WO2012047012A2

WO2012047012A2 - Expanded perlite thermal insulation material using a thermosetting resin, a production method for the same and a product using the same

Info

Publication number: WO2012047012A2
Application number: PCT/KR2011/007364
Authority: WO
Inventors: 백범규; 이상윤; 강태윤
Original assignee: 주식회사 경동세라텍
Priority date: 2010-10-06
Filing date: 2011-10-05
Publication date: 2012-04-12
Also published as: KR101242812B1; KR20120035628A; WO2012047012A3

Abstract

The present invention relates to an expanded perlite thermal insulation material using a thermosetting resin, wherein the thermal insulation material is formed by using a thermosetting resin to adhere expanded perlite and then a heat treatment is carried out, thereby reducing the thickness of the thermal insulation material because of outstanding thermal conductivity not to mention improved workability due to low density, such that it is possible to economise on material and energy costs and to reduce the equipment installation area. The present invention also relates to a production method for the thermal insulation material and to a product using the thermal insulation material.

Description

Expanded perlite insulation using thermosetting resin, manufacturing method thereof and product using same

The present invention relates to an insulated perlite heat insulating material using a thermosetting resin, which is formed by bonding an expanded perlite using a thermosetting resin, forming a heat treatment, and improving the workability due to low density as well as reducing the thickness of the insulating material with excellent thermal conductivity to reduce the material and energy costs. The present invention relates to a heat insulating material, a method for manufacturing the same, and a product using the same, which can reduce and reduce an installation space area.

In the plant industry, such as petrochemicals, power plants, and steel mills, the production process and lines have a complicated structure. In particular, many lines which store or convey a fluid of high temperature or low temperature are used.

Industrial insulation plays a very important role in the high and low temperature plant industry as well as preventing energy loss and having a close relationship with product quality.

In particular, countries that rely mostly on imports for energy are sensitive to the industry as a result of energy savings due to high oil prices and the regulation of carbon emissions under climate change agreements. As a result of this trend, research and efforts to improve the performance and development of materials for various fields of insulation materials used in industrial plants have been continued.

Mainly used for industrial thermal insulation includes inorganic fiber-based, powder-based, foam-based insulation. Fibrous insulation is produced using glass fibers made of glass mineral materials such as silica sand, limestone, feldspar, and soda ash, and mineral fibers such as rock wool, alumina fibers, zirconia fibers and carbon fibers made of blast furnace slag and basalt materials. .

In Korean Patent Publication No. 10-0522568, “Water-repellent insulating pipe using glass fiber and its manufacturing method”, Korean Patent Publication No. 10-0760003 “Round-type glass fiber insulating material for insulating device and its manufacturing method”, etc. As is known, it is prepared by mating using glass long fibers in the inorganic fiber group, needle-punching this mat again in several layers, and impregnating and adhering a binder.

Products manufactured in this way have the advantage of ease of transport and low thermal conductivity compared to the conventional inorganic fiber-based heat insulator due to the characteristics of the fiber type, but has a disadvantage in that the thermal characteristics are not uniform due to the large density variation of the product.

Particularly, it is very vulnerable to moisture, so even if the surface is water repellent, moisture penetrates easily into the cutting surface and the like, so that multiple layers of mats are opened, resulting in rapid thermal conductivity and poor durability of the product.

In addition, the dust of the glass fiber generated during the construction is harmful to the human body to avoid this phenomenon in the workplace.

Powder-based insulation uses calcium silicate, diatomaceous earth, basic magnesium carbonate and the like.

In particular, the calcium silicate heat insulating material that is frequently used is a product obtained by hydrothermally reacting diatomaceous earth and slaked lime with excess water, wet molding in a slurry state, and hardening by heating under high pressure in an autoclave.

It has the advantage of excellent strength in the shape of Tobermorite and Xonotlite depending on the crystal structure at the time of curing, and low thermal conductivity depending on the crystal shape, but the productivity is low due to the complicated manufacturing process due to the curing. In particular, in the case of Tobermorite, there is a problem that can not form a water repellent performance.

Foam-based insulation is an insulator using expanded vermiculite or expanded perlite, the expanded perlite insulation is mainly used for industrial purposes.

Expanded perlite insulation has been used throughout industrial insulation due to its simple manufacturing process, high productivity and low material costs.

However, silicate-based binder, which is an inorganic binder used for expanded perlite insulation, has a disadvantage of high thermal conductivity and low adhesive strength in an amorphous form.As a liquid form, the amount of binder is increased because the binder is absorbed into the cell when mixed with expanded perlite. As a result, the thermal conductivity becomes higher.

In addition, the use of a liquid silicate-based binder causes the expanded perlite surface to contain an excessive amount of water by the binder, and as a result of reduced particle flow due to moisture, it is not easy to fill voids between the particles. In this state, density variation occurs in each part, and excessive fracture and porosity of the cell are increased in the molding process of the insulating material through compression, resulting in an increase in thermal conductivity and cracking.

In addition, since the liquid binder does not have its own volume, the gap between the particles and the particles cannot be filled, and even if the binder is increased, the voids still exist, so that the compression ratio can be increased to minimize the voids. This results in more crushing of the particles and a higher density of the shaped body and an additional increase in thermal conductivity.

In addition, the liquid silicate-based binder shrinks at a high temperature of 500 ° C. or higher, and there is a risk of deformation and cracking of the molded body.

In addition, since the liquid binder is made of 70% or more of water, even if the drying process is sufficiently performed, it is difficult to completely dry the thermal conductivity is further increased by the remaining moisture.

In order to solve the problems caused by the use of expanded perlite and liquid silicate-based binders, researches have been developed in various angles, but there is a limit in overcoming the thermal conductivity degradation due to compression molding due to the manufacturing process. Although a method of baking or curing the binder has been proposed, there are problems in that the manufacturing process becomes complicated and the manufacturing cost increases.

In addition, there are solutions to problems through the use of expanded perlite and other materials.

As known from many materials, such as Korean Patent Publication No. 10-0695910, "High Strength Vermiculite Board", the expansion of vermiculite, which is a foam-based insulation material, is made of reinforcement mixed with expanded perlite, etc. Techniques were proposed.

However, organic curable binders cannot be used at high temperatures, and due to the use of expanded vermiculite having high density and poor thermal conductivity, the overall thermal conductivity is increased, the density of the insulation is increased, and the strength is decreased if sufficient compression is not accompanied. There is this.

Accordingly, the present invention is to solve the above problems in molding the expanded perlite insulation, the present invention is bonded by using a powdery thermosetting binder, by performing a high temperature heat treatment process additionally by carbonizing the expanded perlite molded body, Since the gap between the gap can be filled with a powdery binder, sufficient bonding strength between particles can be ensured even without overcompression, thereby improving the thermal conductivity by preventing density increase and particle crushing due to compression, and performing the heat treatment process. Accordingly, an object of the present invention is to provide an expanded perlite heat insulating material using a thermosetting resin that can block thermal decomposition, which is a problem of organic matter, and ensure thermal stability at high temperature.

In addition, the present invention has a very high adhesive strength compared to the liquid silicate-based binder by using a powdery thermosetting resin, and because there is no absorption by the expanded perlite, it is possible to secure a high adhesive strength even at a low compression ratio to a lower density It is an object of the present invention to provide an expanded perlite heat insulating material using a thermosetting resin that can be formed to improve workability and further improve thermal conductivity.

In addition, the present invention solves particle flowability, which is a problem of liquid silicate-based binders, to reduce porosity and density variation, thereby minimizing breakage of cells during compression, and is due to an extremely low moisture content of powdered resin. The purpose is to provide an expanded perlite insulation using a thermosetting resin that can solve the increase in thermal conductivity due to residual moisture.

The expanded perlite insulation using the thermosetting resin according to the present invention comprises 10 to 84% by weight of expanded perlite, 15 to 85% by weight of an organic curable powder binder, and 0.25 to 5% by weight of reinforcing fiber prepared by drying the ore after expansion. It features.

According to another preferred feature of the present invention, the expanded perlite heat insulating material using the thermosetting resin further includes 5 to 200 parts by weight of a reinforcing agent based on 100 parts by weight of the organic curable powder binder.

Method for producing an expanded perlite heat insulating material using a thermosetting resin according to the present invention comprises the first step of producing expanded perlite by drying and expanding the ore; A second step of preparing a mixture by mixing 10 to 84% by weight of the expanded perlite prepared in the first step, 15 to 85% by weight of the organic curable powder binder, and 0.25 to 5% by weight of the reinforcing fiber; A third step of compressing or extruding the mixture prepared in the second step to form a molded article and first curing the molded article; And a fourth step of post-curing the primary cured molded body in the third step.

The product using the expanded perlite heat insulating material using the thermosetting resin according to the present invention is the expanded perlite heat insulating material using the above-mentioned thermosetting resin, the expanded perlite heat insulating material using the thermosetting resin is characterized in that it is used as a core material of a heat insulating material or a vacuum insulating material.

By means of the above solution, the heat insulating material of the present invention by filling the maximally close by using the expanded perlite to minimize the gap between the particles to improve the workability due to the low density and to reduce the thickness of the heat insulating material to reduce the material and energy costs and the installation space area As a heat insulator to reduce the temperature, it can be used in high temperature and low temperature conditions and can be applied in various forms.

1 shows an open cell expansion perlite,

(A): more than 800㎛ (30 magnification) (B): 800 ~ 500㎛ (32 magnification)

(C): 500 ~ 400㎛ (32 magnifications) (D): 400 ~ 250㎛ (48 magnifications)

(E): 250 ~ 160㎛ (84 magnification) (F): 160 ~ 63㎛ (100 magnification)

(G): 63㎛ (100 magnification)

2 shows a closed cell expansion perlite.

(A): 400 µm or more (32 magnifications) (B): 400 to 250 µm (48 magnifications)

(C): 250 ~ 160㎛ (84 magnification) (D): 160 ~ 63㎛ (100 magnification)

(E): 63㎛ (100 magnification)

Hereinafter, described in detail with reference to the accompanying drawings, preferred embodiments of the present invention.

Expanded perlite heat insulating material using a thermosetting resin according to the present invention for achieving the above object comprises 10 to 84% by weight of expanded perlite, 15 to 85% by weight of the organic curable powder binder and 0.25 to 5% by weight of reinforcing fibers.

The expanded perlite is prepared by drying the perlite ore and then expanding it. The perlite ore is at least one selected from perlite, obsidian, pine rock, and pumice. If the expanded perlite is less than 10% by weight, there is a problem that the thermal conductivity is sharply increased, and if it exceeds 84% by weight, there is a problem that the mechanical properties are reduced. There is no particular limitation on the shape of the particles of the expanded perlite, but preferably the active ingredient of the closed cell expanded perlite includes 50% by weight or more based on the total weight of the expanded perlite.

The organic curable powder binder may be mixed in an amount of 15 to 85% by weight, preferably 20 to 50% by weight based on the total weight%, and when it is 15% by weight or less, it is difficult to secure the adhesive strength. Although it can be secured, problems such as an increase in material cost and thermal conductivity due to the mixing of excess organic materials occur.

The organic curable powder binder may use a phenol novolak resin, but is not particularly limited, and may be a melamine resin, an epoxy resin, or a silicone resin, which is transformed into a powder, and is formed of a polymer through thermal curing to secure mechanical properties. It may include all resins that can be.

The reinforcing fiber uses a reinforcing fiber having a length of 5 to 30 mm to reinforce the formability, bending strength, and workability of the expanded perlite insulation. Reinforcing fibers are used in combination with inorganic fibers or organic fibers, respectively.

In addition, a reinforcing agent may be used to further lower the strength or thermal conductivity.

In order to reinforce the strength, fumed silica and airgel of less than 50 μm may be used, which is formed of nanometer-sized ultra fine cells having excellent thermal conductivity, thereby filling gaps when mixed with expanded perlite. Even if the molding compression ratio is reduced, a compact molding state can be obtained, thereby improving the strength and securing a low thermal conductivity .

On the other hand, the expanded perlite insulation using the thermosetting resin according to the present invention may further comprise a reinforcing agent. The reinforcing agent may be mixed in an amount of 5 to 200 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the organic curable powder binder, and when the reinforcing agent is 5 parts by weight or less, it shows a reduction in thermal decomposition and reinforcement of strength. It is difficult, if more than 200 parts by weight can play a role as a reinforcing agent, but the problem that the thermal conductivity is rapidly increased.

In addition, the expanded perlite insulation using the thermosetting resin according to the present invention may further include a water repellent. The water repellent in the present invention uses a powdery water repellent.

Next, the manufacturing method of the expanded perlite heat insulating material using the thermosetting resin by this invention is demonstrated.

Method for producing an expanded perlite heat insulating material using a thermosetting resin according to the present invention comprises the first step of producing expanded perlite by drying and expanding the ore; A second step of preparing a mixture by mixing 10 to 84% by weight of the expanded perlite prepared in the first step, 15 to 85% by weight of the organic curable powder binder, and 0.25 to 5% by weight of the reinforcing fiber; A third step of heating the mixture prepared in the second step to form a molded body and first curing the molded body; And a fourth step of post-curing or post-curing and heat-treating the first cured molded body in the third step.

Hereinafter, the manufacturing method of the present invention will be described in detail.

In more detail, the first step of producing expanded perlite, the surface is vitrified when a high temperature flame is encountered in the firing process by using water, which is commonly called crystal water, inside natural minerals such as pearl rock, pine rock, obsidian and pumice stone. The water inside is vaporized and expanded.

In this case, the expansion may be performed using a direct flame method or an indirect flame method, and may be prepared by expanding at a time according to a specific particle size distribution range or by separately expanding each particle size and then mixing them.

The shape of the expanded perlite particles is characterized in accordance with the size of the particles before the expansion and the degree of internal crystallization according to the distribution and degree of drying, wherein the shape of the cell is bursting the surface of the particle while the water is over-expanded Figure 1 As described above, the hollow cell may be manufactured in the form of an open cell having a needle structure, or the particle surface may be closed as shown in FIG. 2.

The open cell perlite and the closed cell perlite have a characteristic difference depending on the shape. In the case of the open cell perlite, the inside of the particles is open, and the inside of the particles is also composed of a myriad of cells, which have a large specific surface area and have a gaseous and liquid substance. Closed cell perlite does not have a higher specific surface area than open cells, but has excellent surface breaking strength and excellent particle breaking strength and excellent inter-particle flowability. In accordance with the smooth body filling, the molded article formed of the closed cell perlite has a somewhat better mechanical properties and thermal conductivity than the open cell perlite molded article.

In addition, the strength of the closed cell perlite is excellent and the particle breaking strength is maintained even when expanded to a lower density. However, when the expanded cell perlite is expanded to a lower density, overexpansion of the particles occurs and the crushing of the particles increases, resulting in 40 Kg / ㎥ It is difficult to manufacture and use below.

However, this does not mean that the open cell perlite has a disadvantage compared to the closed cell perlite, and may be selectively used according to the required physical properties and the intended use of the molded product to be manufactured, and the mixed closed cell and open cell perlite may be used. It is also possible.

There is no particular limitation on the content of the open cells in the closed cell expanded perlite, but in view of the function and effect on the thermal conductivity, it is preferable that the active ingredient of the closed cell is 50% by weight or more based on the total weight of the expanded perlite.

In addition, the particle size composition of the closed cell perlite is 15 ± 10% by weight of particles larger than 400 μm, 40 ± 15% by weight of 400-250 μm particles, 20 ± 10% by weight of 250-160 μm particles, and particles less than 160 μm based on the weight of expanded perlite. The particle size distribution of 30 ± 15% by weight had a good filling rate, and the thermal conductivity and strength of the prepared molded body were the best.

Stages 3 and 4 can be given different conditions to maximize their effectiveness.

First, the third step is a step of performing molding and primary curing, a method of curing during intermittent compression molding, which is a manufacturing method of a conventional expanded perlite insulation, or a method of continuous extrusion molding.

In the fourth step, in order to maximize productivity, only the first curing may be performed in the third step and the post-curing may be performed in the fourth step.

In addition, in the fourth step, in order to maximize thermal stability in the high temperature region of the heat insulating material, heat treatment processes such as carbonization, activation, and silicon carbide may be applied during post-curing.

Referring to the three steps of forming and primary curing the heat insulating material in more detail, the production of the heat insulating material using the conventional liquid binder was possible only by compression molding, by using a powder-curable binder, not only general compression molding is possible This has the advantage that continuous extrusion molding is also possible.

This means that when the mixture is manufactured, the flowability of particles in the case of the expanded perlite mixture using the conventional liquid inorganic binder (the flowability expressed here means that the effect of the frictional force and the angle of repose of the particles and particles is low, so that the positional movement is easy). While this is low in use constraints, the powder curable binder is excellent in flowability and can be used in various processes.

When the liquid binder is mixed with the expanded perlite interface, the viscosity and the surface tension of the expanded perlite particles are increased by the adhesive force and moisture of the binder, and the viscosity and the surface tension increase to produce cohesion between particles.

When the cohesive force is reduced, the flowability decreases, so that body milling is not easy, and when extrusion is performed in a state in which the body milling is not easy, the transfer of particles in the extrusion cylinder is not smooth, and thus, it is difficult to realize a required shape. Problems such as loss of adhesion strength and adhesion strength.

Therefore, the molding of the mixture of the liquid binder and the expanded perlite has to inject the mixture into the molding mold according to the required shape and perform compression molding. Since the compaction is not easy to compact, the particle crushing rate is increased. As the density deviation of each part and the porosity increase, the strength and hardness of the molded body decrease and the thermal conductivity increases.

In addition, since the liquid binder does not have a volume and remains coated on the surface of the expanded perlite, the voids between the particles and the particles cannot be filled during compression molding. In order to achieve maximum contact, this requires a high compression ratio, which leads to severe crushing of the particles, and a rapid increase in thermal conductivity due to an increase in the density of the molded body as the compression ratio increases.

In order to compensate for the filling of the compaction during the compression molding, vibration is generated in the mixed material to increase the compactness ratio, but the cohesion force between the locations is high, and the compactness due to the vibration does not occur over a certain range, Since a vibrating process is required, productivity becomes worse.

On the other hand, the thermosetting organic-based powder binder is present in a powder form at room temperature, and when raised above a predetermined temperature, the thermosetting organic powder binder becomes viscous and becomes viscous, and hardens at a specific temperature or more to exhibit adhesive strength.

Therefore, when the expanded perlite and the powder binder are mixed at room temperature, the binder does not have moisture and viscosity, so the perlite is secured, and the extruded materials can be extruded while maintaining a smooth conveyance and body density in a continuous extrusion cylinder. Therefore, sufficient adhesive strength can be ensured.

However, in order to further increase the efficiency of the filling of the body, the third step may be performed after the method of filling the body of the mixture in the second stage by vibrating or impacting the body.

In addition, the powder binder has an advantage that the melting and curing reaction according to the temperature, so that the required shape and production rate can be determined by performing a temperature gradient for each part of the extrusion cylinder.

In addition, the same compression molding is possible as before, and excellent physical properties can be realized compared to the existing heat insulating material. Increased flowability and smooth body milling due to the use of powder binders can apply uniform pressurization during compression, thereby reducing particle crushing rate, minimizing density variation and minimizing porosity of each part, thereby maximizing the strength and hardness of the molded body and excellent thermal conductivity. In addition, even when the vibration is applied to maximize the body ratio, the body can be smoother even under a short period of vibration conditions, thereby ensuring excellent physical properties while suppressing a decrease in productivity.

In addition, the powder binder has its own volume, so that the powder binder is located in the voids between the expanded perlite particles, thereby filling the voids, exhibiting sufficient adhesion even at a low compression ratio, and having a very low water content. It is possible to solve the increase in the thermal conductivity due to the residual moisture.

In addition, the curing temperature of the three steps can be carried out in the range of 80 to 300 ℃, if the curing temperature is less than 80 ℃ or hard curing is required for a long time, if the curing temperature is more than 300 ℃ rapid curing is made Therefore, problems such as a decrease in adhesive strength occur.

In addition, in the fourth step, heat treatment may be further performed to maximize thermal stability in the high temperature region of the insulation.

In more detail with respect to the four steps of performing the post-cure or post-cure and heat treatment, the production of expanded perlite insulation using a powder binder can change the manufacturing process in various forms in order to maximize productivity.

First, in order to maximize productivity in the three steps of molding and curing the mixed material, by compression or extrusion for a short time at a high temperature of 80 to 300 ° C. during compression or continuous extrusion, the surface of the molded body is first cured to support the shape. In the step, post-curing may be performed at a high temperature of 80 to 300 ° C. to completely cure the primary cured molded body.

Accordingly, in order to sufficiently cure during molding, it is possible to secure excellent physical properties while solving a decrease in productivity due to a long heating process being omitted in the mold or the extrusion cylinder.

This is a property of the thermosetting powder binder used in the present invention, and the binder is easily melted and cured in a short time according to the temperature rise, and has a specific temperature range in which melting and curing occur, thereby constituting a manufacturing process. When it can be easily configured in the desired form and section, it can be adjusted to various types of manufacturing conditions.

In addition, in the fourth step, a heat treatment process may be added in addition to the post-curing process to maximize thermal stability at high temperature, improve mechanical properties, and reduce thermal conductivity of the expanded perlite insulation material using the curable powder binder. Adding reinforcing agents can achieve higher heat resistance and mechanical properties. Examples of the heat treatment include carbonization under the atmosphere, carbonization under anoxic, activation and silicon carbide. At this time, only the post-curing is carried out at 80 ℃ to 300 ℃, while the heat treatment is carried out while raising the temperature range of 80 ℃ to 1100 ℃. The reason for the low temperature to the high temperature is that heat deformation may occur when directly affected by the high temperature, and the temperature distribution varies depending on the characteristics of the organic powder binder used.

Post-curing conditions can be carried out from the curing conditions of 80 ℃ in order to allow the normal hardening of the temporarily cured molded body to proceed again, and also proceeds to the maximum curing section of 300 ℃. At this time, it heats up to 1100 degreeC at the time of advancing to heat processing conditions. If the temperature exceeds 1100 ° C., excessive heat treatment may cause deformation and decrease in strength. Therefore, when only the post-cure proceeds from 80 ℃ to 300 ℃, if the post-hardening and heat treatment are carried out together can rise from 80 ℃ to 1100 ℃. However, the heat treatment temperature is possible up to 1100 ℃, and it is used to adjust the temperature below 1100 ℃ according to the actual desired physical properties. In addition, the rate of temperature rise is carried out within a range that does not overdo the process.

Organic binders, in particular thermosetting binders, can secure superior adhesion compared to inorganic binders, and have the advantage of ensuring low density, excellent mechanical properties and thermal conductivity even when the amount of use is reduced, while decomposition of organic materials occurs as the temperature rises. The mechanical properties of the manufactured molded article is reduced and cracks and shrinkage occur.

A representative example of the powdered organic binder mentioned in the present invention may be a novolak phenol resin, and the fully cured novolak phenol cured product can secure high thermal stability compared to other organic binders, but this is also a high temperature of 350 ° C or higher. It is difficult to secure thermal stability.

In particular, industrial high-temperature insulation materials are often used at a temperature of 200 ℃ or more, in the case of the insulation material made of a thermosetting binder, there is a risk that the physical properties of the insulation material is sharply worsened or cracks due to the long-term thermal stability is reduced. .

The problem of the high temperature thermal stability can be solved by heat-treating the powder-type thermosetting resin to a high temperature to replace the resin with a strong carbon-carbon structure to secure high thermal stability, that is, to form carbonization.

This carbonization process can be divided into a carbonization process in atmospheric conditions performed in the presence of oxygen, and a carbonization process in anoxic conditions carried out by blocking oxygen inflow.

In case of carbonization under oxygen condition, carbonization can proceed without additional equipment for removing oxygen.However, when carbonization temperature is within the range of 80 ~ 400 ℃ and exceeds 400 ℃, expansion of chain structure On the other hand, the cracking of the molded product may occur due to overheating. On the other hand, carbonization under anoxic conditions requires additional facilities to remove oxygen, but the carbonization temperature is in the range of 80 to 1100 ° C, and is short for high temperature. It has the advantage of being able to carry out carbonization.

However, when high temperature carbonization is difficult in the atmospheric conditions, it is difficult to secure an appropriate pressure, there is a risk that thermal decomposition of organic matter occurs in the process of forming a carbon-carbon bond structure, thereby reducing the mechanical strength. When the heat insulating material is applied with high pressure, breakage of a cell showing heat insulating efficiency occurs, and thus there is a problem in that sufficient pressure cannot be applied.

In order to solve the problem of carbonization under these earth conditions, an inorganic reinforcing agent that can be melted at a high temperature may be mixed.

Inorganic substances such as boric acid are present in powder form at room temperature, and melt with increasing temperature to form a liquid phase, and solidify at a higher temperature to form a diaphragm.

Therefore, by mixing and molding the expanded perlite, the powdered organic binder and the meltable inorganic reinforcing agent, the adhesive force by the organic binder is primarily secured, and the carbon-carbon bond of the organic binder is progressed through high temperature heat treatment under atmospheric conditions. At the same time, the inorganic reinforcing agent is solidified through the melting process, so that the inorganic reinforcing agent forms a diaphragm on the surface of the organic cured product forming the carbon-carbon bond structure.

As a result, an organic cured product having a carbon-carbon bond structure inside and a composite structure having an inorganic diaphragm having high thermal stability outside forms a high temperature by preventing thermal decomposition that may occur when the structure is changed to a carbon-carbon bond form. Thermal stability is increased, and through the double bonds of carbon-carbon bonds and inorganic melt bonds to enhance the adhesive strength can improve the overall mechanical properties.

The inorganic reinforcing agent may be mixed 5 to 35% by weight, preferably 10 to 30% by weight based on the total weight%, less than 5% by weight is difficult to show the reduction of thermal decomposition and reinforcement of strength, when more than 35% by weight The role as a reinforcing agent can play a sufficient role, but a problem arises in that the thermal conductivity increases rapidly.

In the present invention, the inorganic reinforcing agent may use boric acid, but is not particularly limited, and may use phosphorus or a boron compound, and forms a diaphragm according to high temperature such as ammonium phosphate, aluminum phosphate, zinc phosphate, and boric acid which is an acid compound of boron. It may include all of the phosphorus or boron compound. Inorganic reinforcing agents may be used individually or in combination.

In addition, by performing carbonization under anoxic conditions, the crosslinked structure of the thermosetting resin is prevented to the maximum, the reduction of mechanical properties due to the rapid temperature increase of the molded body is prevented, and the specific surface area is prevented by preventing the closing of particle pores. It is possible to form increased carbon bodies.

In general, the cross-linked structure of the organic cured product secures a strong bonding force by forming a carbon-carbon structure through heat treatment, but a part of the carbon body, that is, the methyl (CH ₂ ) group, which forms the cross-linked structure with oxygen inflow is incinerated. Carbonization yield (meaning yield indicating the degree of carbonization relative to the total weight of organic cured product) is not secured to a certain level, and fine cells generated by carbonization are also collapsed through pyrolysis. As a result, it is difficult to maximize the specific surface area.

Therefore, by heat treatment process under anoxic conditions, it is possible to suppress the thermal decomposition due to oxidation in the process of forming the carbon-carbon structure to increase the carbonization yield to maximize the bonding force, the fine cell produced by carbonization By suppressing collapse, maximization of the specific surface area within the molded body can be achieved.

In addition, by eroding the surface of the carbon body in the carbonization process through a high temperature heat treatment, it is possible to perform an activation process to increase the microporous structure to extremely increase the specific surface area. The process is carried out by inflow of steam in the heat treatment process in the range of 600 to 1100 ℃, or inert gas carbon dioxide after the carbonization process.

In addition, the silicon carbide molded body can be formed by reacting silicon or silicon-containing gas in a carbonized molded body under conditions of an inert gas and a high temperature of 1000 to 1100 ° C., and the silicon carbide structure formed as described above has higher Mechanical properties, thermal stability and low thermal conductivity can be obtained.

The silane monomer system may be coated on the surface of the expanded perlite particles in order to improve the water repellency, the water absorption rate, the flowability, and the like of the insulation prepared by the expanded perlite and the organic curable binder as described above.

Silane-based monomers have alkoxy groups that induce a chemical bond with the ferrite at the end and an alkyl group having a water repellent property. The silane monomer extends to the outside like a twig or a hairball on the entire surface of the ferrite to form a layer, thereby improving the frictional resistance of the surface. By lowering the flowability, the fluidity is better when it is added to the compression molding process, and the effect of permanently repelling the water is obtained.

In the present invention, as a water repellent agent by surface coating for the purpose of showing water repellency, titanate-based or zirconate-based reinforcing strength may be used as well as organic silane, and more specifically, isooctyltrimethoxysilane (i-octyltrimethoxysilane ), Methyltrimethoxysilane, octyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxytriethoxysilane , 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri (2-methoxy-ethoxy) silane [vinyltri ( Organosilane coupling agents including 2-methoxy-ethoxy) silane and neopentyl (diallyl) oxy, trineodecanoyl titanate [neopentyl (diallyl) oxy, trineodecanotitana te], neophenyl (diallyl) oxy, tril (dodecyl) benzene-sulfonyl titanate [neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl titanate], tri (dioctyl) phosphate titanate], neophenyl ( Diallyl) oxy, tri (dioctyl) pyro-phosphatotinaniate [neopentyl (diallyl) oxy, tri (dioctyl) pyro-phsophato titanate], neopentyldiallyloxy, tri (N-ethylenediamino) ethyl Titanate [neopentyl ((diallyl) oxy, tri (N-ethylenediamino) ethyl titanate], neopentyldiallyloxy, tri (m-amino) phenyl titanate [neopentyl (diallyl) oxy, tri (m-amino) pentyl titanate Titanate-based coupling agents including neopentyl (diallyl) oxy, trineodecanonyl zirconate [neopentyl (diallyl) oxy, trineodecano zirconate], neophenyl (diallyl) oxy, tril (dodecyl) ) Neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl zirconate], neophenyl (diallyl) oxy, tri (dioctyl) phosphatojiroconate [neopentyl ( diallyl) oxy, tri (dioctyl) phosphate ziroconate], neophenyl (diallyl) oxy, tri (dioctyl) pyro-phosphatojiroconate [neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphato ziroconate], neo Pentyldiallyloxy, tri (dioctyl) pyro-phosphatojiroconate [neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphato zirconate], neopentyldiallyloxy, tri (N-ethylenediamino) ethyljiro Neopentyl (diallyl) oxy, tri (N-ethylenediamino) ethyl zirconate], neopentyldiallyloxy, tri (m-amino) phenylzirconate [neopentyl (diallyl) oxy, tri (m-amino) phenyl zirconate ] A giroconate coupling agent etc. containing these etc. are included.

The coupling agent is in the form of a liquid phase, and the liquid is sprayed onto the expanded perlite surface, and then heated or dried to combine with the expanded perlite surface through a chemical reaction to form a coating film.

In the present invention, in the production of the insulating material by mixing the expanded perlite and the organic curable powder binder, the powder-type silicone-based water repellent may be mixed and molded before molding in order to improve the water repellency of the molded body and reduce the water absorption.

The powdered water repellent is present in powder form at room temperature, so that it is possible to smoothly carry out the filling of the expanded perlite particles before compression, and the powdered water repellent is also melted at the same time when the organic curable binder is melted according to the elevated temperature. Improves, reinforces the water repellency of the formed molded body and reduces the water absorption.

In addition, after molding of the expanded perlite insulation material, a liquid water repellent may be applied to the surface of the heat insulating material or the molded body may be immersed in the water repellent solution to secure additional water repellency and water absorption. The liquid water repellent may be used in combination with the water repellent in the form of securing water repellency through drying at room temperature, or in the form of securing a higher water repellency through additional drying.

In order to reinforce the formability, bending strength, workability, etc. of the expanded perlite insulation in the present invention includes a reinforcing fiber having a length of 5 ~ 30mm. Reinforcing fibers are used in combination with inorganic fibers or organic fibers, respectively.

In addition, other types of reinforcing agents may be used to further lower the strength or thermal conductivity.

To reinforce the strength, fumed silica of less than 50 μm, aerogels, and white carbon can be used, which are formed of nanometer-sized ultrafine cells with excellent thermal conductivity, and when mixed with expanded perlite, Even if the gap is filled to reduce the molding compression ratio, it has a compact molding state, thereby improving the strength and securing a low thermal conductivity.

In addition, a radiation shield may be used to further lower the thermal conductivity.

This is because in the case of expanded perlite, the effect of radiation increases as the temperature gets higher, and there is a limit to blocking the effect on the radiation. Further, by adding a material that blocks the radiation, the thermal conductivity can be further lowered.

In particular it sees a greater effect in the high temperature region.

In the present invention, the molded product produced by carbonizing or activating the expanded perlite insulation having a hardening structure by an organic binder has a cell structure of a multiple cell structure having both a cell of perlite and a carbonized fine cell. By forming a binder, it can be applied to various applications requiring low thermal conductivity and high specific surface area, and in particular, can be used as a core material of a thermal insulation material or a vacuum insulation material.

Vacuum Insulation Panel has a microporous insulation material as an inner core material in a panel made of a closed type, and vacuums the inside to remove heat transfer by conduction and convection, and thus extremely low thermal conductivity (0.005 W). / mK).

Such vacuum insulation materials are applied to building insulation materials, refrigerators, special packaging containers, etc. due to their extremely low thermal conductivity, and are attracting attention as energy saving and green growth products. Passive house aims to minimize energy consumption. As an insulator necessary for design, it has already been applied and commercialized in developed countries such as Europe and the United States.

Determining the performance of a vacuum insulator, i.e. low thermal conductivity, is the key to the core material, and inorganic fibrous materials are currently used as the core material of the vacuum insulator, which is a mat produced by the multi-orientation and multilayer adhesion of inorganic fibers. It has a high specific surface area in the form of, and it is easy to secure excellent thermal conductivity and stability in use due to low risk of destruction by impact.

However, since the vacuum insulating material of the inorganic fibrous material is easily changed in volume, if the volume changes over time, there is a high possibility that the vacuum is broken and a decrease in the degree of vacuum occurs, and thus the thermal conductivity rapidly increases.

In addition, when using the general expansion perlite, the settlement of the charged expansion perlite occurs, the vacuum degree is lowered by the volume change, so as to solve the problem that the thermal conductivity sharply worsens, the crushed expansion perlite is filled and sealed inside Thereafter, a technique of manufacturing a vacuum insulator by forming a vacuum state is also disclosed. However, since the fine particles reduce work efficiency of the vacuum process, the thermal conductivity is relatively lower than that of fumed silica.

On the other hand, when the carbonized expanded perlite insulation prepared according to the present invention is used as the inner core of the vacuum insulation, the cells of the expanded perlite and the open ultrafine cells produced by carbonization and activation are used. It has a multi-composite structure to obtain a high mechanical strength molded body with a high specific surface area and independent cells, which prevents further volume change, reducing the vacuum degree, and even at low vacuum levels due to the high specific surface area and independent cell structure. It can have excellent thermal conductivity.

In order to explain in more detail based on the above-mentioned contents, it will be described in detail through the following Examples and Experimental Examples, but these do not limit the scope of the present invention.

Example 1 Preparation of Insulation Material 1 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

Density 30 Kg / m 3 using perlite crystallization, based on the total weight of the expanded perlite, particles larger than 400 μm-15 wt%, 400 to 250 μm particles-40 wt%, 250 to 160 μm particles-20 wt%, 160 μm Expanded perlite was prepared having a particle size distribution of less than 30% by weight and a closed cell proportion of 70% by weight.

100 g of the novolak phenolic powder is expanded to 100% by weight of the expanded perlite, 1.5% by weight to the weight of the expanded perlite, and 0.5% by weight of the silicone-based water repellent is added to the weight of the expanded perlite into 1000 g of the closed cell expanded perlite prepared as described above. The mixture was prepared.

The density of the prepared mixture was 65Kg / ㎥, 527g of the mixture was compressed to about 1.8 times the initial volume was molded into a size X horizontal X height X height 300X300X50mm (volume 4.5L). Here, the compression ratio is not artificially adjusted, but is a compression ratio that is generated when the mixture is put into a molded mold heated to 200 ° C. in a volume of 4.5 L based on the bulk volume, and the following Examples and Comparative Examples are also the same. )

At this time, the compacted molded body was heated at 200 ° C. for 1 minute to be primarily cured and then demolded, and the demolded molded body was subjected to post-curing for 1 hour in a 200 ° C. hot air dryer to have an expanded perlite insulation material having a density of 115 ± 5 Kg / m 3. Was prepared.

Example 2 Preparation of Insulation Material 2 Using Expanded Perlite and Organic Curing Powder Binder of the Present Invention

527 g of the mixture prepared in Example 1 was compressed to about 1.8 times the initial volume and molded into a size of 300 × 300 × 50 mm (volume 4.5L).

The compacted molded body was heated at 200 ° C. for 1 hour to proceed to safety hardening to prepare expanded perlite insulation 2 having a density of 115 ± 5 Kg / m 3.

Example 3 Preparation of Insulation Material 3 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

The mixture is prepared in the ratio of each component in Example 1, but a sufficient amount to mix the continuous process, the temperature inside the extrusion cylinder in each of three stages, the initial section is room temperature ~ 40 ℃, intermediate section 80 ~ 120 ℃, the latter section is maintained at 120 ~ 150 ℃, the mold temperature of the final discharge portion was maintained at 150 ~ 200 ℃.

The single-sided extrusion molding machine made the shape of a discharge part metal mold | die 300 mm in width and 50 mm in height. The rotational speed of the screw was set such that the length of the molded body discharged from the discharge part was introduced into the present extrusion molding machine at a feeding speed of 0.2 L / sec through the hopper. The molded object discharged by this was cut | disconnected in 300 mm length unit.

The cut molded product was cured in a hot air dryer at 200 ° C. for 1 hour to prepare an expanded perlite insulating material 3 having a density of 115 ± 5 Kg / m 3. In this case, the manufactured molded article showed a density similar to that obtained by compression 1.8 times in compression molding.

Example 4 Preparation of Insulation Material 4 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

Perlite crystallization, density 40Kg / ㎥, 15% by weight of 800㎛ over-particles based on the total weight of expanded perlite, 40% by weight of 500㎛ particles at 800㎛, 20% by weight of 250㎛ particles at 500㎛, at 250㎛ The particle size distribution of 10 wt% of the 160 μm particles and less than 160 μm of the particles was 15 wt%, to prepare an open cell expanded perlite having a ratio of open cells of 70 wt% to the total weight.

100 g of the novolak phenolic powder is expanded to 100% by weight of the expanded perlite, inorganic fibers 1.5% to the weight of the expanded perlite, and 0.5% by weight of the silicone-based water repellent to 0.5% by weight of the expanded perlite into the open cell expanded perlite prepared as described above. To prepare a mixed material.

The prepared mixture had a density of 72 Kg / m 3, and 583 g of the mixture was compressed to about 1.8 times the initial volume to form a horizontal X vertical X height 300 X 300 X 50 mm (volume 4.5 L).

The compressed molded product was first cured by heating at 200 ° C. for 1 minute, followed by demolding. The expanded molded product was then cured in a 200 ° C. hot air dryer for 1 hour to prepare expanded perlite insulation 4 having a density of 125 ± 5 Kg / m 3. It was.

Example 5 Insulation 5 Preparation Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

An expanded perlite having 50 wt% closed cell expanded perlite and 50 wt% open cell expanded perlite was prepared, and the density of the mixed perlite was 35 Kg / m 3.

100 g of the novolak phenolic powder is added to the mixed expanded perlite by weight of 100% by weight of the expanded perlite, 1.5% by weight of inorganic fiber is added to the weight of the expanded perlite, and 0.5% by weight of the silicon-based water repellent is added to the expanded perlite. Prepared.

The density of the prepared mixture was 70Kg / ㎥, 567g of the mixture was compressed to about 1.8 times the initial volume was molded into a size X horizontal X height X height 300X300X50mm (volume 4.5L).

The compressed molded product was first cured by heating at 200 ° C. for 1 minute, followed by demolding. The expanded molded product was then cured in a 200 ° C. hot air dryer for 1 hour to prepare expanded perlite insulation 5 having a density of 120 ± 5 Kg / m 3. It was.

Example 6 Insulation 6 Preparation Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

In the closed cell expanded perlite having a density of 30 Kg / m 3 prepared in Example 1, methyltrimethoxysilane was prepared by coating 0.5 wt% of the expanded perlite by weight.

100 g of the novolac phenolic powder is expanded to 100% by weight of the expanded perlite, 1.5% by weight to the weight of the expanded perlite, and 0.5% by weight of the silicon-based water repellent is added to the coated closed cell expanded perlite and 0.5% by weight to the weight of the expanded perlite. Prepared.

The prepared mixture had a density of 65 Kg / m 3, and 527 g of the mixture was compressed to about 1.8 times its initial volume and molded into 300 × 300 × 50 mm (volume 4.5L).

The compacted molded body was cured by heating at 200 ° C. for 1 minute and then demolded, and the demolded molded body was subjected to post-curing for 1 hour in a 200 ° C. hot air dryer to prepare an expanded perlite insulating material 6 having a density of 115 ± 5 Kg / m 3.

<Example 7> Preparation of the heat insulating material 7 using the expanded perlite and the organic curable powder binder of the present invention

As in Example 1, the expanded perlite in the form of a closed cell having a density of 30 Kg / m 3 was prepared.

Expanded novolak phenol powder to 1000 g of the prepared closed cell expansion perlite, 90% by weight of the perlite, 10% by weight of the fumed silica as a reinforcing agent, 10% by weight of the inorganic fiber, 1.5% by weight of the perlite, and silicone-based water repellent 0.5 wt% of the weight of the perlite was added and mixed to prepare a mixture.

The density of the prepared mixture was 66Kg / m 3, and 535g of the mixture was compressed to about 1.8 times the initial volume to form a 300 × 300 × 50 mm (volume 4.5L).

The compressed molded product was first cured by heating at 200 ° C. for 1 minute, followed by demolding. The expanded molded product was then cured in a 200 ° C. hot air dryer for 1 hour to prepare expanded perlite insulation 7 having a density of 115 ± 5 Kg / m 3. It was.

Example 8 Manufacture of Insulation Material 8 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

Expanded novolak phenol powder to 1000 g of the manufactured closed cell expanded perlite, expanded 95% by weight of the perlite weight, expanded airgel with a strength enhancer, 5% by weight of the perlite weight, expanded inorganic fiber 1.5% by weight of the perlite weight, and expanded silicone powder water repellent 0.5 wt% of the weight of the perlite was added and mixed to prepare a mixture.

The prepared mixture had a density of 65 Kg / m 3, and 526 g of the mixture was compressed to about 1.8 times its initial volume to form a 300 × 300 × 50 mm (volume 4.5L).

The compressed molded product was first cured by heating at 200 ° C. for 1 minute, followed by demolding, and the demolded molded product was subjected to post-curing for 1 hour in a 200 ° C. hot air dryer to prepare expanded perlite insulating material 8 having a density of 115 ± 5 Kg / m 3. It was.

Example 9 Preparation of Insulation Material 9 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

Expanded novolak phenolic powder to 1000 g of the prepared closed cell expanded perlite, expanded 100% by weight of the perlite, expanded boric acid by inorganic reinforcing agent, 30% by weight of the perlite, expanded inorganic fiber 1.5% by weight of the perlite, and expanded silicone-based water repellent 0.5 wt% of the weight of the perlite was added and mixed to prepare a mixture.

The prepared mixture had a density of 70 Kg / m 3, and 567 g of the mixture was compressed to about 1.8 times its initial volume and molded into 300 × 300 × 50 mm (volume 4.5L).

After the compacted molded body was heated at 200 ° C. for 1 minute for primary curing, demolding was carried out, and the demolded molded body was put into a hot air dryer to raise the temperature from an initial temperature of 200 ° C. to 350 ° C. over 1 hour to conduct post curing and heat treatment. Natural cooling was performed for 1 hour and then discharged from a hot air fan. At this time, the surface temperature of the molded body was a temperature range of 50 ℃ at room temperature. This produced an expanded perlite insulation 9 having a density of 125 ± 5 Kg / ㎥.

<Example 10> Preparation of the heat insulating material 10 using the expanded perlite and the organic curable powder binder of the present invention

In the same manner as in Example 9, but mixed in each component ratio, the powder repellent was prepared in the same process as in Example 9 with a mixed material not mixed. A silicone-based water repellent solution diluted to 1% solids was prepared, and 5 g per 0.01 m 2 of the molded article cross-sectional area was applied to the prepared water-repellent solution.

The molded article coated with the water repellent solution was dried at room temperature for one day at a place with good ventilation to prepare an expanded perlite insulation 10 having a density of 125 ± 5 Kg / m 3.

Example 11 Manufacture of Insulation Material 11 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

In the same manner as in Example 10, but mixed in each component ratio, instead of the closed cell expansion perlite mixed using an open cell expansion perlite, a molded article was prepared in the same process as in Example 9. A silicone-based water repellent solution diluted to 1% solids was prepared, and 5 g per 0.01 m 2 of the molded article cross-sectional area was applied to the prepared water-repellent solution.

The molded article coated with the water repellent solution was dried at room temperature for one day at a place with good ventilation to prepare an expanded perlite insulation 11 having a density of 130 ± 5 Kg / m 3.

Example 12 Preparation of Insulation Material 12 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

The compressed compact was heated at 200 ° C. for 1 minute to be primarily cured, and then demolded. The deformed compact was placed in a chamber in which oxygen was blocked and purged with nitrogen to maintain dissolved oxygen within the chamber at 200% or less. To 500 ° C. over 2 hours, and maintained at 500 ° C. for 1 hour, followed by natural cooling over 2 hours to carry out post curing and carbonization. At this time, the surface temperature of the molded body was a temperature range from room temperature to 50 ℃, through which the expanded perlite insulation 12 having a density of 115 ± 5 Kg / ㎥ was prepared.

Example 13 Manufacture of Insulation Material 13 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

In the same manner as in Example 12, but mixed in each component ratio, the powder repellent was prepared in the same process as in Example 12 with a mixed material not mixed. A silicone-based water repellent solution diluted to 1% solids was prepared, and 5 g per 0.01 m 2 of the molded article cross-sectional area was applied to the water-repellent solution prepared in the molded product.

The carbonized molded article coated with the water repellent solution was dried at room temperature for one day at a place with good ventilation to prepare an expanded perlite insulation 13 having a density of 115 ± 5 Kg / m 3.

Example 14 Manufacture of Insulation Material 14 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

In the same manner as in Example 13, but mixed in each component ratio, but instead of the closed cell expansion perlite, the mixture was prepared in the open cell expansion perlite prepared in Example 4 and the molded body was prepared in the same process as in Example 12. A silicone-based water repellent solution diluted to 1% solids was prepared, and 5 g per 0.01 m 2 of the molded article cross-sectional area was applied to the water-repellent solution prepared in the molded product.

The carbonized molded article coated with the water repellent solution was dried at room temperature for one day at a place with good ventilation to prepare a surface-water-reinforced expanded expanded ferrite insulation 14 having a density of 125 ± 5 Kg / m 3.

Example 15 Manufacture of Insulation Material 15 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

A molded article prepared in the same manner as in Example 12 was heated to 1000 ° C. under an inert gas, and silicon-containing gas was introduced to prepare a silicon carbide expanded perlite insulating material 15.

Example 16 Manufacture of Insulation Material 16 Using Expanded Perlite and Organic Curable Powder Binder of the Present Invention

The molded article manufactured in the same manner as in Example 12 was activated with saturated steam for 1 hour at 600 ° C. in a steam atmosphere, and the inside of the three-sided sealed body having a width of 420 × 420 mm in width X length was put in a vacuum packing material of a composite material. And a vacuum pressure of 3 torr was formed and then sealed to prepare a vacuum insulator 16.

Comparative Example 1 Preparation of Insulation Material 1 Using Expanded Perlite and Sodium Silicate as an Inorganic Liquid Binder

Density 30 Kg / m 3 using perlite crystallization, based on the total weight of the expanded perlite, particles larger than 400 μm-15 wt%, 400 to 250 μm particles-40 wt%, 250 to 160 μm particles-20 wt%, 160 μm An expanded perlite was prepared having a particle size distribution of less than 30% by weight and a closed cell proportion of 70% by weight.

A liquid inorganic binder was prepared by mixing a silicon-based liquid water repellent agent with 0.5 wt% of sodium silicate in 1000 g of 33 Be 'sodium silicate.

433 g of the mixture prepared above and 413 g of the prepared liquid inorganic binder were mixed, and about 3.2 times the initial volume was compressed to prepare a molded article having a size of 300 × 300 × 50 mm.

The formed article was dried in a 200 ° C. hot air dryer for 4 hours to prepare an insulating material 1 using expanded perlite and sodium silicate in an open cell having a density of 130 ± 5 Kg / m 3.

<Comparative Example 2> Preparation of the heat insulating material 2 using the expanded perlite of the present invention and sodium silicate which is an inorganic liquid binder

Perlite crystallization, density 40Kg / ㎥, 15% by weight of 800㎛ over-particles based on the total weight of expanded perlite, 40% by weight of 500㎛ particles at 800㎛, 20% by weight of 250㎛ particles at 500㎛, at 250㎛ The particle size distribution of 10 wt% of 160 μm particles and less than 160 μm particles was 15 wt%, to prepare an open cell expanded perlite having an open cell ratio of 70 wt% to the total weight.

After mixing 576 g of the mixture prepared above and 413 g of the prepared liquid inorganic binder, a compact of 300 × 300 × 50 mm was manufactured by compressing about 3.2 times the initial volume.

The formed article was dried in a 200 ° C. hot air dryer for 4 hours to prepare an insulating material 2 using expanded perlite and sodium silicate in an open cell having a density of 150 ± 5 Kg / m 3.

Comparative Example 3 Production of Insulation Material 3 Using Expanded Perlite and Sodium Silicate as an Inorganic Liquid Binder

In the closed cell expanded perlite having a density of 30 Kg / m 3 prepared in Comparative Example 2, methyltrimethoxysilane was prepared by coating 0.5% by weight of the expanded perlite.

1000 g of the coated closed cell expanded perlite inorganic fiber was added and mixed with 1.5 wt% of the expanded perlite to prepare a mixed material.

1000 g of 33 Be 'sodium silicate alone was prepared as a liquid inorganic binder.

433 g of the mixture and 413 g of the liquid inorganic binder were mixed to compress a size of about 3.1 times the initial volume to prepare a molded body having a size of 300 × 300 × 50 mm.

The formed article was dried in a 200 ° C. hot air dryer for 4 hours to prepare an insulating material 3 using expanded perlite and sodium silicate in an open cell having a density of 130 ± 5 Kg / m 3.

Experimental Example 1 Characterization of Expanded Perlite Insulation

Based on the KS F 4714, the Examples and Comparative Examples were measured and analyzed for thermal conductivity, flexural strength, bowing factor, and water repellency, and are shown in Table 1 below.

Table 1

division	Molding Compression Ratio	Contraction rate	Thermal Conductivity (W / mK)			Flexural strength (N / ㎠)	Water repellency
division	Molding Compression Ratio	Contraction rate	20 ℃	70 ℃	200 ℃	Flexural strength (N / ㎠)	Water repellency
Example 1	1.8	2% or more	-	0.0454	0.0585	44.3	More than 98%
Example 2	1.8		-	0.0447	0.0578	45.4
Example 3	1.8		-	0.0463	0.0591	43.3
Example 4	1.8		-	0.0495	0.0624	40.5
Example 5	1.8		-	0.0469	0.0574	42.1
Example 6	1.8		-	0.0448	0.0568	43.8
Example 7	1.8		-	0.0401	0.0537	47.4
Example 8	1.8		-	0.0378	0.0515	46.2
Example 9	1.8	Within 1%	-	0.0431	0.0552	45.1
Example 10	1.8		-	0.0437	0.0560	46.3
Example 11	1.8		-	0.0461	0.0584	43.4
Example 12	1.8	Within 0.5%	-	0.0441	0.0522	42.1
Example 13	1.8		-	0.0416	0.0534	46.3
Example 14	1.8		-	0.0447	0.0548	43.6
Example 15	1.8		-	0.0450	0.0551	54.3
Example 16	1.8		0.003	-	-	42.1
Comparative Example 1	3.2	Within 2%	-	0.052	0.073	26.4
Comparative Example 2	3.2			0.055	0.077	23.1
Comparative Example 3	3.1		-	0.051	0.070	26.1

In addition, in order to further compare the effect of the expansion perlite type, heat treatment, activation process was measured using a specific surface area meter and are shown in Table 2 below.

TABLE 2

division	Specific surface area (㎡ / g)
Example 1	0.5 to 2
Example 4	5 to 10
Example 10	70-120
Example 11	100 to 150
Example 13	300 to 700
Example 14	550-850
Example 16	1200 to 1700

As shown in Table 1, Examples 1 to 16 of the present invention prepared using the expanded perlite and the powdered organic binder have a lower density than Comparative Examples 1 to 3 using liquid sodium silicate, which is a conventional binder. Flexural strength was measured to be higher than 40 ~ 80%.

In the thermal conductivity, the thermal conductivity was lower than 15% in the temperature range of 70 ℃, and the thermal conductivity was lower than 20% in the 200 ℃ range, which is the actual range of industrial insulation.

This is because the density of the heat insulating material is low, even if the temperature rises, heat transfer is suppressed compared to the existing heat insulating material, and the thermal conductivity is lowered in the high-temperature section. In addition, the conventional binder inorganic silicate silica is amorphous, and the heat transfer is high due to the temperature rise. In the case of the organic curing binder, low heat transfer and little residual moisture indicate that an additional reduction in thermal conductivity can be achieved.

In addition, due to the lack of excessive compression, the particles are prevented from breaking and the loss of thermal insulation is reduced.

Example 1, which performs only the primary curing in the three steps of compression and molding, and post-cure in the fourth step, and Example 2, which performs the complete curing in the third step, and Example 3, which are extruded, have similar bow shrinkage, flexural strength, and thermal conductivity. Indicated.

This indicates that in the case of an expanded perlite heat insulating material using a curable powder binder, excellent physical properties can be secured even if the manufacturing method is changed depending on the form, use, and productivity to be manufactured.

Examples 9 to 14, which were subjected to the heat treatment of the prepared molded body, exhibited lower bow shrinkage, lower thermal conductivity, and overall higher bending strength than those of Examples 1 to 8, which were not subjected to heat treatment.

This is because the thermal stability of the organic binder cross-linked structure through the carbon-carbon bonds to increase the thermal stability was lowered, the mechanical properties increased and the thermal conductivity was reduced due to the formation of fine cells by carbonization.

Examples 10 to 11 and 13 to 14, which applied a liquid repellent agent to a molded article prepared by heat treatment, had a water repellency similar to those of Examples 9 and 12 in which a water repellent was mixed before molding, since the water repellent was dry-bonded on the surface of the insulating material. As a result, the flexural strength also increased slightly.

As can be seen from Table 2, Example 10 and Example 13 subjected to the heat treatment showed a higher specific surface area than Example 1, and Example 11 and Example 14, which heat-treated the molded body made of open cell perlite, were closed cell perlite. When prepared with a higher specific surface area was shown.

This indicates that, in Example 1, which does not perform carbonization of the organic cured product, most of the organic cured products have a closed structure, and in Example 10 that undergoes heat treatment and Example 13, which undergoes carbonization, organic curing In the process of carbonization of water, it shows that the formation of countless micropores and the pores generated are preserved undisintegrated. Examples 11 and 14 made of open cell perlite have a large number of pores of the particles themselves and have a large specific surface area. Greater effect.

In addition, by additionally performing activation through water vapor on the carbonized molded body as in Example 16, the surface of the carbon body could be eroded to generate extremely fine pores.

This means that the heat insulating material manufactured through carbonization and activation of specific surface area, which is a measure of the effect of the core material of vacuum insulation material, can satisfy the condition, and 0.003 W / at 20 ° C as measured thermal conductivity. It showed excellent thermal conductivity of mK, which means that it has a high specific surface area and can form a composite structure of excellent mechanical strength having a cell structure of perlite at the same time, thereby serving as a vacuum insulator. .

Although the above embodiments and experimental examples, in particular structural forms and the like have been described, this does not limit the scope thereof, and those skilled in the art to which the present invention pertains may be modified without departing from the principles of the present invention. It can be seen that.

Claims

An expanded perlite heat insulating material using a thermosetting resin, characterized in that it comprises 10 to 84% by weight of expanded perlite, 15 to 85% by weight of an organic curable powder binder, and 0.25 to 5% by weight of reinforcing fibers prepared by drying the ore.
The expanded perlite heat insulating material according to claim 1, wherein the expanded perlite heat insulating material using the thermosetting resin further includes 5 to 200 parts by weight of a reinforcing agent based on 100 parts by weight of the organic curable powder binder.
The method of claim 1,

The expanded perlite thermal insulation material using a thermosetting resin, characterized in that the active ingredient of the closed cell expanded perlite of the expanded perlite is included by 50% by weight or more based on the total weight of the expanded perlite.
The method of claim 1,

The ore is expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from pearl rock, obsidian, pine rock, and pumice.
The method of claim 1,

The organic-based curable powder binder is a novolak phenol resin or expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from melamine resin, epoxy resin, silicone resin modified in powder form.
The method of claim 1,

The reinforcing fibers are expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from inorganic or organic fibers.
The method of claim 2,

The reinforcing agent is an expanded perlite heat insulating material using a thermosetting resin, characterized in that using an inorganic reinforcing agent.
The method of claim 7, wherein

The inorganic reinforcing agent is an expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from ammonium phosphate, aluminum phosphate, zinc phosphate, boric acid, boron, borax.
The method of claim 7, wherein

The inorganic reinforcing agent is expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from fumed silica, aerogels or white carbon.
The method of claim 1,

The expanded perlite insulation using the thermosetting resin further comprises a powdery water repellent, the expanded perlite insulation using a thermosetting resin.
The method of claim 1,

The expanded perlite heat insulating material using a thermosetting resin, characterized in that the surface of the expanded perlite further comprises one coating film selected from a glass silane coupling agent, titanate coupling agent, zirconate coupling agent.
A first step of preparing expanded perlite by drying and expanding the ore;

A second step of preparing a mixture by mixing 10 to 84 wt% of the expanded perlite prepared in the first step, 15 to 85 wt% of the organic curing powder binder, and 0.25 to 5 wt% of the reinforcing fiber;

A third step of compressing or extruding the mixture prepared in the second step to form a molded article and first curing the molded article; And

And a fourth step of post-curing the primary-cured molded body in the third step.
The method of claim 12,

When preparing the expanded perlite of the first step, the thermosetting resin, characterized in that it is prepared by one of the method of manufacturing by expanding at a time according to a certain particle size distribution range or by separately expanding and then mixing them for each particle size prepared Method for producing an expanded perlite insulation used.
The method of claim 12,

Method of manufacturing an expanded perlite heat insulating material using a thermosetting resin, characterized in that when the expanded perlite of the first step is expanded to at least one selected from a direct flame method or an indirect flame method.
The method of claim 12,

Method for producing an expanded perlite insulation using a thermosetting resin, characterized in that for producing the molded article of the third step, at least one selected from compression molding or continuous extrusion molding.
The method of claim 12,

In the manufacturing of the molded article of the third step, after passing through the body filling method by vibrating or impacting the mixture of the second step, and then proceeding to the third step, the method of producing an expanded perlite heat insulating material using a thermosetting resin.
The method of claim 12,

In the preparation of the mixture of the second step, the organic curable powder binder is novolak phenol resin or the production of expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from melamine resin, epoxy resin, silicone resin modified in powder form Way.
The method of claim 12,

In the preparation of the mixture of the second step, a method for producing an expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from inorganic fibers or organic fibers as a reinforcing fiber.
The method of claim 12,

When preparing the mixture of the second step, the expanded perlite using a thermosetting resin, characterized in that it further comprises a reinforcing agent having a feature that is heat-melted and solidified in a ratio of 5 to 200 parts by weight based on 100 parts by weight of the organic curable powder binder. Method of manufacturing insulation.
The method of claim 19,

The reinforcing agent is a method of producing an expanded perlite heat insulating material using a thermosetting resin, characterized in that at least one selected from ammonium phosphate, aluminum phosphate, zinc phosphate, boric acid, boron, borax.
The method of claim 12,

In the preparation of the mixture of the second step, a method of manufacturing an expanded perlite heat insulating material using a thermosetting resin, characterized in that the powder is further prepared by adding a water repellent.
The method of claim 12,

In the preparation of the mixture of the second step, a method of manufacturing expanded perlite heat insulating material using a thermosetting resin, characterized in that the addition of at least one selected from fumed silica, airgel or white carbon as a reinforcing agent.
The method of claim 12,

When the hardening of the third step, the primary curing at a temperature in the range of 80 to 300 ℃ characterized in that the manufacturing method of the expanded perlite heat insulating material using a thermosetting resin.
The method of claim 12,

When the post-cure of the fourth step, the post-curing at a temperature in the range of 80 to 300 ℃, the method of producing an expanded perlite heat insulating material using a thermosetting resin, characterized in that.
The method of claim 12,

The post-curing of the fourth step, the method of manufacturing an expanded perlite insulation using a thermosetting resin, characterized in that for performing additional heat treatment.
The method of claim 25,

The heat treatment is a method of producing an expanded perlite heat insulating material using a thermosetting resin, characterized in that the carbonization is performed at a temperature in the range of 80 to 1100 ℃ in anoxic conditions.
The method of claim 25,

The heat treatment is in the air Process for producing an expanded perlite insulation using a thermosetting resin characterized in that the carbonization is carried out at a temperature in the range of 80 to 400 ℃.
The method of claim 25 or 26,

After the carbonization, the production method of the expanded perlite heat insulating material using a thermosetting resin, characterized in that for further performing an activation process for introducing steam or carbon dioxide.
The method of claim 25 or 26,

After the carbonization is carried out, the method of producing an expanded perlite heat insulating material using a thermosetting resin, characterized in that further performing a silicon carbide step of introducing a gas containing silicon or silicon.
The method of claim 12,

After the post-curing of the fourth step, the surface of the prepared molded article is coated with a water repellent and dried to prepare a heat insulating material, characterized in that the manufacturing method of expanded perlite heat insulating material using a thermosetting resin.
The expanded perlite heat insulating material using the thermosetting resin according to any one of claims 1 to 11, wherein the expanded perlite heat insulating material using the thermosetting resin is used as a core material of a heat insulating material or a vacuum heat insulating material. Products using perlite insulation.