KR20180050102A - Insulation material comprising nanoclay protective layer for cargo of liquefied petroleum gas carrierand manufacturing method thereof - Google Patents

Abstract

The present invention relates to an insulating material for a liquefied petroleum gas carrier and a manufacturing method therefor. More specifically, the present invention relates to an insulating material for a liquefied petroleum gas carrier and a manufacturing method therefor, wherein the insulating material has excellent mechanical strength, water-resistance, and flame-retarding, and manufacturing costs can be reduced. To this end, the insulating material for a liquefied petroleum gas carrier includes a foam resin layer made of polyurethane foam and a protection layer including nanoclay on one surface of the foam resin layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat insulating material for a liquefied gas-filled cargo window including a nano-clay protective layer and a method of manufacturing the same.

More particularly, the present invention relates to a heat insulating material for a liquefied gas carrier window which is excellent in mechanical strength, water resistance and flame retardancy and can reduce manufacturing cost, and a method for manufacturing the same. .

Liquefied petroleum gas carrier (LPGC) cargo holds insulation to prevent LPG vaporization by atmospheric heat and cooling of hull structure due to low LPG temperature.

However, since the insulation is usually insufficient in mechanical strength and water resistance, it is exposed to the outside alone during the drying of the cargo hold, or the insulation loss is reduced due to physical damage, resulting in deterioration of the insulation performance. Therefore, the liquefied gas carrier cargo holds the insulation (polyurethane foam) A coating (polyurea coating) layer is applied.

The purpose of the protective coating is to strengthen the physical properties such as water resistance, impact resistance and strength of the insulation, and to prevent fire by adding flame retardancy. In most of the currently used insulation systems, a polyurea protective coating is applied to the insulation And the construction cost of the insulation system is increased.

Therefore, it is required to develop an insulation system that can reduce the cost while compensating for the disadvantages of the insulation.

Korean Patent Publication No. 10-0509702

It is an object of the present invention to provide a heat insulating material for a liquefied gas carrier window which is excellent in mechanical strength, water resistance and flame retardancy and can reduce manufacturing cost, and a method for manufacturing the same.

These and other objects and advantages of the present invention will become apparent from the following description of a preferred embodiment.

The object is achieved by a foamed resin layer made of a polyurethane foam; And a protective layer including a nanoclay on one side of the foamed resin layer.

The protective layer may be prepared by mixing a solution of a polyol matrix and a polymeric MDI (polymeric methylene diphenyl diisocyanate) solution containing a polyol, a foam stabilizer, a catalyst, a blowing agent, a crosslinking agent, and a flame retardant agent, and the nano- Montmorillonite), and may be contained in an amount of 1 to 4% by weight based on 100% by weight of the total solution of the polyol matrix solution and the polymer MDI solution.

At this time, the polyol may be an aromatic polyester polyol, the foaming agent may be a silicon-based foaming agent, and the catalyst may include amine and polyisocyanurate (PIR). The blowing agent may include water and C ₃ H ₃ F ₅ (pentafluoropropane), and the cross-linking agent may be at least any one selected from the group consisting of DEOA (Diethanolamine), TEOA (Triethanolamine) and glycerin And the flame retardant may be a phosphorus flame retardant.

The above object can also be accomplished by a method of manufacturing a foamed polyurethane foam, comprising: a first step of foaming a polyurethane composition to form a foamed resin layer; And a second step of forming a protective layer including a nanoclay on one surface of the foamed resin layer.

Preferably, the second step comprises mixing nanoclay, a dispersant and a polymeric MDI (methylene diphenyl diisocyanate) solution; And adding and mixing a polyol matrix solution containing a polyol, a foam stabilizer, a catalyst, a foaming agent, a crosslinking agent, and a flame retardant to the mixed solution.

At this time, the nano-clay may be montmorillonite, and may be contained in an amount of 1 to 4% by weight based on 100% by weight of the total solution of the polyol matrix solution and the polymer MDI solution.

Further, the polyol may be an aromatic polyester polyol, the foaming agent may be a silicon-based foaming agent, and the catalyst may include an amine and polyisocyanurate (PIR). The blowing agent may include water and C ₃ H ₃ F ₅ (pentafluoropropane), and the cross-linking agent may be at least any one selected from the group consisting of DEOA (Diethanolamine), TEOA (Triethanolamine) and glycerin And the flame retardant may be a phosphorus flame retardant.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a heat insulating material having enhanced flame retardancy as well as physical properties such as water resistance, impact resistance and mechanical strength, by laminating a protective layer including nano clay.

In addition, since the polyurea coating protective layer is not used as in the conventional method, it is possible to reduce the production cost (reduce the number of processes and raw materials cost due to shortening of the manufacturing process).

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a schematic cross-sectional view of a heat insulating material for a liquefied gas carrier according to an embodiment of the present invention.
FIG. 2 is a schematic view illustrating a method for manufacturing a heat insulating material for a liquefied gas cargo window according to an embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples and drawings of the present invention. It is to be understood that these examples are offered by way of illustration only and not to limit the scope of the present invention It will be apparent to those skilled in the art that the present invention is not limited thereto.

Also, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains and, where contradictory, Will be given priority.

In order to clearly illustrate the claimed invention, parts not related to the description are omitted, and like reference numerals are used for like parts throughout the specification. And, when a section is referred to as "including " an element, it does not exclude other elements unless specifically stated to the contrary. In addition, "part" described in the specification means one unit or block performing a specific function.

In each step, the identification code (first, second, etc.) is used for convenience of explanation, the identification code does not describe the order of each step, and each step does not explicitly list a specific order in the context May be performed differently from the above-described sequence. That is, each of the steps may be performed in the same order as described, or may be performed substantially concurrently or in the reverse order.

1 is a schematic view showing a cross section of a heat insulating material 100 for a liquefied gas cargo window according to an embodiment of the present invention. Referring to FIG. 1, a heat insulating material 100 for a liquefied gas carrier window according to an embodiment of the present invention includes a foamed resin layer 10 made of a polyurethane foam; And a protective layer 20 including a nanoclay 30 on one side of the foamed resin layer 10. The present invention provides a heat insulating material having improved flame resistance as well as physical properties such as water resistance, impact resistance and mechanical strength by forming the protective layer 20 including the nano clay 30 on one surface of the foamed resin layer 10 And the polyurea coating protective layer can be omitted unlike the prior art, so that the production cost can be reduced.

In one embodiment, the foamed resin layer 10 is made of rigid polyurethane foam, and has heat insulating properties. The polyurethane foam is manufactured by foaming a polyurethane composition obtained by mixing a polymer MDI (polymeric methylene diphenyl diisocyanate) solution (solution) into a polyol matrix solution in which a polyol, a foam stabilizer, a catalyst, a foaming agent, a crosslinking agent and a flame retardant are mixed can do. The foamed resin layer 10 preferably has a thickness of 80 to 100 mm, but is not limited thereto.

In one embodiment, the polyol is not particularly limited, but generally a polyether polyol or a polyester polyol can be used. It is preferable to use an aromatic polyester polyol rather than a linear polyether polyol in terms of improving physical strength.

In one embodiment, the foam stabilizer is used for emulsifying the resin, dispersing the foaming gas, preventing and stabilizing the formation of cells to be formed, and improving heat insulating performance, and silicone foam stabilizers can be used. Silicon-based foam stabilizers and functional groups such as long-chain alkyl-modified oils, amino-modified oils, and epoxy-modified oils adhered to silicon may be used.

In one embodiment, the catalyst may be used for controlling the reaction rate and improving moldability, and it is preferable to use amine and PIR (polyisocyanurate) in combination.

In one embodiment, the blowing agent may include a physical blowing agent that reacts with the isocyanate during the urethane reaction to form bubbles and inflates the polyurethane foam, and a chemical blowing agent to expand the physical blowing agent during the urethane reaction. HFC-245fa (C ₃ H ₃ F ₅ (pentafluoropropane)), which is not flammable, can be used as the physical blowing agent, and water (H ₂ O) can be used as the chemical blowing agent. The chemical foaming agent and the physical foaming agent may be mixed at a weight ratio of 1: 4: 10 to 40:

In one embodiment, the crosslinking agent strengthens intermolecular bonding, and a polyfunctional substance having mainly three or more functional groups can be used. Preferably, at least one selected from the group consisting of DEOA (Diethanolamine), TEOA (Triethanolamine) and glycerin can be used.

In one embodiment, the flame retardant retards the ignition of polymeric materials that are prone to burning, may prevent expansion of combustion, and may cause particle deposition in the polyol matrix solution and wear of the spray device to apply the polyol matrix solution . The flame retardant is preferably a phosphorus flame retardant. Phosphorous flame retardant can simultaneously act in the gas phase and the solid phase, and can form a charge by the dehydration and carbonization by phosphoric acid generated by pyrolysis, thereby physically blocking the heat transfer to the inside. Specifically, the phosphorus-based flame retardant reacts with a combustible material in a combustion process to form a carbonaceous layer on the surface of the polymer, and this carbonization film blocks the oxygen required for combustion and exhibits a flame retardant effect. Particularly, since the phosphorus flame retardant reacts with the oxygen element in the polymer to dehydrate and carbonize the flame retardant effect, the phosphorus flame retardant effectively acts as a flame retardant in the polymer containing oxygen element. As the phosphorus flame retardant, known phosphorus flame retardants may be used. Specifically, phosphorus ester flame retardants, halophosphorus phosphate esters, non-halogen condensate phosphorus, and polyphosphate based flame retardants may be used.

In one embodiment, the polyol matrix solution is prepared by blending 1 to 3 parts by weight of stabilizer, 1 to 5 parts by weight of catalyst, 10 to 40 parts by weight of blowing agent, 5 to 10 parts by weight of crosslinking agent and 10 to 20 parts by weight of flame retardant Section. When the content is less than the above range, the degree of improvement in physical properties such as water resistance and flame retardancy is insignificant, and when it is included beyond the above range, miscibility with the MDI solution described later can be deteriorated and it is not economical. The matrix solution can be improved in physical properties by adding an appropriate amount of various additives as necessary.

In one embodiment, the protective layer 20 is a polyol matrix solution, a polymeric methylene diphenyl diisocyanate (MDI) solution, and a nanoclay, including a polyol, a foam stabilizer, a catalyst, a blowing agent, (30) may be mixed and then coated on one side of the foamed resin layer (10). The protective layer 20 is not particularly limited, but is preferably 20 to 40 mm thick. The protective layer 20 will be described more specifically. However, since the polyol matrix solution is the same as that used in the foamed resin layer 10, detailed description thereof will be omitted. As the polymeric MDI (polymeric methylene diphenyl diisocyanate) solution, those having an isocyanate (-NCO) functional group in an amount of 30 to 32 wt% based on the total weight can be used. Further, it is preferable that the viscosity at 25 캜 is 150 to 600 cps. The polymer MDI solution is preferably mixed with 200 to 250 parts by weight based on 100 parts by weight of the polyol contained in the polyol matrix solution, and the nano clay 30 is mixed with 100% by weight of the total solution in which the polyol matrix solution and the polymer MDI solution are mixed 1 to 4% by weight. When the content of the nano-clay 30 is less than 1% by weight, improvement of the physical properties of the protective layer is insufficient. When the content of the nano clay 30 exceeds 4% by weight, the viscosity of the MDI mixture containing the nano- There are difficult disadvantages.

In one embodiment, the nanoclay 30 is included in the protective layer 20 and refers to a layered silicate. Specifically, the nano-clay 30 has a very large surface area of 800 square meters per gram on average, and is a very thin sheet having a thickness of 1 nm and a length of 30 to 1000 nm. The nano-clay 30 can be stacked in tens to hundreds, The nanoclay 30 is dispersed homogeneously in the protective layer 20 as a filter to improve various physical properties such as mechanical properties, water resistance and heat resistance. The nanoclay 30 is not particularly limited, but quaternary ammonium It is preferable that the montmorillonite is a salt-modified montmorillonite.

Next, a method for manufacturing a heat insulating material for a liquefied gas carrier window will be described. For convenience of explanation, the above-described heat insulating material 100 for a liquefied gas line cargo window will be described as an example, but the present invention is not limited thereto. The detailed description of the overlapping portions will be omitted.

FIG. 2 is a schematic view of a method of manufacturing a heat insulating material for a liquefied gas carrier lined window according to an embodiment of the present invention (S100). Referring to FIG. 2, there is shown a method of manufacturing a heat insulating material for a liquefied gas carrier window according to an embodiment of the present invention S100) comprises: a first step (S10) of foaming a polyurethane composition to form a foamed resin layer 10; And a second step S20 of forming a protective layer 20 including a nanoclay 30 on one side of the foamed resin layer 10. The present invention provides a heat insulating material having improved flame resistance as well as physical properties such as water resistance, impact resistance and mechanical strength by forming the protective layer 20 including the nano clay 30 on one surface of the foamed resin layer 10 And the polyurea coating protective layer can be omitted unlike the prior art, so that the production cost can be reduced.

In one embodiment, the first step S10 is a step of foaming the polyurethane composition (which is a mixture of the polyol matrix solution and the polymer MDI solution) to form the foamed resin layer 10, -up method can be used. That is, a polyol matrix solution containing a polyol, a foam stabilizer, a catalyst, a foaming agent, a crosslinking agent and a flame retardant and a polymer MDI (polymeric methyl diphenyl diisocyanate) solution are strongly injected into the nozzle through high pressure air using a two- The ground layer 10 can be formed. At this time, though not particularly limited, the thickness of the foamed resin layer 10 is preferably 80 to 100 mm, more preferably 90 mm.

The second step S20 is a step of forming the protective layer 20 including the nano-clay 30 on one surface of the foamed resin layer 10 and the step of forming the protective layer 20 including the polyol, the foam stabilizer, A polyol matrix solution containing a crosslinking agent and a flame retardant, a polymeric MDI (polymeric methylene diphenyl diisocyanate) solution, and a nanoclay 30 are mixed, and then a known spray device is used to mix the foamed resin layer 10 (Applied) on one side by high-pressure spraying (coating). Specifically, the second step S20 includes mixing the nanoclay 30, the dispersant, and the polymer MDI (methylene diphenyl diisocyanate) solution; And adding a polyol matrix solution containing a polyol, a foam stabilizer, a catalyst, a foaming agent, a crosslinking agent, and a flame retardant to the mixed solution in the mixing step. The dispersant is used for organizing the nanoclay 30 in the polymer MDI solution, and it is preferable to use toluene. More specifically, following the step of mixing the nanoclay 30 with the polymeric MDI solution using a dispersing agent, treating the ultrasonic wave for several hours to induce evaporation of toluene; And nitrogen, and stirring the mixture. The protective layer 20 is preferably formed to a thickness of 20 to 40 mm, more preferably a thickness of 30 mm.

It is to be understood that the present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

100: Insulation for liquefied gas carrier cargo window
10: foamed resin layer
20: Protective layer
30: Nano clay
S100: Method of manufacturing insulating material for cargo window of liquefied gas line
S10: Step 1
S20: Step 2

Claims (20)

A foamed resin layer made of polyurethane foam; And
And a protective layer including a nanoclay on one surface of the foamed resin layer. The optical information recording medium according to claim 1,
Characterized in that it is produced by mixing a polyol matrix solution containing a polyol, a foam stabilizer, a catalyst, a blowing agent, a crosslinking agent and a flame retardant and a polymeric MDI (polymeric methylene diphenyl diisocyanate) solution. The nanoclay according to claim 1,
Characterized in that it is montmorillonite. 3. The nanoclay according to claim 2,
And 1 to 4% by weight based on 100% by weight of the total solution in which the polyol matrix solution and the polymeric MDI solution are mixed. The polyol according to claim 2,
Wherein the aromatic polyester polyol is an aromatic polyester polyol. 3. The composition according to claim 2,
Characterized in that it is a silicone-based foam stabilizer. 3. The process according to claim 2,
Amine and PIR (polyisocyanurate). ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 2,
Characterized in that it comprises water and C ₃ H ₃ F ₅ (pentafluoropropane). The method according to claim 2, wherein the cross-
Wherein the heat insulating material is at least one selected from the group consisting of DEOA (Diethanolamine), TEOA (Triethanolamine) and glycerin. The flame retardant composition according to claim 2,
Wherein the phosphorus-based flame retardant is phosphorus-based flame retardant. A first step of foaming the polyurethane composition to form a foamed resin layer; And
And a second step of forming a protective layer including a nanoclay on one surface of the foamed resin layer. 12. The method of claim 11,
Mixing a nanoclay, a dispersant and a polymeric MDI (methylene diphenyl diisocyanate) solution; And
And adding a polyol matrix solution containing a polyol, a foaming agent, a catalyst, a foaming agent, a crosslinking agent and a flame retardant to the mixed solution, and mixing the mixture. 12. The nano-clay according to claim 11,
Characterized in that the material is a montmorillonite. 13. The nanoclay according to claim 12,
And 1 to 4% by weight based on 100% by weight of the total solution in which the polyol matrix solution and the polymeric MDI solution are mixed. 13. The polyurethane foam according to claim 12,
A method for producing a heat insulating material for a liquefied gas cargo window, characterized by being an aromatic polyester polyol. 13. The composition according to claim 12,
A method for manufacturing a thermal insulation material for a liquefied gas-line cargo window, characterized by being a silicone-based foam stabilizer. 13. The process according to claim 12,
Amine and PIR (polyisocyanurate). ≪ RTI ID = 0.0 > 11. < / RTI > 13. The method according to claim 12,
Water and C ₃ H ₃ F ₅ (pentafluoropropane). 13. The method according to claim 12, wherein the cross-
Wherein the at least one selected from the group consisting of DEOA (Diethanolamine), TEOA (Triethanolamine), and glycerin is at least one selected from the group consisting of DEOA (Diethanolamine), TEOA (Triethanolamine) and glycerin. 13. The method according to claim 12,
Wherein the phosphorus-based flame retardant is phosphorus-based flame retardant.

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