KR101704783B1 - Outer packaging materials for vacuum insulation panel, method for manufacturing thereof and Vacuum insulation panel comprising the same - Google Patents

Abstract

The present invention relates to an outer cover material for vacuum insulation materials, a method for producing the same, and a vacuum insulation material containing the same. More particularly, the outer cover material for vacuum insulation materials is remarkably excellent in gas barrier property, moisture barrier property and heat shielding property, To a method for producing the same, and a vacuum insulation material containing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an outer cover material for a vacuum insulation material, a method of manufacturing the same, and a vacuum insulation material including the outer insulation material,

The present invention relates to an outer cover material for vacuum insulation materials, a method for producing the same, and a vacuum insulation material containing the same. More particularly, the outer cover material for vacuum insulation materials is remarkably excellent in gas barrier property, moisture barrier property and heat shielding property, To a method for producing the same, and a vacuum insulation material containing 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, such a vacuum insulation material is not easy to handle because the density of the panel is about 200 kg / m 3 to 300 kg / m 3, and there is a problem that it has a risk factor due to the sharpness of the joint part of the vacuum insulation material. . 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.

In order to manufacture such an outer covering material, 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, and then the second barrier material 520 The adhesive agent layer 520b and the first barrier material 510 are laminated on the exposed one side of the adhesive layer 520. If a plurality of barrier materials are provided, There is a 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 of the barrier material, accelerating the inflow of moisture / gas into the separated gap, Etc., 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 .

Therefore, even when a plurality of barrier materials are included, the flexibility of the outer covering material can be ensured, so that the outer covering material is prevented from being damaged by the manufacturing process of the product and / It is urgently necessary to develop an outer shell material remarkably excellent in basic properties such as heat insulation and water / gas shielding that should be provided as an outer shell material of a vacuum insulation material and to manufacture such an outer shell material with higher productivity .

It is an object of the present invention to provide a method for manufacturing an outer covering material for a vacuum insulator that significantly improves productivity through shortening of a barrier material laminating step in the process of manufacturing an outer covering material. .

A second problem to be solved by the present invention is to provide a method for manufacturing a vacuum insulation material and / or a method for manufacturing a vacuum insulation material, which is excellent in the effects of insulation, moisture / gas shutoff and the like, In which the physical damage to the outer covering material is minimized during use of the outer covering material and the vacuum insulation material including the outer covering material.

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 base material layer by evaporation coating an aluminum layer, And a third barrier material having an aluminum layer deposited and coated on one end face of the third base material 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 the first barrier material to the third barrier material; And (3) forming an adhesive layer on the upper portion of the second barrier material or a lower portion of the third barrier material, and forming a heat-sealable layer on the lower portion of the adhesive layer.

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, 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-based component.

According to another preferred embodiment of the present invention, the vinyl alcohol-based component may include at least one of ethylene vinyl alcohol and polyvinyl alcohol.

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, and the acrylate Acrylic acid ester monomer, and alkyl acrylate ester monomer, and the methacrylate may include at least one of methacrylate ester monomer and alkyl methacrylate ester monomer.

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 optical density (OD) of the aluminum layer included in the barrier material of at least one of the second barrier material and the third barrier material, 5.5.

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 linear low density polyethylene may be metallocene linear low density polyethylene (m-LLEPE).

According to another aspect of the present invention, there is provided a semiconductor device comprising: a barrier layer having a plurality of barrier layers stacked; A heat-sealable layer formed on the lower portion of the barrier layer; And an adhesive layer interposed between the barrier layer and the heat-sealable layer, wherein the plurality of barrier materials include a first barrier material, a second barrier material, and a third barrier material, wherein the first barrier material is provided on both sides 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 is deposited on each barrier material And a resin layer interposed between the second barrier material and the third barrier material so that the coated aluminum layer faces each other and between the respective barrier materials to improve adhesion and flexibility of the barrier materials .

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

According to another preferred embodiment of the present invention, the resin layer may have an average thickness of 10 mu m to 30 mu m.

According to another preferred embodiment of the present invention, the average thickness of the adhesive layer may be 2 to 5 탆.

According to another preferred embodiment of the present invention, the outer covering material may have a total thickness of 90 mu m to 200 mu m.

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 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, the vacuum insulation material may further include a getter material provided in the encapsulated outer material.

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 laminating process of the barrier materials to be provided, and the outer covering material to be manufactured can be a basic material property to be possessed by the vacuum insulation material such as vacuum degree maintenance, insulation, And has excellent flexibility and durability. Thus, it is possible to maintain long-lasting excellent physical properties by minimizing the physical damage that may occur in the manufacturing process of the vacuum insulation material and / or during use of the product, Due to its excellent properties, it can be widely used where various insulation materials such as building materials, containers for storage and transportation, refrigeration equipment, and heat insulation equipment are required.

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 of a manufacturing process according to a preferred embodiment of the present invention.
4 is a schematic view of a manufacturing process according to another preferred embodiment of the present invention.
5 is a cross-sectional view of an outer covering according to a preferred embodiment 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 components not only cause a crack in the vapor deposition layer, which is a metal layer provided in the barrier material, but also have poor adhesive force, separation phenomenon frequently occurs between the barrier materials, and acceleration of water / gas inflow into the separated gap, There is a problem that the physical properties can not be completely attained and the use period of the insulation 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.

(1) a first barrier layer on which an aluminum layer is deposited and coated on both sides of a first base layer, a second barrier layer on one end surface of the second base layer by vapor-coating an aluminum layer and a second barrier layer on an end surface of the third base layer Preparing a third barrier material having an aluminum layer deposited and coated thereon; (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 the first barrier material to the third barrier material; And (3) forming an adhesive layer on the upper portion of the second barrier material or the lower portion of the third barrier material, and forming a heat-sealable layer on the lower portion of the adhesive layer. In the method of manufacturing an outer material for vacuum insulator, And solved the problem. As a result, productivity can be remarkably improved by shortening the laminating process of the barrier materials, and the produced outer covering material is excellent in the effects of maintaining the basic properties of the outer covering material for vacuum insulation such as vacuum degree maintenance, insulation, water / gas shutoff, The physical damage that may occur in the outer covering material during the manufacturing process of the vacuum insulation material and / or the use of the product is minimized, and the 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 the first base material layer, a second barrier material having an aluminum layer deposited and coated on the end surface of the second base material, A step of preparing a third barrier material having an aluminum layer deposited and coated on the end face thereof.

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 the content of acrylate or methacrylate is not satisfied, the resin is disadvantageous in flexibility, so that interfacial peeling between the barrier material and the resin layer frequently occurs, the resin layer is broken and the good adhesion retention between the barrier material can not be exhibited, Or the flow of water / gas is accelerated by the peeled gap, 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. It may also be a copolymer of ethylene-methacrylic acid (EMAA), ethylene-methacrylic acid-acrylic acid, which can be extruded at a temperature of 220-250 ° C.

Next, in step (3) according to the present invention, an adhesive layer is formed on the upper portion of the second barrier material or the lower portion of the third barrier material, and a thermal fusion layer is formed on the lower portion of the adhesive layer.

The heat-sealable 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 the core material 300 shown in FIG. 4) is inserted into the inside of the outer sealing material. The heat sealable layer is composed 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 (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 surface of the second barrier material or the lower surface of the third barrier material, that is, the upper or lower surface of the laminate stacked through the step (2) It can be joined with a sieve. 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.

As described above, the outer covering material manufactured through the above-described manufacturing method includes a barrier layer in which a plurality of barrier materials are stacked; A heat-sealable layer formed on the lower portion of the barrier layer; And an adhesive layer interposed between the barrier layer and the heat-sealable layer, wherein the plurality of barrier materials include a first barrier material, a second barrier material, and a third barrier material, wherein the first barrier material is provided on both sides 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 is deposited on each barrier material And a resin layer interposed between the second barrier and the third barrier so that the coated aluminum layer faces each other and between the respective barrier materials to improve adhesion and flexibility of the barrier materials.

4 is a cross-sectional view of an outer wrapper according to an exemplary embodiment of the present invention. As shown in FIG. 4, a third metal barrier layer 230, a first metal barrier layer 240, The first barrier material 230 and the second barrier material 240 are stacked in this order and the adhesive layer 260 is interposed between the thermal barrier layer 210 and the third barrier material 230, The resin layers 221 and 222 interpose between the barrier layers 232 and 242 and 243 and 252 facing each other between the barrier layers. .

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 layer formed of the adhesive is preferably formed to have an average thickness of 2.5 to 5 μm, preferably an average thickness of 3.0 to 4.5 μm. If the thickness is less than 2.5 μm, there is a problem that the adhesion between the layers is too weak 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.

It is preferable that the thicknesses of the first to third barrier materials are independently from 8 탆 to 30 탆, preferably from 10 탆 to 26 탆, more preferably from 12 탆 to 24 탆, If it is less than 8 mu m, there is a problem that the strength is weak and the moisture permeability is deteriorated. If it exceeds 30 mu m, there is a problem in thinning. 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.

It is preferable that the thickness of the covering material formed by laminating the above components is 70 to 200 m, preferably 80 to 140 m, and if the thickness is less than 70 m, the strength of the vacuum insulator pouch is weak , It may be disadvantageous to maintain the vacuum state. If it exceeds 200 mu m, it may be disadvantageous for thinning.

In addition, the upper portion of the outer covering member may further include an impact protection layer such as glass fiber, and the impact protection layer may be selected according to the purpose known in the art and is not particularly limited in the present invention, The total thickness of the outer covering material is preferably from 140 to 360 μm, more preferably from 150 to 310 μm, and if the total thickness is less than 140 μm, the mechanical properties of the outer covering material may decrease, If the total thickness exceeds 360 탆, the mechanical properties and the like are excellent, but the flexibility of the outer covering material for vacuum insulation decreases, and the folding workability and workability are deteriorated.

The present invention also relates to a vacuum insulator comprising a core material which is encapsulated with the outer material and the outer material according to the present invention and contains at least one selected from glass fiber, glass wool, polyurethane, polypropylene and polyester .

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.

≪ Example 1 >

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-acrylate (Dupont, Nucrel AN4211-5C (MI 32, melting point: 94 캜)) at a temperature of -10 ° C to a temperature of -30 ° C to obtain a first barrier material / And extrusion laminated to produce a laminate. (M-PE Film) (manufactured by Korea Pre-Pack Co., Ltd., trade name: M-PE Film) having an average thickness of 30 탆 and having an average thickness of 30 탆 was coated on one side of the laminate with an adhesive agent (Urethane adhesive) Was laminated to produce an outer covering material having a total thickness of 120 占 퐉. At this time, the average thickness of the adhesive layer was 3.3 占 퐉, and the average thickness of the resin layer was 15 占 퐉.

≪ 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 .

≪ Comparative Example 1 &

(Urethane adhesive) was applied between the barrier materials as shown in Fig. 1, and then the barrier material was dry-laid. Then, And laminated by a lamination method to produce 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 3.5 占 퐉.

≪ Comparative Example 2 &

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

<Experimental Example 1>

The following properties of the outer cladding material prepared through Examples and Comparative Examples were evaluated and shown in Tables 1 and 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) 0.05 0.09 0.05 0.05 0.06 0.05 Water vapor permeability (g / m ² · day) 0.005 0.008 0.005 0.006 0.007 0.006 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 / 15 Urethane Adhesive / 15 A / 15 Oxygen permeability (cc / m 3 · day) 0.05 0.11 0.06 0.07 0.07 Water vapor permeability (g / m ^{2 ·} day) 0.008 0.032 0.005 0.009 0.008 durability Aluminum layer 0 0 5 4 0 Resin layer 0 0 5
(fracture) 5
(Peeling) 4
(Peeling) productivity(%) 150 150 150 100 100 1) terpolymers of ethylene-methacrylic acid-acrylate

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

In Example 3 in which the optical density of the aluminum layer of the first barrier material was more than 3.5, the durability of the aluminum layer was remarkably lowered compared with Example 1, and thus it can be expected that the amount of oxygen and the amount of moisture permeated are significantly increased.

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

In Example 8 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 lowered.

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, the kind of the resin layer was changed to EMAA, but it was confirmed that the durability problem was not solved because the material of the layer facing each of the resin layers was different as in Comparative Example 1. 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 >

(EMAA) and ethylene-methacrylic acid-acrylate terpolymer used as a resin layer were prepared in the same manner as in Example 1, except that the resin shown in the following Table 3 was used instead of the copolymer of ethylene-methacrylic acid 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.

<Experimental Example 2>

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 95 10.0 Melting point (캜) 94 92 104 94 97 Manufacturer / Product Name Dupont / Nucrel 4211-5C Dupont /
Nucrel
925 Dupont /
Nucrel
0609 Dupont /
Nucrel
0699 Dupont /
Nucrel 3990L Coating temperature (캜) 230 230 280 210 270 Oxygen permeability (cc / m 3 · day) 0.05 0.06 0.07 0.06 0.07 Water vapor permeability (g / m ² · day) 0.005 0.006 0.009 0.005 0.007 durability Aluminum layer 0 2 3 0 4 Resin layer 0 One One One 3 productivity(%) 150 150 150 150 150 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 melt index of the resin layer was less than 20 g / 10 min, cracks of the aluminum layer occurred significantly 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.

In Example 13 using EAA as a component of the resin layer, it was confirmed that the durability of the aluminum layer and the resin layer was not significantly better than that of Example 1, and the physical properties were worse even though the melt index was similar to that of Example 2. [

110, 120, 130: Feed rollers 141, 142: Extruder
150: cooling roll 151: rubber roll
152: backup roll 160:
210: heat fusion layer 221, 222: resin layer
230, 240, 250: barrier material 260: adhesive layer
300: core material

Claims (20)

(1) a first barrier material on both sides of the first base material layer, on which an aluminum layer is vapor-deposited and coated, a second barrier material on one side of the second base material layer, and an aluminum layer on one side of the third base material layer Preparing a coated 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 the first barrier material to the third barrier material; And
(3) forming an adhesive layer on the upper portion of the second barrier material or the lower portion of the third barrier material, and forming a thermal fusion layer on the lower portion of the adhesive layer,
Wherein the resin layer is a copolymer comprising ethylene, acrylate and methacrylic acid as monomers and has a melt index (MI, ASTM D1238) of 25 g / 10 min or more and a melting point of 100 캜 or less.
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. Way
3. The method of claim 2,
Wherein one of the first base layer, the second base layer and the third base layer contains a polyester-based component,
Wherein the other base layer comprises at least one of a polyamide-based component and a vinyl alcohol-based component.
3. The method of claim 2,
Wherein the vinyl alcohol-based component comprises at least one of ethylene vinyl alcohol copolymer and polyvinyl alcohol.
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 6,
Wherein an optical density (OD) of the aluminum layer included in at least one of the second barrier material and the third barrier material formed at the upper portion and the lower portion of the first barrier material is 3.0 to 5.5, Way.
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 9. The method of claim 8,
Wherein the linear low density polyethylene is metallocene linear low density polyethylene (m-LLDPE).
delete A barrier layer on which a plurality of barrier materials are stacked;
A heat-sealable layer formed on the lower portion of the barrier layer; And
And an adhesive layer interposed between the barrier layer and the heat-sealable layer,
Wherein the plurality of barrier materials comprise 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 substrate layer,
Wherein the second barrier material and the third barrier material comprise an aluminum layer deposited and coated on one surface of a second substrate layer and a third substrate layer,
The first barrier material is interposed between the second barrier material and the third barrier material so that the aluminum layer vapor-coated on each barrier material faces each other,
And a resin layer between the respective barrier materials to improve adhesion and flexibility of the barrier materials,
Wherein the resin layer is a copolymer comprising ethylene, acrylate and methacrylic acid as monomers and has a melt index (MI, ASTM D1238) of 25 g / 10 min or more and a melting point of 100 캜 or less.
13. The method of claim 12,
Wherein the barrier material has an average thickness of 8 to 30 占 퐉 and the resin layer has an average thickness of 10 to 30 占 퐉.
delete 13. The method of claim 12,
Wherein the adhesive layer has an average thickness of 2 to 5 占 퐉.
13. The method of claim 12,
Wherein the outer covering material has a total thickness of 90 占 퐉 to 200 占 퐉.
13. The method of claim 12,
Wherein the optical density (OD) of the aluminum layer of the first barrier material is 2.5 to 3.5, 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. .
An outer covering material for vacuum insulation material according to any one of claims 12 to 13, 15 to 16, 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.
19. The method of claim 18,
Wherein the vacuum insulation material further comprises a getter material provided inside the encapsulated outer material.
19. The method of claim 18,
Wherein the vacuum insulator is used for building materials, containers for storage and transportation, and refrigeration appliances.

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