KR102225651B1 - Manufacturing method of vacuum panel having honeycomb core - Google Patents

Abstract

A method of manufacturing a vacuum panel having a honeycomb core according to the present invention includes a first step of applying a filler including a composite fiber including a modified glass fiber and expanded vermiculite powder to a honeycomb core having a hole formed on a side thereof; A second step of manufacturing a honeycomb panel by attaching the honeycomb core and the upper and lower surface plates through an adhesive; A third step of penetrating at least one through hole in the honeycomb panel along an imaginary straight line; And a fourth step of vacuum-processing the honeycomb panel to complete the vacuum panel.
According to the present invention, durability and strength can be improved by manufacturing a vacuum panel with a honeycomb core, and excellent heat insulation performance can be expected.

Description

Manufacturing method of vacuum panel with honeycomb core {MANUFACTURING METHOD OF VACUUM PANEL HAVING HONEYCOMB CORE}

The present invention relates to a method of manufacturing a vacuum panel having a honeycomb core, and if described in more detail, durability and strength can be improved by manufacturing a vacuum panel with a honeycomb core, and excellent insulation performance can be expected. It relates to a method of manufacturing a vacuum panel provided with a honeycomb core.

First of all, a panel is commonly referred to as a panel, and is used as a composite material for structural strength and a building material. Insulation can be included inside the panel, so the construction can be finished with a simple process, and it can be used without requiring a separate finish internally and externally, and it can be reused when dismantling as an assembly-type structure. Recently, various product lines have been formed. It has the advantage of having a wide range of choices depending on the use and use. Such panels can be made of various materials such as thin and flat wood, plywood, metal, and urethane, and are applied and used for interior/exterior walls, floor plates, and roofing materials of buildings. These panels have high thermal insulation performance and thus play a role as a thermal insulation material.

Panels have the above-described advantages, but because they are made of thin steel plates, they are weak at a certain strength and are more susceptible to fire than brick or frame buildings.

At this time, with regard to the technology for manufacturing a vacuum panel, Korean Patent Registration No. 10-1942405 (name of the invention: a method for manufacturing a functional composite material reinforced vacuum insulation panel using a fiber-reinforced composite material) is a cut fiber for strength reinforcement and a foam resin. It relates to a method for manufacturing a functional composite material-reinforced vacuum insulation panel using a fiber-reinforced composite material, characterized in that the fiber-reinforced composite material blended with a structure that surrounds the outside of the vacuum insulation panel makes a functional composite material-reinforced vacuum insulation panel.

The prior art includes a lower strength reinforcement application step of applying a strength reinforcement to the inner bottom surface of the lower mold; A vacuum insulation panel disposing step of disposing the vacuum insulation panel on the inner upper surface of the edge circumferential surface of the strength reinforcing material; A side and upper strength stiffener applying step of applying a strength stiffener to the upper part of the vacuum insulation panel, and applying a strength stiffener to the circumferential surface of the lower strength stiffener so that the strength stiffener surrounds the vacuum insulation panel; Including the step of forming a composite material-reinforced vacuum insulation panel by closing the mold and forming the composite material-reinforced vacuum insulation panel by foaming reaction molding, and then separating the composite material-reinforced vacuum insulation panel from the mold through demoulding. As a fiber-reinforced composite resin, which is a mixture of cut long fibers for reinforcement, and the cut long fibers for reinforcement are selected from glass fiber, carbon fiber, or ceramic fiber, functional composite material reinforcement vacuum insulation using fiber-reinforced composite materials. It presents the panel manufacturing method.

The prior art has the advantage that strength is reinforced by containing a strength reinforcement material using a fiber-reinforced composite material inside the vacuum panel, and heat retention and heat resistance can also be improved. Therefore, there is a disadvantage in that there is a limit to improving the durability.

Therefore, there is a need to develop a vacuum panel having a honeycomb core in order to solve the above-described problems.

The present invention was conceived to overcome the problems of the above technology, and the main purpose is to manufacture a vacuum panel that is equipped with a honeycomb core, which has excellent durability and strength, and that the heat insulation effect can be improved by vacuum processing the inside. The purpose.

Another object of the present invention is to manufacture a vacuum panel that can have an excellent vacuum holding ability by improving the adhesion of the upper and lower surface plates and the honeycomb core by applying an adhesive.

Another object of the present invention is to manufacture a vacuum panel with improved heat insulation and thermal insulation effects by filling the inside of the vacuum panel by applying a filler.

In order to achieve the above object, the method of manufacturing a vacuum panel having a honeycomb core according to the present invention is applied to a honeycomb core having a through hole formed on the side of the honeycomb core with a composite fiber including a modified glass fiber and a filler having expanded vermiculite powder. To do, the first step; A second step of manufacturing a honeycomb panel by attaching the honeycomb core and the upper and lower surface plates through an adhesive; A third step of penetrating at least one through hole in the honeycomb panel along an imaginary straight line; And a fourth step of vacuum-processing the honeycomb panel to complete the vacuum panel.

In addition, the adhesive is prepared by mixing 15 to 25% by weight of 1,6-hexanediol, 10 to 20% by weight of 1,4-butanediol, and 60 to 75% by weight of a solvent based on the total weight of the first solution. To, a first solution preparation step; A second solution preparation step of preparing a second solution by mixing 85 to 90% by weight of the first solution, 5 to 10% by weight of TDI, and 0.1 to 5% by weight of DBTDL based on the total weight of the second solution; It is prepared through the step of completing the adhesive after aging the secondary solution at room temperature for 24 to 72 hours, and the solvent is 20 to 35% by weight of acetone, 20 to 35% by weight of ethyl acetate, methyl It is characterized in that it is a mixture of 35 to 50% by weight of ethyl ketone.

In addition, the filler is, based on the total weight of the primary material, 30 to 45% by weight of expanded vermiculite powder, 30 to 45% by weight of perlite powder, 20 to 40% by weight of the composite fiber, and then 5 to 30 at 80 to 95°C. A step of preparing a primary material by heating for minutes to prepare a primary material; To prepare a secondary material by mixing 75 to 90% by weight of the primary material, 1 to 5% by weight of oxalic acid, 5 to 15% by weight of colloidal silica, and 1 to 10% by weight of HPMC, based on the total weight of the secondary material, 2 Tea material manufacturing steps; It characterized in that it is manufactured through the step of heat-treating the secondary material at 100 to 130 °C to complete the filler.

Further, the composite fiber, a sub-material manufacturing step of preparing a sub-material by mixing 60 to 85% by weight of a silazane precursor and 15 to 40% by weight of a modified glass fiber based on the total weight of the sub-material; A first heat treatment step of performing the first heat treatment for 3 to 8 hours by heating the sub-material to 100 to 130°C at a heating rate of 1°C/min in a vacuum atmosphere; A second heat treatment step of heating the sub-material subjected to the first heat treatment to 180 to 220° C. at a temperature increase rate of 1° C./min and performing secondary heat treatment for 2 to 5 hours; It characterized in that it is manufactured through the step of completing the composite fiber by stretching the secondary heat-treated sub-material.

A method of manufacturing a vacuum panel having a honeycomb core according to the present invention,

1) It has excellent durability and strength and can improve insulation effect,

2) The adhesion of the upper and lower surface plates and the honeycomb core is improved due to the application of the adhesive, so that it can have an excellent vacuum holding ability.

3) Insulation and thermal insulation effects can be improved due to the application of the filler.

1 is a perspective view showing the overall appearance of the vacuum panel of the present invention.
Figure 2 is a flow chart showing the manufacturing method of the vacuum panel of the present invention.
Figure 3 is a flow chart showing a method of manufacturing the adhesive of the present invention.
Figure 4 is a flow chart showing a method of manufacturing a filler of the present invention.
5 is a graph showing the experimental results for the vacuum panel of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The accompanying drawings are not drawn to scale, and the same reference numerals in each drawing refer to the same components.

First of all, a panel is commonly referred to as a panel, and is used as a composite material for structural strength and a building material. Panels can include insulation inside, so the construction can be completed with a simple process, and can be used without separate finishing internally and externally, and can be reused when dismantling as a prefabricated structure. Recently, various product lines have been formed. It has the advantage of having a wide range of choices depending on the use and use. Such panels can be made of various materials such as thin and flat wood, plywood, metal, and urethane, and are applied and used for interior/exterior walls, floor plates, and roofing materials of buildings.

Although such a panel has the above-described advantages, since it is made of a thin steel plate, it is weak at a certain strength and has a disadvantage in that it is more susceptible to fire than a brick or framed building.

At this time, as a security material for the disadvantages of the above-described panel, the honeycomb panel, in detail, among the various types of panels, includes top and bottom surface plates, and a honeycomb core 300 in the shape of a plate in which polygons or circles are densely formed in the form of a honeycomb between them. ), the upper and lower surface plates (100,200) and the honeycomb core (300) are arranged in series, and the presence of the honeycomb core (300) has an empty space in the product configuration, so it is light, but tensile and compressive strength, etc. It is a building material with excellent strength and performance compared to the weight ratio because of its excellent durability.

These panels have high thermal insulation performance and thus play a role as a thermal insulation material. Insulation material is a material used to keep warm or block heat. As a representative insulation material, glass fiber, felt, and foam plastic, which are difficult to conduct heat, are used. Insulation material keeps the warm indoor temperature in winter and prevents internal heat from leaking out as much as possible, and serves to cut off the cold energy of the outside. In addition, in summer, it is possible to keep the interior comfortable and cool by blocking the heat from outside hot solar radiation. At this time, in order to further improve the heat insulation performance of the panel, it is possible to block the transfer of heat due to conduction and convection by manufacturing a vacuum panel by maintaining the inside of the panel in a vacuum state. When the inside of the panel is in a vacuum state, the flow of air molecules can be suppressed and heat loss can be reduced. In addition, when such a vacuum panel is applied to a fire door, it is possible to exhibit a more excellent flame penetration prevention effect in the event of a fire, and thus provide an important function in preventing fire damage.

Accordingly, in the present invention, by manufacturing a vacuum panel having the honeycomb core 300, durability and strength are improved, and a panel having more excellent heat insulation performance can be realized.

1 is a perspective view showing the overall appearance of the vacuum panel of the present invention, Figure 2 is a flow chart showing a manufacturing method of the vacuum panel of the present invention.

A method of manufacturing such a vacuum panel may include a first step (S100), a second step (S200), a third step (S300), and a fourth step (S400).

First, the first step (S100) is a process of applying a filler including a composite fiber including a modified glass fiber and expanded vermiculite powder to the honeycomb core 300 in which the through hole 320 is formed on the side surface. At this time, a filler including composite fibers including modified glass fibers and expanded vermiculite powder was applied to the honeycomb core 300 to improve the durability and heat insulation effect of the vacuum panel, and the honeycomb core 300 was in the form of a honeycomb. It has a plate shape with dense polygons or circles. At this time, as the material of the honeycomb core 300, urethane, aluminum, cement, etc. may be used, and there is no limitation.

Next, the second step (S200) is a process of manufacturing a honeycomb panel by attaching the honeycomb core 300 and the upper and lower surface plates 100 and 200 through an adhesive. At this time, the honeycomb core 300 is disposed in series between the upper and lower surface plates 100 and 200. When the honeycomb core 300 is disposed between the upper and lower surface plates 100 and 200, the honeycomb panel may have excellent durability. In addition, urethane, aluminum, cement, etc. may be used as the material of the upper and lower surface plates 100 and 200, similar to the material of the honeycomb core 300 described above, and there is no limitation. Here, to explain the arrangement order of the honeycomb core 300 and the upper and lower surface plates 100 and 200, the upper and lower surface plates 100 and? Honeycomb Core (300) ?? The lower surface plate 200 is arranged in order. In addition, the adhesive has been applied for adhesion between the upper and lower surface plates 100 and 200 and the honeycomb core 300, and a specific method of manufacturing the adhesive will be described later. In this case, the adhesive may be applied to a portion where the upper and lower surface plates 100 and 200 contact the honeycomb core 300, and the above-described filler may be filled in the honeycomb core 300.

Thereafter, the third step (S300) is a process of penetrating at least one through hole 320 along an imaginary straight line 310 in the honeycomb panel, and proceeds for vacuum treatment, which will be described later. Referring to FIG. 1, the virtual straight line 310 passes in the horizontal direction of the vacuum panel to form a through hole 320 on the side of the honeycomb core 300. However, the virtual straight line 310 may be formed at an angle other than the method shown in FIG. 1 to allow the through hole 320 to be formed in the upper and lower surface plates 100 and 200 and the honeycomb core 300, and FIG. 1 Although one imaginary straight line 310 is shown, a plurality of imaginary straight lines 310 may exist, and the number is not limited. This virtual straight line 310 may be formed through a drilling process.

Finally, the fourth step (S400) is a process of vacuum-processing the honeycomb panel to complete the vacuum panel.

This process may be performed through a vacuum processing device such as a vacuum pump or a vacuum chamber, and air inside the honeycomb panel may be removed by the above-described through hole 320 to be vacuum-treated. After such a vacuum treatment process, a process of sealing the above-described through hole 320 must be performed to maintain a vacuum state inside the vacuum panel.

Through this process, the vacuum panel provided with the honeycomb core 300 can have excellent durability and physical strength due to the honeycomb core 300, and the heat insulation and thermal insulation effects are improved due to the vacuum treatment and the application of the filler inside. Can be.

3 is a flow chart showing a method of manufacturing the adhesive of the present invention.

In this case, the adhesive of the first step (S100) described above may be manufactured through a first solution manufacturing step (S110), a second solution manufacturing step (S120), and an adhesive completion step (S130).

First, the first solution preparation step (S110) is performed by mixing 15 to 25% by weight of 1,6-hexanediol, 10 to 20% by weight of 1,4-butanediol, and 60 to 75% by weight of a solvent based on the total weight of the first solution. This is the process of preparing the first solution. Here, 1,6-hexanediol (1,6-Hexanediol) and 1,4-butanediol (1,4-butandiol) are polyester-based polyols, which are the main materials of the adhesive, and are bonded with isocyanates to be described later to represent adhesive components. In addition, 1,6-hexanediol is a higher alcohol having a hydroxyl group at both ends, and this functional group is very suitable for use in adhesives because of its high chemical reactivity.

In addition, the solvent is characterized in that it is a mixture of 20 to 35% by weight of acetone, 20 to 35% by weight of ethyl acetate, and 35 to 50% by weight of methyl ethyl ketone, based on the total weight of the solvent. At this time, acetone, ethyl acetate, and methyl ethyl ketone were used because they played a role as organic solvents and were less harmful to the human body than other solvents used industrially.

Next, the second solution preparation step (S120) is heated to 70 to 90°C after mixing 85 to 90% by weight of the first solution, 5 to 10% by weight of TDI, and 0.1 to 5% by weight of DBTDL, based on the total weight of the second solution. This is a process of preparing a secondary solution. Here, TDI (Toluene Diisocyanate) has an isocyanate group (NCO-) at the end, so it is mixed and polymerized with polyester polyols in the first solution, so that it has adhesion, and DBTDL (di-n-butyl tin dilaurate) reacts. As a catalyst for conversion, it catalyzes the reaction of polyester-based polyol and TDI to accelerate the rate of completion of an adhesive.

Thereafter, the adhesive completion step (S130) is a process of completing the adhesive after aging the secondary solution at room temperature for 24 to 72 hours.

The adhesive prepared in this way has excellent adhesion by maintaining strong adhesion between the upper and lower surface plates 100 and 200 and the honeycomb core 300, so that the vacuum structure inside the vacuum panel can be maintained for a long time, and the durability of the vacuum panel is also It can be improved, and heat resistance is also excellent, which can help in the heat insulation effect of the vacuum panel.

Figure 4 is a flow chart showing a method of manufacturing a filler of the present invention.

At this time, by applying a filler to the honeycomb core 300 to fill the inside of the honeycomb core 300, the heat resistance and heat retention effect of the vacuum panel may be improved. The filler in the above-described third step (S300) may be manufactured through a first material manufacturing step (S140), a second material manufacturing step (S150), and a filler completion step (S160).

First, the first material manufacturing step (S140) is performed at 80 to 95°C after mixing 30 to 45% by weight of vermiculite powder, 30 to 45% by weight of perlite powder, and 20 to 40% by weight of composite fibers based on the total weight of the first material. It is a process of preparing a primary material by heating for 5 to 30 minutes.

At this time, when the vermiculite powder and the perlite powder are subjected to heat above a certain temperature, they can expand into an ultra-lightweight material that is lighter than water. Here, vermiculite powder is an inorganic mineral produced by plasticizing mica (clay mineral) at high temperature (about 1100°C), and has a buffering effect, has excellent thermal insulation and thermal insulation effects, and perlite powder has excellent thermal insulation properties and is used as a sound absorbing material. It is used, and vermiculite powder and perlite powder are preferably pulverized to a size of 5 to 15 mesh. In addition, the composite fiber manufactured including the glass fiber is a material showing an excellent heat insulating effect, and a specific manufacturing method will be described later.

Thereafter, the second material manufacturing step (S150) comprises 75 to 90% by weight of the primary material, 1 to 5% by weight of oxalic acid, 5 to 15% by weight of colloidal silica, and 1 to 10% by weight of HPMC, based on the total weight of the secondary material. It is a process of preparing a secondary material by mixing.

Here, colloidal silica is a kind of inorganic ceramic, and in this process, it plays a role as an adhesive that allows primary materials to adhere to each other, and HPMC (Hydroxy propyl methyl Cellulose) is a material that controls the viscosity of the filler. It was used to improve the overall viscosity to form a sludge.

At this time, because colloidal silica exhibits anionic properties, the thermal insulation effect may be halved due to collisions with cations. Therefore, in order to prevent this, oxalic acid can be added to induce collision with the carboxyl group (COOH) of oxalic acid and other cations, and then the cations can be precipitated and removed.

Finally, the filling material completion step (S160) is a process of heat-treating the secondary material at 100 to 130°C to complete the filling material, and is a process of stabilizing the filling material through heat treatment.

The filler prepared through this process is made of inorganic ceramic materials such as natural minerals having excellent thermal stability, and is filled inside the honeycomb core 300 to improve heat insulation and heat retention of the vacuum panel.

In this case, the manufacturing method of the composite fiber may be manufactured through a sub-material manufacturing step, a first heat treatment step, a second heat treatment step, and a composite fiber completion step.

First, the sub-material manufacturing step is a process of preparing a sub-material by mixing 60 to 85% by weight of a silazane precursor and 15 to 40% by weight of a modified glass fiber based on the total weight of the sub-material, and mixing the silazane precursor and the modified glass fiber It is a process of bonding.

Next, the first heat treatment step is a process of heating the sub-material to 100 to 130°C at a heating rate of 1°C/min in a vacuum atmosphere for 3 to 8 hours, and crosslinking the silazane precursor and the modified glass fiber. It is the process of proceeding the process.

Thereafter, the second heat treatment step is a process of heating the first heat-treated sub-material to 180 to 220°C at a heating rate of 1°C/min and performing the second heat treatment for 2 to 5 hours. This is the process of carrying out the crosslinking process.

Finally, the composite fiber completion step is a process of stretching the secondary heat-treated sub-material to complete the composite fiber, and the tensile process can be performed through a roller, and through this process, the composite fiber with increased elasticity and strength is completed. .

At this time, the above-described method of manufacturing the modified glass fibers may be manufactured through a first mixed solution preparation step, a second mixed solution preparation step, a filtration step, and a modified glass fiber completion step.

First, the first mixed solution preparation step is a first mixing by mixing 80 to 90% by weight of ethanol, 5 to 15% by weight of water, and 1 to 10% by weight of 3-aminopropitriethoxysilane based on the total weight of the first mixed solution. It is the process of preparing a solution. Here, ethanol and water serve as solvents, and 3-aminopropytriethoxysilane was added as a silane coupling agent to modify the surface of the glass fiber, which will be described later.

Next, the second mixed solution preparation step is a process of preparing a second mixed solution by mixing 60 to 85% by weight of the first mixed solution and 15 to 40% by weight of the glass fiber, based on the total weight of the second mixed solution. This is a process of impregnating the first mixed solution for 20 to 60 minutes. Here, the glass fiber is a long fiber state by melting glass in a platinum furnace and dropping it into a small hole. It has good heat resistance, durability, sound absorption, and electrical insulation, and is used as a heat insulator, air filter material, electrical insulation, and sound-absorbing material. It is the material that becomes. At this time, the types of glass fibers include E-glass, S-glass, C-glass, D-glass, etc. In the present invention, E-glass will be used. E-glass is the most commonly used fiberglass, where E means electrical. E-glass has the advantage of excellent insulation due to its low electrical conductivity and low content of alkali, which is also called alkali-free glass fiber, and is inexpensive and easy to obtain commercially.

In this process, the glass fibers are surfaced by 3-aminopropytriethoxysilane in the first mixed solution, so that the bonding property with the silazane precursor to be described later may be improved.

Thereafter, the filtration step is a process of filtering the second mixed solution and then washing the residual intermediate fiber 1 to 3 times with ethanol, and in the completion of the modified glass fiber, the intermediate fiber is heated at 100 to 120° C. for 1 to 5 hours. This is a process of drying at room temperature for 12 to 36 hours to complete the modified glass fiber. Modified glass fibers prepared through this process may improve bonding properties with silazane precursors to be described later by surface-treating the glass fibers through 3-aminopropytriethoxysilane.

In addition, the silazane precursor of the above-described impregnation solution may be prepared through a first mixed solution preparation step, a second mixed solution preparation step, and a silazane precursor completion step.

First, the first mixed solution preparation step is a process of preparing a first mixed solution by mixing 50 to 80% by weight of OPSZ and 20 to 50% by weight of CTS based on the total weight of the first mixed solution, and stirring for 1 to 10 minutes. It is desirable to do it.

Here, OPSZ (Organopolysilazane) is a basic precursor to form a network of silazane precursors, and CTS (2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane) is also a basic precursor and serves to increase the molecular weight of the silazane precursor. Perform.

Next, the second mixed solution preparation step is a secondary mixing by mixing 95 to 99% by weight of the first mixed solution, 0.5 to 4% by weight of DCP, 0.1 to 1% by weight of a hydrosilylation catalyst, based on the total weight of the second mixed solution. As a process of preparing a solution, it is preferable to proceed by stirring for 5 to 20 v.

Here, DCP (dicumyl peroxide) plays a role as a reaction catalyst that accelerates the progress of the reaction, and a platinumdivinyltetramethydisiloxane complex solution may be used as the hydrosilylation catalyst, and plays a role in inducing a hydrosilylation reaction. Here, the hydrosilylation reaction is a crosslinking reaction in which a Si-CH2-CH2-Si structure is formed by a Si-H bond and a bonding group Pt catalyst of a vinyl group. Due to this crosslinking reaction, chains are linked to form a network.

Finally, in the completion of the silazane precursor, the second mixed solution is first heated at 40 to 60° C. for 20 to 60 minutes, and then secondary heated at 100 to 150° C. for 10 to 15 hours to complete the silazane precursor. It's a process. Here, the first heating process was performed to remove air bubbles from the second mixed solution, and the second heating process was performed for the crosslinking process of the second mixed solution. Here, organic components are removed through a crosslinking process through a secondary heating process, and may be converted into ceramic.

The silazane precursor prepared through this process may be crosslinked with the above-described modified glass fiber to produce a composite fiber. These composite fibers have improved physical durability and strength, and have excellent thermal stability, so that they can perform thermal insulation and heat resistance functions.

As another embodiment, by adding a flame-retardant auxiliary material to the above-described filler and manufacturing a flame-retardant filler, the heat stability of the vacuum panel may be improved.

At this time, the flame-retardant filler is characterized in that it is a mixture of 70 to 90% by weight of the filler and 10 to 30% by weight of the flame-retardant auxiliary material, based on the total weight of the flame-retardant filler, and the mixed flame-retardant filler is honey according to the first step (S100). It is applied to the comb core 300.

The method of manufacturing the flame retardant auxiliary material may be prepared through a first solution preparation step, a first product obtaining step, a second product obtaining step, a second solution preparation step, a third solution preparation step, and a flame retardant auxiliary material completion step.

First, in the first solution preparation step, 5 to 25% by weight of butanediol, 35 to 55% by weight of adipic acid, 15 to 35% by weight of trimethylolpropane, and 1 to 20% by weight of dimethylphenyl phosphate are mixed with respect to the total weight of the first solution. As a process of preparing the first solution, it is preferable to stir at a speed of 200 to 300 rpm, and butanediol, adipic acid, trimethylolpropane, and dimethylphenylphosphate are It is synthesized in this process and becomes a reactant for polyester synthesis, which is a primary product to be described later.

Next, in the step of obtaining the first product, the first solution is heated to 220° C. at a rate of 10° C./hr to obtain a first product. In this reaction, the temperature conditions are preferably raised from 70°C to 220°C, and then the reaction is terminated, and the butanediol, adipic acid, trimethylolpropane, which were mixed in the dehydration reaction and the first solution preparation step through the heating process, The dimethylphenyl phosphate reacts and the synthesis reaction to polyester proceeds.

Thereafter, the step of obtaining the second product is a process in which the first product is precipitated in either water or normal hexane and then dried under reduced pressure to obtain a second product. The polyester produced in the step of obtaining the first product is It becomes a residue, ie a secondary product.

Here, the reason for precipitating the first product in water and normal hexane is to remove unreacted substances that do not participate in the reaction of the first product.

Next, the second solution preparation step is based on the total weight of the second solution, the second product 30 to 50% by weight, butyl acetate 15 to 30% by weight, ethyl acetate 15 to 30% by weight, toluene 5 to 15% by weight, dispersant As a process of preparing a second solution by mixing 0.1 to 5% by weight, the second product is diluted in a solvent.

Here, butyl acetate, ethyl acetate, and toluene are mixed and used as a solvent for the secondary product to react in the step of completing the flame retardant auxiliary material to be described later.

Thereafter, the third solution preparation step is a process of preparing a third solution by mixing 40 to 60% by weight of polyisocyanate, 20 to 40% by weight of cellosolve acetate, and 20 to 40% by weight of xylene based on the total weight of the third solution. , This is the process of making a solution that hardens the flame retardant auxiliary material.

Here, polyisocyanates are materials with excellent adhesion and play a role as hardeners, and Cellosolve Acetate and xylene are materials that are generally used as solvents for paints and play a role as a solvent in this step. Carry out.

Finally, the step of completing the flame-retardant auxiliary is a process of completing the flame-retardant auxiliary by mixing 50 to 70% by weight of the second solution and 30 to 50% by weight of the third solution, based on the total weight of the flame-retardant auxiliary. The flame-retardant auxiliary material has excellent non-flammable and flame-retardant properties, and it is mixed with the filler to become a flame-retardant filler, so that it can be applied to a vacuum panel and exhibit excellent thermal stability.

As another embodiment, it is possible to improve thermal insulation and heat resistance by additionally including an insulating auxiliary material to the above-described filler, and to manufacture an insulating filler capable of effectively blocking the flow of heat from inside/outside.

At this time, the insulating filler is characterized in that it is a mixture of 70 to 90% by weight of the filler and 10 to 30% by weight of the insulating auxiliary, based on the total weight of the insulating filler, and the heat insulating filler mixed in this way is honey according to the first step (S100) described above. It is applied to the comb core 300.

These insulating auxiliary materials may be manufactured through an initial material manufacturing step and an insulating auxiliary material completion step.

First, the initial material preparation step is a mixture of 60 to 85% by weight of modified silica, 5 to 30% by weight of silicon carbide, and 1 to 15% by weight of ceramic fibers relative to the total weight of the initial material at a speed of 150 to 1000 rpm for 10 to 30 minutes. This is the process of manufacturing the initial material.

At this time, the modified silica is a material obtained by modifying the surface of the silica and preferably has a size of 0.2 to 0.3 µm, and is a material that is a main raw material of the heat insulating auxiliary material, and a specific method of manufacturing it will be described later. In addition, silicon carbide is a shielding material capable of shielding radiation at high temperatures, and it is preferable to use one having a size of 3 to 30 μm. Here, as the size of the silicon carbide decreases, the thermal conductivity decreases, thereby increasing the thermal insulation performance. In addition, alumino-silicate ceramic fiber and glass fiber may be used as the ceramic fiber that can serve as a structural reinforcing material and heat-insulating and heat-resistant material, and it is preferable to use one having a size of 50 mesh or less.

Through the above-described steps, the modified silica nanoparticles are coated on the ceramic fiber, and the modified silica particle coating of the ceramic fiber is performed to prevent the phenomenon of solid thermal conductivity.

Next, the step of completing the insulating auxiliary material is a process of forming the initial material at a pressure of 1 to 3 MPa to complete the insulating auxiliary material having a density of 0.2 to 0.4.

The insulating auxiliary material manufactured through this process exhibits excellent insulating performance due to its low thermal conductivity, and thus, it is mixed with the filler to become an insulating filler, thereby improving the insulating performance of the vacuum panel.

At this time, the modified silica of the initial material may be prepared through a solvent solution preparation step, a hydrolysis solution preparation step, a modified solution preparation step, a modified silica acquisition step, and a drying step.

First, the solvent solution preparation step is a process of preparing a solvent solution by mixing 60 to 85% by weight of ethanol and 15 to 40% by weight of ultrapure water based on the weight of the total solvent solution and then mixing for 5 to 30 minutes at a speed of 100 to 500 rpm. . In this case, D.I Water means water from which all dissolved ions have been removed. Here, ethanol and ultrapure water function as solvents in the modified silica process.

Next, the step of preparing the hydrolysis solution is to prepare a hydrolysis solution by mixing 95 to 99% by weight of the solvent solution and 1 to 5% by weight of BTMA based on the weight of the total hydrolysis solution and mixing at a rate of 100 to 500 rpm for 5 to 30 minutes. As a process, the surface of silica, which will be described later, can be modified by adding BTMA (bis[3-(trimethoxysilyl)propyl]amin), which is a silane coupling agent.

Thereafter, in the step of preparing the modified solution, 90 to 99% by weight of the hydrolysis solution and 1 to 10% by weight of silica are mixed and then mixed at a rate of 100 to 500 rpm for 10 to 60 minutes to prepare a modified solution based on the total weight of the modified solution. It's a process. Here, the size of silica is preferably about 12 nm, and is a material having excellent heat resistance, thermal shock resistance, and chemical resistance. In this process, BTMA, which is a component of the hydrolysis solution, and silica are mixed, thereby modifying the surface quality of the silica.

Next, the step of obtaining the modified silica is a process of centrifuging the modified solution at a speed of 2000 to 4000 rpm for 10 to 60 minutes, and then obtaining a modified silica as a precipitate.

Here, the precipitate refers to a material from which the supernatant is removed after centrifugation.

Finally, in the drying step, the obtained modified silica is washed 1 to 5 times with water and 1 to 5 times with ethanol, and then dried at 40 to 70° C. for 10 to 60 minutes.

The reactivity of the modified silica through this process is improved, so that the reactivity with the silicon carbide and the ceramic fiber is improved in the manufacturing process of the above-described insulation auxiliary material, and thus the insulation performance can be further improved.

5 is a graph showing experimental results for the vacuum panel of the present invention.

Hereinafter, in order to specifically describe the present invention, it will be described by comparing examples and control examples. For Examples and Control Examples to be described later, after preparing 10 Examples and Control Examples, respectively, the vacuum holding ability (panel adhesion ability) and the thermal insulation effect were measured, and the measured values were very good (5) and good (4), respectively. ), normal (3), bad (2), and very bad (1) were converted into five stages and the average score was determined.

At this time, the vacuum holding ability is the vacuum holding ability inside the panel (panel adhesion ability) after the same time passes between the vacuum panel to which the adhesive of the present invention is applied and the commercial vacuum panel under the same conditions (temperature, time of manufacture, place, etc.) The evaluation was indicated by giving a score for the vacuum holding ability (that is, how long the initial vacuum inside the panel was maintained, or how well the panel was adhered) accordingly. The higher the vacuum holding ability (panel adhesion ability) of the vacuum panel coated with the adhesive agent of the present invention and the commercially available vacuum panel is measured, the closer to very good (5), and the lower the vacuum holding ability is, the very poor (1). I tried to evaluate it closely.

In addition, the thermal insulation effect is measured by measuring the thermal insulation effect through the panel under the same conditions (temperature, time of manufacture, place, etc.) on the vacuum panel coated with the filler of the present invention and the commercial vacuum panel, and accordingly, the thermal insulation effect (ie, how much The evaluation was indicated by giving a score on whether to preserve internal and external heat well). The higher the thermal insulation effect of the vacuum panel coated with the filler of the present invention and the commercially available vacuum panel was measured, the closer to very good (5), and the lower the thermal insulation effect was, the very poor (1).

<Example 1>

First, 1,6-hexanediol 20g, 1,4-butanediol 15g, and solvent 60g were mixed to prepare a first solution, and then 85g of the first solution, 5g of TDI, and 1g of DBTDL were mixed and aged for 36 hours. Completed.

Next, 35 g of vermiculite powder, 35 g of perlite powder, and 25 g of composite fibers were mixed and heated at 90° C. for 20 minutes to prepare a primary material, and 80 g of the primary material, 3 g of oxalic acid, 10 g of colloidal silica, and 5 g of HPMC were mixed. After the tea material was prepared, it was heat-treated at 120°C to complete the filler.

Finally, an adhesive and a filler were applied to the honeycomb core 300 and then attached to the upper and lower surface plates to prepare a honeycomb panel, followed by vacuum treatment to manufacture a vacuum panel.

<Example 2>

A vacuum panel was manufactured in the same manner as in Example 1, except that a commercially available adhesive was applied to the vacuum panel instead of the adhesive of the present invention.

<Example 3>

A vacuum panel was manufactured in the same manner as in Example 1, except that no filler was applied to the vacuum panel.

<Control example>

Commercial vacuum panels.

<Figure 1: Table of experimental results for the manufacturing method of the sub-agent of the present invention>

As shown in Figure 1, the evaluation team measured the vacuum holding ability (panel adhesion ability) and thermal insulation effect of the vacuum panels manufactured as Examples and Control Examples, and the results were expressed as an average score and presented in a table. Examples 1 to 3 obtained high evaluation scores compared to the control example. Accordingly, it can be seen that the vacuum panels (Examples 1 to 3) of the present invention have superior vacuum holding ability (panel adhesion ability) and thermal insulation effect than that of a commercially available vacuum panel as a control example.

Through this, it is possible to check the vacuum holding ability (panel adhesion ability) through the adhesive and the thermal insulation effect through the filler, so that the importance of the adhesive and filler manufacturing process can be grasped.

As described so far, the method of manufacturing a vacuum panel having a honeycomb core according to the present invention has been described in the above description and drawings, but these are only described as examples, and the spirit of the present invention is not limited to the above description and drawings. Of course, various changes and changes are possible within the scope of the technical idea of the present invention.

100: upper surface plate 200: lower surface plate
300: honeycomb core 310: virtual straight line
320: through hole S100: first step
S200: second step S300: third step
S400: the fourth step S110: the first solution preparation step
S120: Second solution manufacturing step S130: Adhesive completion step
S140: primary material manufacturing step S150: secondary material manufacturing step
S160: Filling material completion stage

Claims (11)

As a method of manufacturing a vacuum panel with a honeycomb core,
A first step of applying a filler including composite fibers including modified glass fibers and expanded vermiculite powder to a honeycomb core having a through hole formed on a side thereof;
A second step of manufacturing a honeycomb panel by attaching the honeycomb core and the upper and lower surface plates through an adhesive;
A third step of penetrating at least one through hole in the honeycomb panel along an imaginary straight line;
Including; a fourth step of vacuum-processing the honeycomb panel to complete a vacuum panel,
The filler,
Based on the total weight of the primary material, 30 to 45% by weight of expanded vermiculite powder, 30 to 45% by weight of perlite powder, and 20 to 40% by weight of the composite fiber are mixed and heated at 80 to 95°C for 5 to 30 minutes to obtain a primary material. To prepare, the first material manufacturing step;
To prepare a secondary material by mixing 75 to 90% by weight of the primary material, 1 to 5% by weight of oxalic acid, 5 to 15% by weight of colloidal silica, and 1 to 10% by weight of HPMC, based on the total weight of the secondary material, 2 Tea material manufacturing steps;
Heat-treating the secondary material at 100 to 130° C. to complete a filler material; characterized in that it is manufactured through a method of manufacturing a vacuum panel. The method of claim 1,
The adhesive,
Preparing a first solution by mixing 15 to 25% by weight of 1,6-hexanediol, 10 to 20% by weight of 1,4-butanediol, and 60 to 75% by weight of a solvent based on the total weight of the first solution step;
A second solution preparation step of preparing a second solution by mixing 85 to 90% by weight of the first solution, 5 to 10% by weight of TDI, and 0.1 to 5% by weight of DBTDL based on the total weight of the second solution;
It is prepared through the step of completing the adhesive after aging the secondary solution at room temperature for 24 to 72 hours,
The solvent is a mixture of 20 to 35% by weight of acetone, 20 to 35% by weight of ethyl acetate, and 35 to 50% by weight of methyl ethyl ketone, based on the total weight of the solvent. delete The method of claim 1,
The composite fiber,
A sub-material manufacturing step of preparing a sub-material by mixing 60 to 85% by weight of a silazane precursor and 15 to 40% by weight of a modified glass fiber based on the total weight of the sub-material;
A first heat treatment step of performing the first heat treatment for 3 to 8 hours by heating the sub-material to 100 to 130°C at a heating rate of 1°C/min in a vacuum atmosphere;
A second heat treatment step of heating the sub-material subjected to the first heat treatment to 180 to 220° C. at a temperature increase rate of 1° C./min and performing secondary heat treatment for 2 to 5 hours;
A method of manufacturing a vacuum panel, characterized in that it is manufactured through the step of stretching the secondary heat-treated sub-material to complete the composite fiber. The method of claim 4,
The modified glass fiber,
A first mixed solution for preparing a first mixed solution by mixing 80 to 90% by weight of ethanol, 5 to 15% by weight of water, and 1 to 10% by weight of 3-aminopropytriethoxysilane based on the total weight of the first mixed solution Manufacturing steps;
A second mixed solution preparation step of preparing a second mixed solution by mixing 60 to 85% by weight of the first mixed solution and 15 to 40% by weight of glass fibers based on the total weight of the second mixed solution;
Filtering the second mixed solution and washing the residual intermediate fiber 1 to 3 times with ethanol;
The intermediate fiber is heated at 100 to 120° C. for 1 to 5 hours and then dried at room temperature for 12 to 36 hours to complete the modified glass fiber. The method of claim 5,
The silazane precursor,
A first mixed solution preparation step of preparing a first mixed solution by mixing 50 to 80% by weight of OPSZ and 20 to 50% by weight of CTS based on the total weight of the first mixed solution;
Secondary mixing to prepare a second mixed solution by mixing 95 to 99% by weight of the first mixed solution, 0.5 to 4% by weight of DCP, and 0.1 to 1% by weight of a hydrosilylation catalyst based on the total weight of the second mixed solution Solution preparation step;
The second mixed solution is first heated at 40 to 60° C. for 20 to 60 minutes, followed by secondary heating at 100 to 150° C. for 10 to 15 hours to complete a silazane precursor, completing a silazane precursor; A method for manufacturing a vacuum panel, characterized in that it is manufactured through. The method of claim 1,
The filler,
It is a flame retardant filler that additionally includes a flame retardant auxiliary material,
The flame-retardant filler including the flame-retardant auxiliary material,
A method for manufacturing a vacuum panel, characterized in that it is a mixture of 70 to 90% by weight of the filler and 10 to 30% by weight of the flame-retardant auxiliary material based on the total weight of the flame-retardant filler. The method of claim 7,
The flame retardant auxiliary material,
To prepare a first solution by mixing 5 to 25% by weight of butanediol, 35 to 55% by weight of adipic acid, 15 to 35% by weight of trimethylolpropane, and 1 to 20% by weight of dimethylphenyl phosphate, based on the total weight of the first solution, Preparing a first solution;
Obtaining a first product by heating the first solution to 220° C. at a rate of 10° C./hr to obtain a first product;
Precipitating the first product in any one of water and normal hexane and then drying under reduced pressure to obtain a second product, obtaining a second product;
By mixing 30 to 50% by weight of the second product, 15 to 30% by weight of butyl acetate, 15 to 30% by weight of ethyl acetate, 5 to 15% by weight of toluene, and 0.1 to 5% by weight of a dispersant based on the total weight of the second solution. Preparing a second solution, preparing a second solution;
A third solution preparation step of preparing a third solution by mixing 40 to 60% by weight of polyisocyanate, 20 to 40% by weight of cellosolve acetate, and 20 to 40% by weight of xylene based on the total weight of the third solution;
A method of manufacturing a vacuum panel, characterized in that it is manufactured through a step of completing a flame retardant auxiliary material by mixing 50 to 70 wt% of the second solution and 30 to 50 wt% of the third solution based on the total weight of the flame retardant auxiliary agent. The method of claim 1,
The filler,
It is a thermal insulation filler that additionally includes an insulation auxiliary material including modified silica,
The insulating filler including the insulating auxiliary material,
A method of manufacturing a vacuum panel, characterized in that it is a mixture of 70 to 90% by weight of the filler and 10 to 30% by weight of the insulating auxiliary material based on the total weight of the insulating filler. The method of claim 9,
The insulation auxiliary material,
To prepare an initial material by mixing 60 to 85% by weight of modified silica, 5 to 30% by weight of silicon carbide, and 1 to 15% by weight of ceramic fibers relative to the total weight of the initial material for 10 to 30 minutes at a speed of 150 to 1000 rpm, Initial material preparation steps;
Forming the initial material at a pressure of 1 to 3 MPa to complete a heat insulation auxiliary material having a density of 0.2 to 0.4; characterized in that the vacuum panel manufacturing method. delete

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