WO2017164469A1

WO2017164469A1 - Method for preparing thermally conductive polymer resin by using recycled ash conductive filler

Info

Publication number: WO2017164469A1
Application number: PCT/KR2016/009769
Authority: WO
Inventors: 현봉수
Original assignee: 주식회사 제이에스엠
Priority date: 2016-03-21
Filing date: 2016-09-01
Publication date: 2017-09-28
Also published as: KR101696901B1

Abstract

The present invention relates to a method for preparing a thermally conductive polymer resin by using a recycled ash conductive filler and, more specifically, to a method for preparing a thermally conductive polymer resin by using a recycled ash conductive filler, the method being capable of preparing a thermally conductive polymer resin having high insulation and thermally conductive properties by using discarded flooring materials (flooring materials remaining after the incineration of daily waste), such that the recyclability of resources can be increased and environmental pollution caused by the burying of the flooring materials can be prevented. To this end, the present invention comprises: a mixing step of mixing flooring materials with aluminum powder; a primary pulverizing step of pulverizing the mixture mixed in the mixing step; a sintering step of sintering mixture powder generated in the primary pulverizing step; a secondary pulverizing step of re-pulverizing the sintered materials generated in the sintering step; and a filling step of mixing a conductive filler generated in the secondary pulverizing step with a base resin so as to form a thermally conductive polymer resin.

Description

Method for manufacturing thermally conductive polymer resin using waste incineration flooring heat radiation filler

The present invention relates to a method for manufacturing a thermally conductive polymer resin using a waste incineration flooring heat dissipation filler, and more specifically, to a thermally conductive polymer resin having high insulation and thermal conductivity properties using a discarded flooring material (a flooring material remaining after incineration of domestic waste). The present invention relates to a method for producing a thermally conductive polymer resin using a recycled ash conductive filler (RACF) that can not only increase the recyclability of resources but also prevent environmental pollution due to the landfill.

Various electronic parts such as semiconductors, PCBs, and display devices are accompanied by heat generation during operation of the device due to the characteristics of the material itself and the electrical resistance generated at the connection parts of the components.

Heat generated in this way acts as a cause of shortening the endurance of electronic equipment by increasing the temperature of operating parts, especially circuits and lamps of CPU, memory, plasma display monitor or liquid crystal display monitor. The various electronic circuit elements of the device tend to malfunction or exhibit the maximum performance of the part above a certain temperature.

In recent years, miniaturization and integration of electronic components have caused more serious heat generation due to an increase in the number of circuits included in a unit area, and thus cooling of such electronic components has become a very important problem.

Therefore, various means have been proposed to improve this, and in particular, a passive cooling method of dissipating heat to the outside by using a heat sink or a casing of an electronic device is used as an important means.

However, when cooling by heat conduction by the heat sink or the device shell as described above, it is important to effectively transfer the heat generated from the electronic device to the heat sink or the shell.

In general, in case of simply leaving an empty space between the electronic circuit and the heat sink or the outer shell, due to the high heat insulating ability of the air (thermal conductivity 0.0234 W / mK), effective heat diffusion is not achieved. It is necessary to exclude as much as possible the air layer between the heat sink and the heat sink or shell.

In addition, the heat sink or the outer shell should be made of metal-based material because it should be able to protect the product and should look good and at the same time be able to diffuse heat effectively.

Therefore, in the case of designing contact between the electronic circuit and the heat sink or the outer skin to remove the insulation effect caused by the air layer, the current applied to the electronic circuit may be shorted, which may cause malfunction of the electronic device. At least, even if the normal operation of the device is possible, the use efficiency of the power drops drastically, and there is a risk of electric shock to the user.

Thus, in order to solve this problem, the technology described in Korean Patent No. 10-1333260 as shown in FIG. 1 has been proposed, and its technical features include a thermally conductive ceramic compound including alumina (Al 2 O 3); Graphene oxide; And a thermosetting resin; wherein the graphene oxide is obtained from graphite oxide having a d-spacing of 8.700 kPa or more, and further includes graphene, and graphene oxide and graphene The weight ratio of the fin is 9: 1 to 6: 4, wherein the thermosetting resin is characterized in that it comprises at least one member selected from the group consisting of epoxy resin, polyimide resin, phenoxy resin and acrylic resin.

By the way, the technology described in Korean Patent No. 10-1333260 has the advantage of providing a resin composition that can implement excellent thermal conductivity while maintaining insulation using a thermally conductive ceramic compound containing alumina, but such insulation and thermal conductivity characteristics Since only a general resin and a thermally conductive material are used in manufacturing the resin composition having all of them, the manufacturing cost is high, and there is a problem in that there is no chance of recycling waste materials such as flooring materials, which are generated in recent years.

That is, in recent years, waste materials are causing a lot of problems in various industries, such waste materials are generated in each field, such as construction materials, industrial materials, household, general waste, and also difficult to separate collection.

These waste materials are mixed with various kinds of metals, plastics, inorganics, organics, scrap metals, and cause environmental problems even when they are landfilled. Therefore, most of them are incinerated at temperatures around 1000 ° C and then used as building materials.

However, when used as a building material, such as brick, there is a problem that the economical efficiency is lowered because the quality of the product is not high and the manufacturing cost is high.

The present invention has been made in order to solve the above problems, the object of the present invention is to reclaim the land waste by incineration of the flooring remaining by using it as a component of the thermally conductive polymer resin used as a heat dissipating material of electronic products without simply filling Provides a method of manufacturing thermally conductive polymer resins using recycled ash conductive fillers (RACFs) to recycle waste floors to prevent waste of resources and to prevent environmental pollution due to landfills. It is.

In addition, another object of the present invention is to crush the floor in the process of manufacturing a recycled ash conductive filler (RACF) for manufacturing a thermally conductive polymer resin, and then mixed with aluminum to increase the overall thermal conductivity to increase the heat dissipation effect In addition, during the firing of the flooring powder and the aluminum powder, oxygen is supplied to oxidize the outermost surface of the aluminum exposed to the outside of the flooring to form alumina (Al ₂ O ₃ ), and the part exposed to the outside to have insulation. In addition to ensuring complete insulation, the aluminum contained in the flooring material remains aluminum with high thermal conductivity, which ensures insulation and has maximum thermal conductivity. Recycled Ash Conductive Filler (RACF) To provide a method for producing a thermally conductive polymer resin using .

The present invention for solving this problem;

A mixing step of mixing the flooring material and the aluminum powder, a first grinding step of pulverizing the mixture mixed in the mixing step, a firing step of firing the mixed powder produced in the first grinding step, and the firing step And a filling step of forming a thermally conductive polymer resin by filling the base resin with a secondary crushing step of pulverizing the fired material again and a heat dissipating filler (RACF) generated in the second crushing step. do.

Here, the bottom ash is characterized in that formed by separating the foreign matter after incineration at domestic waste temperature 800 ~ 1,000 ℃.

And, the mixing step is characterized in that the mixing of 50 to 70 parts by weight of the flooring material and 30 to 50 parts by weight of aluminum powder.

On the other hand, in the firing step, the plastic working at a temperature of 700 ~ 800 ℃, by supplying excess air into the firing furnace is characterized in that the aluminum exposed to the outside of the flooring.

Here, the secondary grinding step is characterized in that the fired material is ground to an average particle size of 40 ~ 100㎛ size.

At this time, the secondary grinding step is characterized in that by supplying excess air to oxidize the aluminum exposed to the outside of the floor during the grinding process.

And, the filling step is characterized in that for mixing the heat dissipation filler 30 to 50 parts by weight and the base resin 50 to 70 parts by weight.

In addition, the filling step is characterized by adding 10 to 30 parts by weight of an additive including an antioxidant, a heat stabilizer, a flame retardant, a flow enhancer.

Here, the base resin is characterized in that the heat deflection temperature (HDT, ASTM D648, 18.6Kgf standards) is made of a thermoplastic engineering plastic (engineering plastic) higher than 150 ℃.

At this time, the filling step is characterized by supplying the base resin and the additive to the extruder to melt at a set temperature, and then filling the heat dissipation filler (RACF, Recycled Ash Conductive Filler) and characterized in that the extrusion process into a pellet shape.

In addition, when the heat dissipation filler (RACF, Recycled Ash Conductive Filler) is filled, it is characterized in that it is supplied by preheating to 150 ℃.

According to the present invention of the above configuration, by incineration of the domestic waste and using the remaining flooring material as a component of the thermally conductive polymer resin used as a heat dissipating material of electronic products without simply landfill, by recycling the flooring to be discarded to prevent waste of resources It can be, and there is an effect to prevent environmental pollution due to the flooring buried.

In addition, the present invention is not only to increase the overall heat conductivity by increasing the overall thermal conductivity by crushing the flooring material in the process of manufacturing a recycled ash conductive filler (RACF, Recycled Ash Conductive Filler (RACF) for manufacturing a thermally conductive polymer resin to increase the heat dissipation effect, During the firing of the flooring powder and the aluminum powder, oxygen is supplied to oxidize the outermost surface of aluminum exposed to the outside of the flooring to form alumina (Al ₂ O ₃ ), so that the part exposed to the outside is completely insulating. In addition to being insulated, the aluminum contained in the interior of the flooring material has the effect of having the maximum thermal conductivity while ensuring insulation while leaving the aluminum with high thermal conductivity as it is.

1 is a conceptual diagram of a state where a conventional resin composition for high thermal conductivity insulating material is applied.

Figure 2 is a flow diagram of a method for manufacturing a thermally conductive polymer resin using a waste incineration bottom ash heat radiation filler (RACF, Recycled Ash Conductive Filler) according to the present invention.

3 is a conceptual diagram of filling a heat radiation filler in the base resin in the method of manufacturing a thermally conductive polymer resin using a waste incineration bottom ash heat radiation filler (RACF, Recycled Ash Conductive Filler) according to the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the present invention. The same reference numerals are used for the same elements in the drawings, and duplicate descriptions of the same elements are omitted. And, it is to be understood that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth.

2 is a flow chart of a method for manufacturing a thermally conductive polymer resin using a waste incineration bottom ash heat dissipation filler (RACF, Recycled Ash Conductive Filler) according to the present invention, Figure 3 is a waste incineration bottom ash heat dissipation filler (RACF, Recycled Ash Conductive) In the method of manufacturing a thermally conductive polymer resin using a filler) is a conceptual diagram of filling the heat radiation filler in the base resin.

The present invention relates to a method for producing a thermally conductive polymer resin using a flooring material for recycling the floorings generated from household waste or flooring, as shown in Figure 2, the composition is a mixing step of mixing the flooring material and aluminum powder (S100) and the mixing In the first grinding step (S200) for grinding the mixed mixture in step (S100), the firing step (S300) for firing the mixed powder produced in the first grinding step (S200), and in the firing step (S300) Secondary crushing step (S400) for pulverizing the produced plastic material, and the filling step (S500) to form a thermally conductive polymer resin by mixing the heat-dissipating filler and the base resin generated in the second crushing step (S400). .

Here, the flooring used in the mixing step (S100) is formed by firing the household waste or building flooring, incineration of household waste and building flooring at a temperature of 800 ~ 1,000 ℃, foreign matters such as glass, scrap metal, ceramics, etc. To remove the flooring material.

At this time, in the mixing step (S100), the flooring material and the aluminum powder is mixed, 50 to 70 parts by weight of the flooring material and 30 to 50 parts by weight of the aluminum powder is mixed to form a mixture, the aluminum powder has a particle size (254㎛) of 100mesh or more Powder having the following particle size) is used.

Here, the components of the flooring material include silicon dioxide (SiO ₂ ) of about 32%, iron oxide (Fe ₂ O ₃ ) of about 8%, aluminum oxide (alumina, Al ₂ O ₃ ) of about 8%. However, the overall thermal conductivity is not high.

Therefore, when the flooring material is mixed in an amount of more than 70 parts by weight or less than 30 parts by weight of aluminum powder, the flooring material has a thermal conductivity of more than a certain level, but because it is not high, the overall thermal conductivity is lowered, so it is not suitable for use as a heat dissipating material. When using less than 50 parts by weight of the flooring material or more than 50 parts by weight of aluminum powder, even if a large amount of aluminum powder having good thermal conductivity is not significantly improved thermal conductivity.

That is, in the firing step (S300) and the second crushing step (S400) to be described later, the aluminum exposed to the outside of the flooring material is oxidized with alumina to increase insulation, whereas the thermal conductivity of aluminum is 208W / m _· k, whereas the thermal conductivity of alumina Since 20W / m _· k is low, most aluminum in excess of 50 parts by weight is oxidized to alumina state, so the thermal conductivity cannot be significantly improved. Thus, 50 to 70 parts by weight of flooring material and 30 to 50 parts by weight of aluminum powder are mixed and insulated. It is possible to achieve the best thermal conduction efficiency.

In addition, the primary crushing step (S200) is to crush the mixture of the flooring material and the aluminum powder formed in the mixing step (S100), it is pulverized so that the average particle size of the mixture is 4 to 5 mm.

At this time, when the average particle size of the mixture is too large, when filling the base resin, it is difficult to evenly dispersed in the base resin has a problem that the thermal conductivity is lowered.

Here, after mixing the aluminum powder and the flooring material in advance in the mixing step (S100), by passing through the first grinding step (S200), the flooring particles and the aluminum powder in the grinding process to be evenly mixed.

In the firing step (Sintering, S300), the mixture of the flooring particles and the aluminum powder is heated to a temperature of 700 to 800 ° C., and the plastic processing is performed. The melting point of the floor material is about 1200 ° C. and the melting point of aluminum is about 660.32 ° C. Therefore, only aluminum is melted so that the flooring particles are bonded to the aluminum and aggregated into a single mass.

Here, in the firing step (S300), the excess air (excess air) is supplied to the inside of the firing furnace in the plastic working process, the excess air contains a large amount of oxygen.

Therefore, excess air containing a large amount of oxygen comes into contact with aluminum exposed to the outside of the flooring material, thereby oxidizing the exposed aluminum to alumina (Al ₂ O ₃ ).

At this time, aluminum has high electrical conductivity, while aluminum is oxidized to alumina, so that the insulating material is insulated, and together with the insulating flooring material, all parts exposed to the outside are oxidized to alumina, thereby making the whole insulating material.

On the other hand, in the firing step (S300) is maintained at a firing temperature of 700 to 800 ℃, the melting point of the aluminum is about 660 ℃, the melting point of the flooring is about 1200 ℃, so that the aluminum is melted by firing at a temperature in between You can combine the grains.

Here, if the firing temperature is higher than 800 ℃ energy consumption is high, but there is no effect, so it is maintained below 800 ℃, when firing at a temperature lower than 700 ℃ is higher than the melting point of aluminum, but it takes a lot of time Therefore, it maintains 700 to 800 ℃.

In addition, in the firing step (S300), the mixture of the bottom ash and the aluminum united together is pulverized into small particles to perform a secondary crushing step (S400) of manufacturing a recycled ash conductive filler (RACF). In the secondary grinding step (S400) using a ball mill or an air jet mill and the like to grind to have an average particle of 40 to 100㎛.

At this time, when the particle size is larger than 100㎛, it is not evenly mixed when mixing with the base resin in the filling step (S500) to be described later, when the particle size is 40㎛ small because excessive cost is consumed to form the particle size and economic efficiency is deteriorated The particle size is maintained at 40 to 100 μm.

On the other hand, in the secondary crushing step (S400) is to supply the excess air as in the above-described firing step (S300), the excess air contains a large amount of oxygen.

Thus, when the aluminum portion is exposed to the outside in the process of grinding in the secondary grinding step (S400), it is oxidized to alumina by oxygen contained in the excess air, is exposed to the outside in the secondary grinding step (S400) By oxidizing all aluminum with alumina, insulation is improved.

In addition, the firing step (S300) and the secondary grinding step (S400) to maintain the water content (water content) to 0.1% or less.

And, the filling step (S500) is, as shown in Figure 3, by using an extruder 100 is filled with a heat dissipation filler (RACF, Recycled Ash Conductive Filler) formed in the secondary grinding step (S400) to the base resin In addition, additives including antioxidants, heat stabilizers, flame retardants, flow enhancers, and the like are added to prevent the base resin from being more resistant to heat, not burning well, and oxidizing.

At this time, the base resin used in the filling step (S500) is to use a thermoplastic engineering plastic (heat deformation temperature (HDT, ASTM D648, 18.6Kgf basis)) higher than 150 ℃, for example PA66, PPS, By using PAI, PAA, PA46, PA9T, PEI, PSU, etc., even if high heat is generated from electronic components, it is possible to stably release heat to the outside without deformation.

On the other hand, the filling step (S500) is to use an extruder 100, the extruder 100 is to maintain a suitable temperature higher than 150 ℃ to maintain a stable molten state according to the material of the engineering plastic used do.

Here, all of the extruder 100 has a primary supply port 110 formed at the top to inject a base resin and a functional additive at the same time to melt the base resin, the second supply located in the rear of the extruder 100 Filled with a heat-dissipating filler (RACF, Recycled Ash Conductive Filler) through the sphere (120), when filling a heat-resistant filler (RACF, Recycled Ash Conductive Filler), the heat-resistant filler (RACF, Recycled Ash Conductive Filler) to 150 ℃ By pre-heating and supplying, the base resin is prevented from being hardened by the low temperature of the Recycled Ash Conductive Filler (RACF), thereby ensuring stable filling.

Thus, the inside of the extruder 100 is filled with a heat dissipating filler (RACF, Recycled Ash Conductive Filler) in the base resin through the outlet 130 formed in the rear end of the extruder 100, the pellet-shaped recycled thermal conductive polymer resin is discharged Will be.

On the other hand, the base resin is added to 30 to 50 parts by weight, and the additive is 10 to 30 parts by weight of a heat dissipation filler (RACF, Recycled Ash Conductive Filler) in 50 to 70 parts by weight.

At this time, when filling the base resin with a heat-dissipating filler (RACF, Recycled Ash Conductive Filler), when less than 30 parts by weight of a heat-dissipating filler (RACF, Recycled Ash Conductive Filler) is used as a heat dissipating material is lowered The following becomes unsuitable.

In addition, in order to obtain high thermal conductivity, it is to increase the content of the recycled ash conductive filler (RACF) in the resin together with the efficient dispersion of the recycled ash conductive filler (RACF). Increasing the content of Ash Conductive Filler) increases the viscosity, and if the viscosity is increased, the heat dissipating filler (RACF, Recycled Ash Conductive Filler) is not effectively dispersed and rather degrades the thermal conductivity. Conductive Filler) is filled to 50 parts by weight or less.

Therefore, the heat dissipation filler in the 50 to 70 parts by weight of the base resin is filled in 30 to 50 parts by weight to maintain the best thermal conductivity by efficiently distributing the heat dissipation filler (RACF, Recycled Ash Conductive Filler) in the base resin.

Although the preferred embodiments of the present invention have been described above, the scope of the present invention is not limited thereto, and the scope of the present invention extends to the scope of the present invention to those which are substantially equivalent to the embodiments of the present invention. Various modifications can be made by those skilled in the art without departing from the scope of the present invention.

The present invention relates to a method for manufacturing a thermally conductive polymer resin using a waste incineration flooring heat dissipation filler, and more specifically, to a thermally conductive polymer resin having high insulation and thermal conductivity properties using a discarded flooring material (a flooring material remaining after incineration of domestic waste). The present invention relates to a method for manufacturing a thermally conductive polymer resin using a recycled ash conductive filler, which can not only increase resources recyclability but also prevent environmental pollution caused by landfilling.

Claims

A mixing step of mixing the flooring material with the aluminum powder,

A first grinding step of grinding the mixture mixed in the mixing step,

A firing step of firing the mixed powder produced in the first grinding step;

A second crushing step of pulverizing the fired product produced in the calcination step;

A thermally conductive polymer resin using a waste incineration flooring material heat dissipation filler comprising: a filling step of forming a thermally conductive polymer resin by filling a base resin with a heat dissipating filler (RACF) generated in the second milling step; Manufacturing method.
The method of claim 1,

The flooring material is a thermal conductive polymer resin manufacturing method using a waste incineration flooring heat dissipation filler, characterized in that formed by separating the foreign matter after incineration at domestic waste temperature 800 ~ 1,000 ℃.
The method of claim 1,

In the mixing step, 50 to 70 parts by weight of the flooring material and 30 to 50 parts by weight of aluminum powder, the method for producing a thermally conductive polymer resin using a waste incineration flooring heat radiation filler.
The method of claim 1,

In the firing step, the plastic working at a temperature of 700 ~ 800 ℃,

A method of producing a thermally conductive polymer resin using a heat dissipating filler incineration flooring waste, characterized in that for oxidizing aluminum exposed to the outside of the flooring material by supplying excess air into the kiln.
The method of claim 1,

The secondary crushing step is a thermal conductive polymer resin manufacturing method using a heat dissipation filler waste incineration flooring, characterized in that the pulverized material is crushed to an average particle size of 40 ~ 100㎛ size.
The method of claim 5,

The secondary grinding step is a method of producing a thermally conductive polymer resin using a heat dissipating filler incineration floor ash, characterized in that for supplying excess air to oxidize aluminum exposed to the outside of the floor during the grinding process.
The method of claim 1,

In the filling step, 30 to 50 parts by weight of the heat dissipation filler and 50 to 70 parts by weight of the base resin, the method for producing a thermally conductive polymer resin using a waste incineration bottom ash heat dissipation filler.
The method of claim 7, wherein

The filling step is a method for producing a thermally conductive polymer resin using a heat dissipating waste incinerator bottom ash, characterized in that the addition of 10 to 30 parts by weight of an additive including an antioxidant, a heat stabilizer, a flame retardant, a flow enhancer.
The method of claim 8,

The base resin is a thermally conductive polymer resin manufacturing method using a heat dissipation filler waste incineration flooring material, characterized in that the heat distortion temperature (HDT, ASTM D648, 18.6Kgf standards) of higher than 150 ℃ thermoplastic engineering plastics.
The method of claim 9,

In the filling step, the base resin and the additives are supplied to an extruder to be melted at a set temperature, and then a heat dissipation filler (RACF, Recycled Ash Conductive Filler) is filled and extruded into pellets. Method for producing a polymeric polymer resin.
The method of claim 10,

When filling the heat dissipation filler, a thermal conductive polymer resin manufacturing method using a heat dissipation filler incineration flooring waste, characterized in that preheated to 150 ℃.