KR101260306B1 - Multilayered super barrier sealing member for vacuum insulation materials having excellent gas barrier property - Google Patents

Abstract

The present invention relates to a multilayer super barrier sealing member for vacuum insulation having excellent gas barrier properties, and more particularly, to a multilayer encapsulation for vacuum insulation having a heat sealing layer as an innermost layer, a metal layer as a blocking layer and a protective layer as an outermost layer. A multilayer super barrier encapsulation member for a vacuum insulator, characterized in that the protective layer comprises an inorganic oxide deposited polyethylene terephthalate layer as a member. The vacuum insulation material including the sealing member according to the present invention as an outer shell material is particularly suitable for construction of 30 years or more, which is excellent in durability as well as initial heat insulation performance and long-term use compared to conventional products, which is durable.

Description

Multilayered super barrier sealing member for vacuum insulation materials having excellent gas barrier property}

The present invention relates to a multilayer super barrier sealing member for vacuum insulation having excellent gas barrier properties, and more particularly, to a multilayer encapsulation for vacuum insulation having a heat sealing layer as an innermost layer, a metal layer as a blocking layer and a protective layer as an outermost layer. A multilayer super barrier encapsulation member for a vacuum insulator, characterized in that the protective layer comprises an inorganic oxide deposited polyethylene terephthalate layer as a member. The vacuum insulation material including the sealing member according to the present invention as an outer shell material is particularly suitable for construction of 30 years or more, which is excellent in durability as well as initial heat insulation performance and long-term use compared to conventional products, which is durable.

Vacuum insulation is a material that exhibits more than 5 times better insulation performance than existing organic / inorganic insulation by blocking the convection inside the insulation by vacuuming the inside of the insulation. This vacuum insulator generally consists of a core material, a super barrier sealing member (cover material), and a gas adsorbent (Getter). Among them, the outer shell material has a multilayer film structure in which aluminum foil and plastic layer are normally laminated, and performs a function of primarily blocking internal high vacuum and external atmospheric pressure to continuously maintain a high vacuum state inside the vacuum insulator, thereby ensuring long-term vacuum insulation. Guaranteed durability.

As such, the outer cover material is an indispensable element for maintaining the vacuum degree of the vacuum insulator, and serves to primarily maintain the vacuum degree inside the vacuum insulator. Therefore, when the air-resistant sealing member having low blocking performance is applied to a vacuum insulation product as an outer cover material, external gas and moisture may flow in with the product for a long time, and in this process, the degree of vacuum is lowered, which in turn lowers the insulation performance. Let's go.

Existing vacuum insulating material breathable sealing member is made of nylon or polyethylene terephthalate (PET) as a protective layer, aluminum (Aluminum) metal as a barrier layer and polyethylene (polyethylene) as a heat seal layer By construction, this is a general shell material composition most commonly used as a vacuum insulation shell material for a refrigerator having a durability of 10 to 15 years.

However, the most important physical properties of the vacuum insulation material is not only the initial heat insulation performance but also durability performance according to long-term use, there is a limit that can not be utilized for construction for more than 30 years durable with the general conventional shell material composition as described above. Since the material that has the greatest influence on maintaining the thermal insulation performance of the vacuum insulator is an outer material, it is required to develop a jacket for the vacuum insulator that can exhibit excellent gas barrier performance despite long-term use.

The present invention is to solve the problems of the prior art as described above, the outer shell material having improved breathability than the conventional outer shell material for vacuum insulation and by applying the same to prevent the deterioration of properties even in the long-term use and high physical properties reliability It is a technical object of the present invention to provide a vacuum insulating material, in particular, a vacuum insulating material for building, which can maintain excellent heat insulating performance.

In order to achieve the above technical problem, the present invention has a heat-sealing layer as an innermost layer, a metal layer as a blocking layer and a protective layer as an outermost layer, and the protective layer includes a polyethylene terephthalate layer on which an inorganic oxide is deposited. Provided is a multilayer super barrier sealing member for vacuum insulator.

According to another aspect of the present invention, there is provided a vacuum insulating material, preferably a building vacuum insulating material, characterized in that the multilayer super barrier sealing member is included as an outer covering material.

Vacuum insulating material applying the multi-layered super barrier sealing member according to the present invention as an outer shell material can exhibit a long-term durability of more than 30 years can be suitably used for a conventional refrigerator, as well as for construction requiring high reliability and long-term durability.

1 is a schematic diagram of a layer structure of an embodiment of a multilayered super barrier encapsulation member according to the present invention.

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

The multilayer sealing member of the present invention basically has a heat sealing layer as the innermost layer, a metal layer as the blocking layer and a protective layer as the outermost layer.

The innermost heat-sealing layer is a layer that enables heat-sealing between the outer shell materials and closely adheres to the core material when the multi-layered sealing member is applied to the vacuum insulation material as the outer shell material, and serves as a sealing material. In the multilayer sealing member of the present invention, as the material of the heat-sealing layer, not only the heat-sealing layer material commonly used in the existing vacuum insulation shell material but also other materials having other special functions may be used, for example, LLDPE (linear low density). Polyethylene-based conventional polymeric materials such as polyethylene), LDPE (low density polyethylene), HDPE (high density polyethylene), etc. may also be used, but as in preferred embodiments of the present invention, are commonly used in heat-sealing layers for special functions. In addition to butene PE and octene PE, metallocene PE or PE copolymer (Copolymer or Terpolymer), ionomer polymer, EAA (Ethylene Acrylic Acid) to improve the performance of resin layer's flexibility, tightness and piercing resistance , EMAA (Ethylene Meta Acrylic Acid) may be used.

There is no particular limitation on the thickness of the heat fusion layer, and may have a heat fusion layer thickness generally applied in existing vacuum insulation shell materials. For example, a heat seal layer having a thickness in the range of 20 μm to 100 μm, more specifically 30 μm to 70 μm may be applied. In a preferred embodiment of the invention, the heat seal layer thickness is about 50 μm.

As the barrier layer, the metal layer serves to prevent ventilation, and aluminum foil (Aluminum Foil) is commonly used, but is not limited thereto. If necessary, vapor-deposited polyethylene terephthalate (inorganic oxide / metal deposition PET), EVOH (Ethylene Vinyl Alcohol) A material such as may replace aluminum, or may form a barrier layer with aluminum.

The thickness of the blocking metal layer is not particularly limited, and may have a metal layer thickness that is conventionally applied in the existing vacuum insulation shell material. For example, a barrier metal layer having a thickness in the range of 5 μm to 15 μm, more specifically 5 μm to 10 μm may be applied. In a preferred embodiment of the present invention, the aluminum foil layer thickness is 6.5 to 9 µm.

The outermost protective layer is characterized in that it comprises an inorganic oxide deposited polyethylene terephthalate (inorganic oxide deposited PET) layer. Inorganic oxide-deposited PET has an advantage of improving the blocking performance and complementing the blocking performance of a metal layer, such as aluminum foil, compared to the PET used in the conventional outer cover material for vacuum insulation. PET is used only to protect aluminum thin films in conventional envelopes using only PET, whereas inorganic oxide-deposited PET improves the durability of the envelope itself and also ensures gas barrier properties. It is possible to further improve, thus making it possible to manufacture a high-performance breathable sealing member for vacuum insulator with long-term durability.

Examples of the inorganic oxide deposited on the PET to form the inorganic oxide deposition layer include aluminum oxide (AlOx), silica oxide (SiOx), and the like, with aluminum oxide being preferred. The thickness of the inorganic oxide layer deposited on the PET may, for example, be in the range of 100 GPa to 500 GPa, more preferably 200 GPa to 400 GPa, but is not necessarily limited thereto.

The thickness of the PET layer including the inorganic oxide deposited layer is not particularly limited, and may have a protective layer thickness that is commonly applied in the existing vacuum insulation shell material. For example, an inorganic oxide deposited PET layer having a thickness in the range of 5 μm to 20 μm, more specifically 5 μm to 15 μm may be applied. In a preferred embodiment of the present invention, the inorganic oxide deposited PET layer has a thickness of 10 to 15 µm.

The outermost protective layer may further include a nylon layer to improve durability. Nylon layer has excellent abrasion resistance, pinhole resistance and flexibility to prevent pinholes from impacts from the outside, and it can be used in the handling and secondary processing (folding, bending, adhesion, etc.) of aluminum materials such as aluminum foil. It is possible to maintain the airtightness by preventing damage to the metal layer and can be preferably used.

When the nylon layer is additionally introduced into the protective layer, the thickness thereof is not particularly limited, and may be, for example, 10 μm to 30 μm, more specifically 15 μm to 30 μm, but is not necessarily limited thereto. . In a preferred embodiment of the invention the nylon layer thickness is about 25 μm.

When the nylon layer is additionally introduced into the protective layer, there is no particular limitation on the stacking order of the inorganic oxide deposited PET layer and the nylon layer. In other words, the inorganic oxide deposited PET layer may be the outermost layer, and conversely, the nylon layer may be the outermost layer. In either case, it is preferable that the inorganic oxide deposited surface be placed in the nylon layer direction (ie, between the PET layer and the nylon layer). The nylon layer may also be further applied to serve as a protective layer between the barrier layer and the heat seal layer. If pinhole resistant and toughness nylon is applied between the barrier layer and the heat-sealed layer, the barrier layer is damaged by the glass wool core (in particular, a non-fibrous glass mass material, which may be present) in contact with the heat-sealed layer. It is possible to protect the barrier layer by preventing wear.

The multilayer encapsulation member of the present invention may include one or more of the functional layers described above as necessary. In addition, since the encapsulation member of the present invention has a multi-layered structure, adhesion between layers is required, and for this purpose, an interlayer boundary (for example, between a heat seal layer and a metal layer, a metal layer and a protective layer (inorganic oxide deposited PET layer or nylon layer) for adhesion is required. In each case, the adhesive layer is included between the inorganic oxide deposited PET layer and the nylon layer). There are no particular limitations on the adhesives that can be used, and preferably, as the two-component adhesives, polyester urethane polyols, and curing agents are used in which the main component is aromatic polyisocyanate, but is not necessarily limited thereto. In order for the sealing member to effectively block the impact from the outside, it is preferable that the adhesive force between each layer is the same as possible. When each layer is strongly bonded to the same level, there is an advantage that the overall durability is greatly increased while maintaining the characteristics of each layer. Therefore, in the preferable embodiment of this invention, the kind of two-component adhesive apply | coated between each layer, application amount and an equivalence ratio, press pressure, heating temperature, etc. are all made to the same level.

The multi-layered encapsulation member of the present invention can be produced, for example, as follows according to the material and lamination order of each layer described above: The surface of the encapsulation member using 10 μm to 15 μm of PET deposited with inorganic oxide as the outermost layer. The protection and blocking performance is primarily performed. The reason why the inorganic oxide deposited PET is applied is that secondary barrier performance can be added by aluminum oxide deposition, which further lowers the oxygen permeability of the encapsulation member, and the moisture resistance of the PET further lowers the moisture permeability of the encapsulation member. . The second laminated film is nylon (preferred thickness is about 15 μm to 30 μm). (In this case, the order of lamination of the inorganic oxide-deposited PET and nylon may be changed as necessary.) The third laminated film based on the outermost layer film is an aluminum metal film (preferable thickness is about 6.5 to 9 µm). The aluminum metal film finally adds the blocking performance of the sealing member to impart perfect blocking performance to the sealing member. Finally, about 50 micrometers of LLDPE which is a heat-seal layer is laminated as an innermost layer. In order to protect the barrier layer from damage by the glass wool core material, a nylon layer (preferable thickness of about 15 μm to 30 μm) may be additionally applied between the aluminum metal film and the heat seal layer.

Multi-layered encapsulation member of the present invention, by including the inorganic oxide-deposited PET in the surface protection layer of the encapsulation member to exhibit the moisture permeability of the existing PET, as well as to minimize the gas permeability, as a result the perfect blocking performance (For example, gas permeability = 0.05 cc / m 2 day or less, moisture permeability = 0.005 g / m 2 day or less) A super barrier breathable sealing member can be produced.

Since the vacuum insulation material to which the super barrier breathable sealing member of the present invention is applied as an outer cover material has a long-term durability of 30 years or more, it can be used for a vacuum insulation material for construction as well as existing refrigerators.

Accordingly, according to another aspect of the present invention, there is provided a vacuum insulating material, preferably a building vacuum insulating material, comprising the multilayer super barrier sealing member of the present invention as an outer covering material.

The vacuum insulator according to the present invention also includes a core material, which is a core material, and a gas adsorbent. It is preferable to use a glass wool needling process as the core material, and CaO (quick lime) and / or other metal powder getters are preferably used as the gas adsorbent, but the present invention is not limited thereto. A feature of the vacuum insulator according to the present invention is that the multilayer super barrier encapsulation member of the present invention is included as an outer cover material, and other configurations can be appropriately selected as necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by these examples.

Example  One

Aluminum oxide deposited inorganic oxide deposited PET 12㎛ as the outermost layer, and 25㎛ nylon and aluminum metal film 9㎛ were laminated in order below, the innermost layer was laminated to LLDPE 50㎛ to prepare a sealing member.

Using the encapsulant as an outer shell material, a vacuum insulation material was fabricated at a high vacuum of 10 ^-4 torr using a glass wool core material and a gas adsorbent (simultaneous adsorption of water and gas).

The core material applied was a core material needling glass wool, and the gas adsorbent was a combo-type gas adsorbent containing a metal component (Ba, Li, etc., gas adsorption) on a CaO (quick lime, water adsorption) base.

Example  2

In the same manner as in Example 1, 10 µm of inorganic oxide-deposited PET was applied as the outermost layer of the encapsulation member, and 25 µm of nylon and 6.5 µm of aluminum metal film were sequentially laminated on the lower part thereof, and LLDPE 50 µm was laminated as the innermost layer. The sealing member was manufactured.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Example  3

In the same manner as in Example 1, 12 µm of inorganic oxide-deposited PET was applied as the outermost layer of the encapsulation member, and 25 µm of nylon and 7 µm of aluminum metal film were sequentially laminated on the lower part thereof, and 15 µm of nylon was added to the lower part thereof. The LLDPE 50㎛ laminated as the innermost layer to prepare a sealing member.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Example  4

In the same manner as in Example 1, except that 25 µm of nylon was applied as the outermost layer of the encapsulation member, and 12 µm of inorganic oxide PET and 9 µm of an aluminum metal film were laminated in the order below, and the innermost layer was LLDPE 50. The sealing member was manufactured by laminating | stacking micrometer.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Example  5

In the same manner as in Example 1, the inorganic oxide deposited PET was 12 µm as an outermost layer, and 25 µm of nylon and 7 µm of aluminum metal film were sequentially stacked on the bottom thereof, and the metallocene PE 50 µm was laminated as the innermost layer. The member was manufactured

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Comparative example  One

In the same manner as in Example 1, 12 μm of normal (no vapor deposition) PET was applied as the outermost layer of the encapsulation member, and 25 μm of nylon and 9 μm of aluminum metal film were sequentially laminated on the lower part thereof, and the innermost layer was LLDPE 50. The sealing member was manufactured by laminating | stacking micrometer.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Comparative example  2

In the same manner as in Example 1, 10 μm of normal (no vapor deposition) PET was applied as the outermost layer of the encapsulation member, and 25 μm of nylon and 6.5 μm of aluminum metal film were sequentially laminated on the bottom thereof, and LLDPE 50 was used as the innermost layer. The sealing member was manufactured by laminating | stacking micrometer.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Comparative example  3

In the same manner as in Example 1, nylon 15㎛ was applied to the outermost layer of the sealing member, and 15㎛ nylon and 7μm aluminum metal film were sequentially laminated on the lower portion thereof, and 15㎛ nylon was added to the lower portion thereof. The LLDPE 50 micrometers were laminated | stacked in the innermost layer, and the sealing member was manufactured.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Comparative example  4

In the same manner as in Example 1, except that 25 µm of nylon was applied as the outermost layer of the encapsulation member in a reverse order, and 12 µm of normal (no deposition) PET and 9 µm of an aluminum metal film were laminated in the order below. LLDPE 50 µm was laminated to prepare a sealing member.

A vacuum insulator was produced in the same manner as in Example 1 using the encapsulant as an outer cover material.

Processing conditions and results of the above Examples and Comparative Examples Test results of the insulating material are shown in Table 1 below.

       * Durability figures refer to thermal conductivity (W / mK) values.

As can be seen from the test results of Table 1, the performance of the example sealing member to which the inorganic oxide deposited PET was applied showed physical properties superior to that of the comparative example sealing member using normal (no deposition) PET. In particular, there was a big difference in initial failure rate and durability, but since the initial failure rate and long-term durability of vacuum insulation materials are primarily determined by the encapsulant, the composition of the shell material is the most important for improving these properties. That is, as a result of fabricating a vacuum insulation material and measuring the thermal conductivity using the same core material and gas adsorbent in the encapsulation member for each example and comparative example, the vacuum insulation material of the embodiment to which the inorganic oxide deposited PET was applied is less than 0.0030W / mK. Excellent physical properties are shown. In addition, even in the case of the occurrence of defective products in the manufacturing process of the vacuum insulation material, the defect rate of the vacuum insulation material product made by using the encapsulation member using inorganic oxide deposited PET was only 3% or less, and the vacuum insulation material of the comparative example using no deposition PET even in the durability performance. It showed excellent quality, such as showing more than twice the physical properties (based on the deterioration rate of thermal insulation performance with time). Analyzing the thermal conductivity and product defect rate results of the vacuum insulator shown in Table 1, it can be concluded that inorganic oxide deposited PET has better barrier performance and durability than the general PET, thus ensuring high long-term durability of the vacuum insulator.

Polyethylene terephthalate (PET)
2. Inorganic oxide deposition layer
※ 1 + 2: Inorganic oxide deposited PET layer
3. Nylon layer
4. Aluminum foil layer
5. LLDPE film layer
6.1, 6.2, 6.3: urethane adhesive layer

Claims (12)

A heat seal layer as the innermost layer; Barrier layer; And a protective layer as the outermost layer,
Wherein the protective layer comprises an inorganic oxide deposited polyethylene terephthalate layer and at least one nylon layer, wherein the inorganic oxide deposited surface of the inorganic oxide deposited polyethylene terephthalate layer is placed in the direction of the nylon layer,
Multilayer sealing member for vacuum insulator. The method of claim 1, wherein the heat-sealing layer is composed of at least one material selected from the group consisting of LLDPE, LDPE, HDPE, butene PE, octene PE, metallocene PE, PE copolymer, ionomer polymer, EAA and EMAA. Seal member to be made. The sealing member according to claim 1, wherein the blocking layer is an aluminum foil layer. The encapsulation member of claim 1, further comprising at least one nylon layer between the barrier layer and the heat seal layer. The sealing member according to claim 1, further comprising an adhesive layer at the boundary of each layer. 6. The sealing member according to claim 5, wherein the adhesive is a two-component adhesive comprising a polyester urethane polyol base and an aromatic polyisocyanate curing agent. The sealing member according to claim 5, wherein the adhesive type and the application amount of each adhesive layer are the same. A vacuum insulating material comprising the sealing member according to any one of claims 1 to 7 as an outer covering material. The vacuum insulator according to claim 8, which is for construction. delete delete delete

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