluminum layer and the resin layer is remarkably superior to that of Example 1 and Example 10 in the case of using the resin layer of Example 10 in the case of Examples 1 and 10 in which the melting point and the melting point of the resin layer are similar.

In Example 11, in which the resin layer had a melt index of less than 20 g / 10 min, and the coating temperature was high, it was confirmed that the aluminum layer was significantly cracked as compared with Example 1, and the durability of the resin layer was also poor.

It can be seen that Example 12 in which the melt index of the resin layer is remarkably large has a problem of generation of Neck In at the time of processing.

Further, in using EAA as a component of the resin layer Example 13, it can be confirmed that the durability of the aluminum layer and the resin layer are significantly better than in Example 1.

&Lt; Comparative Examples 14 to 16 >

Except that the isocyanate-based AC coating agent, the titanate-based AC coating agent, the polyimide-based AC coating agent, and the butadiene-based AC coating agent were used as the AC coating agent in the same manner as in Example 1, Was prepared.

The adhesive strength, water resistance, cold resistance and heat resistance of the outer covering material for vacuum insulation material prepared in Example 1 and Comparative Examples 3 to 5 were measured by the following methods and the results are shown in Table 4, The better, the better.

division Example 14 Example 15 Example 16 Example 1 Types of AC coating agents Titanate series Polyimide system Butadiene series Isocyanate system Adhesion ○ ○ ○ ○ Water resistance × × △ ○ Cold resistance × × × ○ Heat resistance △ △ △ ○

As a result of the test results shown in Table 4, all of Examples 14 to 16 using the titanate AC coating agent, the polyimide AC coating agent and the butadiene AC coating agent, and the Example 1 using the isocyanate AC coating agent were excellent in adhesion, It was confirmed that Examples 14 to 16 were inferior in overall water resistance, cold resistance and heat resistance as compared with Example 1 using an isocyanate-based AC coating agent, and it was confirmed that using an isocyanate-based AC coating agent was advantageous in terms of physical properties .

&Lt; Example 17 >

First, a cross-sectional barrier material (trade name: CORON, trade name: CGP-21) having an average thickness of 12 占 퐉 and an aluminum layer having an optical density of 3.3 deposited on only one side of the base material layer of PET material with an optical density of 4.0 is made of PET A double-sided barrier material having an average thickness of 12 占 퐉 deposited on both surfaces of the substrate layer was prepared. The prepared double-faced barrier material is fed to the first barrier material 111 shown in Fig. 3, the barrier material is fed to the second barrier material 121 and the third barrier material 131, and fed to the extruders 141 and 142 at 230 ° C Extruding a terpolymer resin of ethylene-methacrylic acid-acrylic acid (Dupont, Nucrel AN4211-5C (MI 32, melting point 94 ° C)) at a temperature of -10 ° C. to obtain a first barrier material / second barrier material and a first barrier material / And the barrier layer was extrusion-laminated. An adhesive (Urethane adhesive) was applied as an adhesive layer to the lower surface of the third barrier material of the extruded laminated barrier layer and a 50 탆 average thickness metallocene linear low density polyethylene (m-LLDPE) film (manufactured by Korea Pre-pack, trade name: M-PE Film) was laminated as a heat-sealable layer, and the average thickness of the adhesive layer was 3.3 m and the average thickness of the resin layer was 15 m.

Thereafter, an adhesive (Urethane adhesive) was applied to the upper surface of the second barrier material among the extruded laminated layers, and woven glass fibers (E-glass, SiO ₂ 52.8% by weight, Al ₂ O ₃ 14 wt%, B ₂ O ₃ 8.3 wt.%, MgO 1.5 wt.%, MaO 21.5 wt%, 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) were laminated to produce an outer covering material for a vacuum insulator. At this time, the average thickness of the adhesive layer between the glass fiber and the second barrier was 3.3 탆.

&Lt; Comparative Example 3 &

An outer cover material for a vacuum insulator was produced in the same manner as in Example 1 except that the laminate itself without the formation of the impact protection layer (polyethylene layer-AC coating layer-glass fiber layer) was made of an outer covering material.

&Lt; Comparative Examples 4 and 5 >

A pouch-type composite reinforced flame retardant outer covering material for vacuum insulation material was prepared in the same manner as in Example 1 except that the thickness of the heat-sealable layer or the thickness of the impact protection layer was as shown in Table 5 below.

The following properties were evaluated for the outer shells prepared in Examples 1 and 17 and Comparative Examples 3 to 5, and are shown in Table 5 below.

1. Evaluation of Flammability

According to the UL 94 method, the outermost layer of the outer cladding material was contacted with a flame for 10 seconds to visually observe the combustion. On the other hand, the flame retardancy evaluation results of Example 1 and Comparative Example 3 are shown in Fig.

2. Evaluation of heat resistance

The shrinkage was visually observed by placing the specimen at a distance of 10 cm for 10 seconds in an electric heater (electric heater, spiral type) having a heater surface temperature of 300. On the other hand, the heat resistance evaluation results of Example 1 and Comparative Example 3 are shown in Fig.

3. Evaluation of Flexibility and Foldability

The center portion was folded and then reciprocated ten times with a 2 kg roller, folded in reverse, and reciprocated ten times, and then observed for formation of cracks, pinholes and folding property of the aluminum thin film layer. The results were as follows: 5 for abnormal results, 4 ~ 0 for more severe cases.

In Comparative Example 3, since no impact protection layer was formed, folding property and flexibility were not evaluated

4. Tensile strength and burst strength

The tensile strength was measured according to ASTM D-882 method, using Instron 4465 instrument.

In addition, the tear strength was measured in accordance with ASTM D-3786 method, using an EL device manufactured by TOYOSEIKI. At this time, the tear strength was measured in the direction from the glass fiber layer to the heat-seal layer.

On the other hand, in the case of Comparative Example 5, the tensile strength and fracture strength properties were not evaluated due to problems in folding.

division Example 1 Example 17 Comparative Example 3 Comparative Example 4 Comparative Example 5 Thermal Fusion Layer (占 퐉) 50 50 50 20 32 Shock
Protective layer
(탆) PE layer 15 - - 15 8 A.C coating layer 1.2 - - 1.2 0.3 Glass fiber layer 100 100 - 90 140 Properties Flammability Good Good Burned. Good Good Heat resistance Good Good Shrinkage occurs Good Good Flexibility and
Foldability 5 5 Property evaluation
Unfinished 5 0
(Occurrence of peeling between the laminate and the impact protection layer) Heat Seal Strength (kg / 15mm) 8.5 8.3 7.5 4.2 6.2 The tensile strength
(Kg / mm < 2 & 26.5 25.8 10.6 24.5 Property evaluation
Unfinished Burst strength
(Kg / cm2) 31.7 31.1 14.2 28.6 Property evaluation
Unfinished

In the case of the composite reinforced flame retardant outer cover material for vacuum insulation according to the preferred embodiment of the present invention in Example 1, excellent results were obtained in terms of flame retardancy, heat resistance, flexibility, and foldability. Specifically, FIG. 10A is a photograph of a surface of the composite reinforced flame-retardant outer covering material for vacuum insulation material directly contacting the flame after evaluation of the flame retardancy, and it is confirmed that the flame-retardant property is excellent because flame does not adhere and only a little soot is generated. In addition, FIG. 10B shows that the flame does not affect the opposite surface at all at the other surface of FIG. 10A. Fig. 11A is a photograph of the composite reinforced flame-retardant outer covering material for vacuum insulator after evaluating the heat resistance, and it was confirmed that the shrinkage and combustion did not occur and the heat resistance was excellent.

On the other hand, in the case of Comparative Example 3 having no impact protection layer, as shown in FIG. 10B, it was confirmed that a hole was formed in a portion where the flame came into contact in the evaluation of the flame retardancy. In the heat resistance evaluation, And the heat resistance is not very good.

In addition, the tensile strength and the tear strength were significantly lowered than in Example 1, indicating that the mechanical strength was very low.

On the other hand, in Comparative Example 4, the thickness of the heat-sealable layer was too thin, indicating that the heat seal strength was significantly lower than in Example 1.

In the case of Comparative Example 5 in which the PE layer of the impact protection layer was less than 10 탆 and the AC coating layer was formed at 0.5 탆 or less, the adhesion between the impact protection layer and the upper surface of the laminate was weak, It can be confirmed that the problem of peeling occurs.

&Lt; Examples 18 to 19 >

(LLDPE film, Korea Pre-Pack, L-LDPE) instead of a metallocene linear low density polyethylene film (m-LLDPE, Korea PrePack, M-PE Film) (LDPE film, Korea Pre-pack, and LDPE Film), respectively, to prepare a composite reinforced flame-retardant covering material as shown in Table 6 below.

The heat seal strength of the composite reinforced flame retardant outer covering for vacuum insulators prepared in Examples 1, 15 and 16 was measured using an Instron 4465 instrument according to ASTM D-882, and the results are shown in Table 6 Respectively.

division Example 1 Example 18 Example 19 Heat Seal Strength (kg / 15㎜) 8.5 6.8 5.7

Example 1 using a metallocene linear low density polyethylene film (m-LLDPE, Korea Pre-pack, M-PE Film) as a heat-sealable layer compared with Example 18 using a linear low density polyethylene film and Example 19 using a low density polyethylene film It can be confirmed that the heat sealing strength is the most excellent.

&Lt; Comparative Example 6 >

An adhesive (Urethane adhesive) was applied to one side of an aluminum foil (average thickness 7 mu m, Sanaa Aluminum Co., Ltd., 8079 material) using the dry lamination process as shown in Fig. 5 and then a PET film having an average thickness of 25 mu m was laminated, Barrier material (Al thin film layer-PET layer).

Next, using the same dry lamination method, an aluminum layer having an optical density of 4.0 on the upper surface of the first barrier material was deposited on only one side of the PET base material layer, (M-LLDPE) film (having a thickness of 50 mu m) was laminated on the lower surface of the first barrier material without the second barrier material by using the same dry lamination method (Heat-sealable layer-first barrier material-second barrier material) were laminated (or adhered) with a heat-sealable layer of M-PE film (Korea Pre-pack, M-PE film).

Next, a linear low density polyethylene (LLDPE) film (Korean prepack, LDPE Film) having an average thickness of 30 占 퐉 was laminated on the upper surface of the second barrier material of the first laminate using the same dry lamination method to form a second laminate - first barrier material - second barrier material - low density polyethylene layer).

(2) Impact protective layer lamination

1) Glass woven fabric (E-glass, SiO2 52.8% by weight, Al2O3 14% by weight, B2O3 8.3% by weight, MgO 1.5% by weight, An AC coating (CaO, T-160) was coated on one side of a substrate (21.5 wt% of MaO, 0.6 wt% of Na2O, 0.7 wt% of K2O, 0.3 wt% of TiO2 and 0.3 wt% of Fe2O3) Then, the polyethylene resin was extruded with a T-die having an average temperature of 300 as an extruder to form an impact protection layer on the upper surface of the second laminate to prepare an outer cover material for vacuum insulation.

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

The thermal conductivity of the vacuum insulation material prepared in Example 1, Comparative Example 1 and Comparative Example 6 was measured in the vertical and horizontal directions, and the results are shown in Table 7 below.

Direction of measurement of thermal conductivity Example 1 Comparative Example 1 Comparative Example 6 Vertical direction (W / mK) 0.2161 0.2162 0.2411 Horizontal direction (W / mK) 2.2326 2.2323 17.2370

Specifically, as can be seen from Table 7, the thermal conductivity in the vertical direction was similar to that in Comparative Example 6 using the Al thin film layer, but the thermal conductivity in the horizontal direction was significantly higher than that in Example 1 It was confirmed that the heat insulating property of Example 1 was excellent.

On the other hand, although Example 1 includes the double-sided type barrier material, it can be confirmed that the thermal conductivity is similar and superior to that of Comparative Example 1 composed of the single-sided type barrier material.

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.

Claims

(1) a first barrier material on both sides of the first base material layer, on which an aluminum layer is deposited and coated, a second barrier material on one side of the second base material layer, and a second barrier material on which an aluminum layer is vapor- Preparing a third barrier material;
(2) A second barrier material and a third barrier material are disposed on the upper and lower portions of the first barrier material so that the aluminum layers face each other, and a resin layer is interposed between the barrier materials facing each other to improve adhesion and flexibility between the barrier materials Extrusion lamination of a first barrier material to a third barrier material, and forming a thermal fusion layer below the third barrier material to produce a laminate; And
(3) forming an impact protection layer including a glass fiber layer on the upper side of the laminate
Wherein the resin layer is a copolymer comprising ethylene, acrylate and methacrylic acid as monomers.

The method according to claim 1,
Wherein the first base layer, the second base layer and the third base layer each independently comprise at least one of a polyester-based component, a polyamide-based component, and a vinyl alcohol-based component. Method of manufacturing outer shell material

3. The method of claim 2,
Wherein the first base layer is a polyamide-based component or a vinyl alcohol-based component, and the second base layer and the third base layer comprise a polyester-based component.

delete

The method according to claim 1,
Wherein the optical density (OD) of the aluminum layer of the first barrier material is 2.5 to 3.5.

The method according to claim 1,
The heat-sealable layer may be formed 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 (EMA), ethylene methacrylic acid ), Ethylene methyl methacrylate (EMMA), ionomer (Ionomer, IO), and ethylene ethyl acrylate (EEA).

delete

The method according to claim 1,
In the step (2), a laminate is manufactured such that a linear low density polyethylene layer is further formed on the second barrier material,
In the step (3), an impact protection layer is formed on the upper side of the laminate by extrusion lamination such that the polyethylene resin layer is interposed between the upper part of the linear low density polyethylene layer of the laminate and the glass fiber layer coated on one side of the AC coating layer METHOD FOR MANUFACTURING COMPOSITE REINFORCED FLAMMABLE COVERS FOR VACUUM INSULATOR

9. The method of claim 8,
Wherein the AC coating layer is formed on one surface of the glass fiber layer with an isocyanate-based AC coating agent in a coating amount of 0.5 to 1.5 g / m < 2 >.

The method according to 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 method according to claim 1,
Wherein the glass fiber layer comprises 50 wt% to 60 wt% of SiO ₂ , 10 wt% to 20 wt% of Al ₂ O ₃ , 8 wt% to 10 wt% of B ₂ O ₃ , 1 wt% to 2 wt% of MgO, 20 wt% % to 24 wt%, Na ₂ O 0.1 wt.% to 1 wt%, K ₂ O 0.1 wt.% to 1 wt%, TiO ₂ 0.01 wt.% to 0.05 wt% and Fe ₂ O ₃ 0.01 wt.% to 0.5 wt.% Wherein the method comprises the steps of:

The method according to claim 1,
The optical density (OD) of the aluminum layer of each of the second barrier material and the third barrier material is independently 3.0 to 5.5,
Wherein the resin layer comprises a copolymer comprising ethylene, acrylate and methacrylic acid as monomers.

A plurality of barrier materials including a first barrier material, a second barrier material and a third barrier material, wherein the first barrier material comprises an aluminum layer deposited and coated on both sides of the first base material layer, the second barrier material and the third The barrier material comprises an aluminum layer vapor-coated on one side of the second substrate layer and the third substrate layer, respectively, and a first barrier material is interposed between the second barrier material and the third barrier material so that the aluminum layer deposited and coated on the barrier material faces each other A barrier layer interposed between each of the barrier materials to be laminated, the barrier layer including a resin layer for improving adhesion and flexibility of the barrier materials;
A heat-sealable layer formed on the lower portion of the barrier layer; And
And an impact protection layer comprising a glass fiber layer formed on the upper portion of the barrier layer
Wherein the resin layer is a copolymer containing ethylene, acrylate, and methacrylic acid as monomers, and is a composite reinforced flame retardant outer material for vacuum insulators.

14. The method of claim 13,
Wherein the barrier material has an average thickness of 8 to 30 占 퐉 and the resin layer has an average thickness of 8 to 30 占 퐉.

14. The method of claim 13,
Wherein the outer covering material has a total thickness of 140 mu m to 360 mu m.

14. The method of claim 13,
And the optical density (OD) of the aluminum layer of the second barrier material and the third barrier material are independently 3.0 to 5.5.

14. The method of claim 13,
The heat-sealable layer is formed on the lower portion of the third barrier material,
Further comprising a linear low density polyethylene layer between the second barrier material and the impact protection layer,
Wherein the impact protection layer comprises a polyethylene layer, an AC coating layer and a glass fiber layer in this order,
Wherein the polyethylene layer of the impact protection layer is formed to face the linear low density polyethylene layer.

18. The method of claim 17,
Wherein the polyethylene layer has an average thickness of 10 占 퐉 to 20 占 퐉, the AC coating layer has an average thickness of 0.5 占 퐉 to 1.5 占 퐉, and the glass fiber layer has an average thickness of 30 占 퐉 to 200 占 퐉.

17. The method of claim 16,
Wherein the composite reinforced flame retardant outer covering material is bonded to the glass fiber layer of the impact protection layer through a second layer of the second barrier material, which is the uppermost layer of the barrier layer, with an adhesive layer interposed therebetween.

An outer covering material for vacuum insulation according to any one of claims 13 to 19. And
And a core member which is sealed by the outer covering member and comprises at least one member selected from the group consisting of glass fiber, glass wool, polyurethane, polypropylene and polyester.

21. The method of claim 20,
And a getter material contained in the vacuum insulation material.

21. The method of claim 20,
Wherein the vacuum insulator is used for building materials, containers for storage and transportation, and refrigeration appliances.