KR20230104576A - Gas barrier, lng ship and lng storage container including same, and manufacturing method thereof - Google Patents

Abstract

Disclosed herein are a gas barrier with enhanced cold resistance and flexibility, an LNG ship and an LNG storage container including the same, and a manufacturing method thereof.

Description

Gas barrier, LNG vessel and LNG storage container including the same, and manufacturing method thereof

The present specification relates to a gas barrier having enhanced cold resistance and flexibility, an LNG ship and an LNG storage container including the same, and a manufacturing method thereof.

Currently, a liquefied natural gas cooling system is widely used in LNG (Liquefied Natural Gas) ships and LNG storage containers. In the gas barrier of the cold storage system, the primary barrier is configured using a stainless steel metal having corrosion resistance, and the system is completed through the secondary barrier. The secondary barrier is usually referred to as SB (Secondary Barrier), which is divided into RSB (Rigid Secondary Barrier) and FSB (Flexible Secondary Barrier).

Here, the FSB is used for attachment with the RSB among the secondary barriers, and is attached between modules and at right angles. For this purpose, sealing performance is improved as flexibility increases.

However, the conventional FSB has a problem in that the intermediate aluminum surface treatment method is complicated, and the flexibility varies depending on the MDO / TDO, so that the airtightness is poor when attached to the right angle surface.

Therefore, it is necessary to have high sealing performance while having high mechanical stability under cryogenic temperatures due to an increase in demand for cryogenic cooling systems.

Korean Patent Publication No. 10-2009-0104688 (2009.10.06.)

The present specification is to provide a gas barrier with enhanced cold resistance and flexibility, an LNG ship and an LNG storage container including the same, and a manufacturing method thereof.

In exemplary embodiments of the present invention, aluminum foil first treated with chromate, plasma or corona; and an adhesive layer positioned on both outer surfaces of the aluminum foil, wherein the adhesive layer is composed of two layers of a urethane layer and a polyamide layer.

In one aspect of the present invention, a gas barrier having improved adhesion between aluminum and a glass reinforcing material is provided.

In another aspect of the present invention, a gas barrier having no deterioration in airtightness even when attached to a right angle surface is provided.

In another aspect of the present invention, a gas barrier having excellent sealing performance even at extremely low temperatures is provided.

In another aspect of the present invention, a method for manufacturing a gas barrier that simplifies the aluminum surface treatment method and reduces cost and process time is provided.

1 is a structural diagram of a gas barrier according to an embodiment of the present invention.
2 is a schematic view of a method for measuring the flexibility of a film according to an embodiment of the present invention.

In this specification, when a certain component is said to "include", it means that it may further include other components, not excluding other components unless otherwise stated.

Hereinafter, exemplary embodiments of the present invention are described in detail.

1 is a structural diagram of a gas barrier according to an embodiment of the present invention.

In exemplary embodiments of the present invention, the aluminum foil 10 is primarily treated with chromate, plasma or corona; and an adhesive layer 20 positioned on both outer surfaces of the aluminum foil, wherein the adhesive layer is composed of two layers of a urethane layer 21 and a polyamide layer 22.

In the conventional gas barrier, the aluminum surface treatment method is complicated, and flexibility varies depending on MDO/TDO, so there is a problem in that airtightness is poor when attached to a right angle surface.

In one aspect of the present invention, the aluminum surface treatment method is simplified to reduce costs and processes, and the adhesive film between aluminum and glass reinforcing material is composed of two layers (urethane layer and polyamide layer) to improve adhesion and flexibility. can improve

The aluminum foil 11 is subjected to primary treatment (12) with chromate, plasma or corona, and according to one embodiment of the present invention, the adhesive layer is composed of two layers, and the adhesive layer and adhesive strength are sufficient only by primary treatment of aluminum. can improve

The chromate may be treated using a gravure coater, the plasma may be treated using a plasma device, and the corona may be treated using a corona treatment machine.

Among the adhesive layers, the urethane layer may include a urethane-based resin, and may further include an epoxy-based resin, a rubber-based resin, a polyester-based resin, or an amide-based resin in addition to the urethane-based resin.

The polyamide layer of the adhesive layer may include a polyamide-based compound, and may further include an epoxy-based resin, a rubber-based resin, a polyester-based resin, or an amide-based resin in addition to the polyamide-based compound.

In an exemplary embodiment, the urethane layer and the polyamide layer of the adhesive layer may be chemically and physically bonded to each other. Compared to the case where polyamide is treated on aluminum, the adhesive strength between polyamide and urethane is better, and the adhesive strength and flexibility can be optimized by adjusting the ratio of the constituent layers.

Polyamide is a coating method, and urethane is formed in a film type, and the polyamide layer on top of the conventional urethane film is made of a web-type (non-woven fabric) film in 2-layer (urethane-polyamide (2-layer) / Compared to aluminum), adhesion is improved with a high surface area with urethane and aluminum, and it is possible to use less energy during laminating, so productivity can be improved.

In one embodiment, the weight ratio of polyamide and urethane may be polyamide : urethane = 10-90 : 90-10.

In an exemplary embodiment, the polyamide layer of the adhesive layer may contact the outer surface of the aluminum foil.

In an exemplary embodiment, a glass reinforcing member 30 positioned on an outer surface of the adhesive layer may be further included. The glass reinforcing material may include glass fibers, and may further include at least one of polyethylene fibers, carbon fibers, aramid fibers, and fiber-reinforced composite materials.

For example, the gas barrier is glass reinforcement 30 / urethane adhesive layer 22 / polyamide adhesive layer 21 / chromate, plasma or corona treatment surface 12 / aluminum 11 / chromate, plasma or corona treatment surface 12 )/ polyamide adhesive layer 21/ urethane adhesive layer 22/ glass reinforcing material 30.

In an exemplary embodiment, the gas barrier may be for a liquefied natural gas cold storage system.

In an exemplary embodiment, the gas barrier may be for a flexible secondary barrier (FSB).

In another exemplary embodiment of the present invention, an LNG vessel including the gas barrier described above is provided.

In still other exemplary embodiments of the present invention, an LNG storage vessel including the aforementioned gas barrier is provided.

In another exemplary embodiment of the present invention, the method for manufacturing the gas barrier described above includes primary treatment of aluminum with chromate, plasma or corona; and laminating a polyamide adhesive layer and a urethane adhesive layer on both sides of the primary treated aluminum in order.

In an exemplary embodiment, in the laminating step, a glass reinforcing material may be further included on the urethane adhesive layer, and the polyamide adhesive layer, the urethane adhesive layer, and the glass reinforcing material may be sequentially laminated on both sides of the primarily treated aluminum.

Specifically, after surface treatment to increase adhesion and durability of Al foil, a gas barrier having mechanical anchoring power can be manufactured by performing roll lamination of glass fiber/adhesive film/aluminum with a thermal laminating machine.

For example, lamination is performed at 120° C. to 200° C. with a thermal laminating machine, and the operation speed of roll lamination may be set to 1 m/min to 5 m/min.

In an exemplary embodiment, the step of cutting both ends of the laminated barrier may be further included.

Hereinafter, specific embodiments according to exemplary embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and only the following examples will complete the disclosure of the present invention and at the same time, common in the art. It will be understood that the intention is to facilitate practice of the invention to those skilled in the art.

Example

Example 1 Invention

The product structure was prepared and laminated in the order of fiber layer (glass reinforcing material)/urethane adhesive layer/polyamide adhesive layer/Al-foil/polyamide adhesive layer/urethane adhesive layer/fiber layer (glass reinforcing material).

Specifically, after chromating the aluminum foil, it was used at 120 ° C to 200 ° C as a thermal bonding machine, and the operating speed was set to 1 m / min to 5 m / min.

Comparative Example 1 Existing component layer A product

It was prepared in the same manner as in Example 1, but without the polyamide adhesive layer, and laminated in the order of fiber layer (glass reinforcing material) / Urethane film / Al-Foil / Urethane film / fiber layer (glass reinforcing material).

Comparative Example 2 Existing component layer B product

Fiber layer (glass reinforcing material)/Olefin film/Al-Foil/Olefin film/fiber layer (glass reinforcing material) were laminated in this order.

Test Example - Flexibility Measurement Result

With respect to the gas barriers prepared in Examples and Comparative Examples, experiments were conducted as shown in the following description and FIG. 2 .

1. Produce specimens of the same size for each sample (2.5cm * 30cm)

2. Test the R value step by step as above

3. Steps are divided according to the degree of adhesion between the test bar (R measurement) and the sample (step 4)

4. Samples satisfying a small R value are judged to have improved adhesion area and sealing property at the corner.

Specifically, referring to FIG. 2, when the sheet-like material is spread and bent after being in close contact with the cylindrical bar (⊂ shape), the radius of the cylinder is indicated as an R value, and the lower the R value, the more flexible the sample is without damage It can be judged to be excellent. Those of ordinary skill in the art can easily understand.

5. Confirm that there is no damage to the sample after testing

division Example 1 Comparative Example 1 Comparative Example 2 R value 4 △ ⅹ ⅹ R value 6 ○ △ ⅹ R value 8 ◎ ○ △ R value 10 ◎ ○ ○ R value 12 ◎ ◎ ◎ R value 24 ◎ ◎ ◎

Excellent ( ◎ ), Good ( ○ ), Normal ( △ ), Unsatisfactory (ⅹ ).

In addition, as the elastic force was measured, the device used was a universal testing machine, and a 50 mm x 300 mm rectangular film type was used as the specimen shape. After fixing both ends of the film with a jig, when the jig moves 50% in the compression direction, the elastic force to return the specimen to its original direction is measured.

As a result of the elastic force measurement, the lower the elastic force measured value, the better the flexibility. The value of Comparative Example 1 (Company A) was MD 0.702N / TD 1.06N, and the value of Comparative Example 2 (Company B) was MD 0.742N / TD 1.41 The value of N, Example 1 was measured as MD 0.606N / TD 0.802N.

Claims (7)

Primary treatment of aluminum foil with one of chromate, plasma and corona; and
Laminating an adhesive layer and a glass reinforcing material located on the outer surface of the adhesive layer on both outer surfaces of the primary treated aluminum foil;
Including,
The adhesive layer is composed of two layers of a urethane layer and a polyamide layer chemically and physically bonded to each other,
The weight ratio of the polyamide and the urethane is polyamide: urethane = 10 to 90: 90 to 10,
By the lamination, a polyamide layer and a urethane layer are laminated in order on both outer surfaces of the primarily treated aluminum foil,
A method of manufacturing a flexible gas barrier, wherein the polyamide layer of the adhesive layer is in contact with the outer surface of the aluminum foil. A flexible gas barrier prepared according to claim 1,
Aluminum foil primarily treated with one of chromate, plasma and corona;
Adhesive layers located on both outer surfaces of the aluminum foil; and
Glass reinforcing material located on the outer surface of the adhesive layer;
including,
The adhesive layer is composed of two layers of a urethane layer and a polyamide layer,
The weight ratio of the polyamide and the urethane is polyamide: urethane = 10 to 90: 90 to 10,
A flexible gas barrier, wherein the polyamide layer of the adhesive layer is in contact with the outer surface of the aluminum foil. According to claim 2,
The urethane layer and the polyamide layer of the adhesive layer are chemically and physically bonded to each other, a flexible gas barrier. According to claim 2,
The flexible gas barrier is for a liquefied natural gas cold storage system. According to claim 2,
The flexible gas barrier is for a flexible secondary barrier (FSB), a flexible gas barrier. An LNG vessel comprising the flexible gas barrier according to any one of claims 2 to 5. An LNG storage container comprising the flexible gas barrier according to any one of claims 2 to 5.

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