KR20140073866A

KR20140073866A - Carbon nano-material solids and a method for solidifying the powder of carbon nano-material

Info

Publication number: KR20140073866A
Application number: KR1020120141837A
Authority: KR
Inventors: 류상효; 최상규; 황호수; 정충헌; 오동훈; 이연자; 장영찬
Original assignee: 금호석유화학 주식회사
Priority date: 2012-12-07
Filing date: 2012-12-07
Publication date: 2014-06-17

Abstract

The present invention relates to a carbon nanomaterial powder solid and a manufacturing method thereof, and more specifically, to a carbon nanomaterial solid and a method for manufacturing a solid using carbon nanomaterial powder, wherein the method can prevent powder from being scattered due to the application of existing carbon nanomaterial powder to a polymer composite through a simple process; improves physical properties; and reduces packing and logistic costs by manufacturing a solid with a specific shape and high bulk density using only a tablet press without adding a solvent or additives to the carbon nanomaterial powder.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a carbon nano-

The present invention relates to a carbon nanomaterial solid body and a manufacturing method thereof. More particularly, the present invention relates to a carbon nanomaterial solid body and a method of manufacturing the carbon nanomaterial body by using a rotary tablet machine without mixing a solvent or an additive, It is a simple manufacturing process that solves the scattering problem of powder generated when applying carbon nanomaterial as powder to polymer composite material and can improve the physical properties by application and drastically reduce packing and distribution costs. To a method of producing a solid from a carbon nanomaterial powder.

Carbon nanomaterials include fullerene, carbon nanotube (CNT), graphene, and graphite nano plate, depending on the shape of the material. Among them, carbon nanotubes have one The hexagonal honeycomb-shaped graphite surface bonded to three different carbon atoms of carbon atoms is a nano-sized, round-shaped, macromolecule with unique physical properties depending on its size and shape. Carbon nanotubes are light in weight and have good electrical conductivity as good as copper. Their thermal conductivity is as good as diamond and their tensile strength is just as good as steel. And may be divided into single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), and multi-walled carbon nanotubes (RNCs)

Due to its excellent physical properties, these carbon nanotubes are most popular as fillers for various polymer composite materials such as antistatic polymer composite materials, electromagnetic wave shielding polymer composite materials, heat radiation polymer composite materials, and high strength polymer composite materials, and carbon nanotubes Many researches and developments have been made for the commercialization of polymer composite materials.

However, in spite of much research and development, it is suggested that carbon nanotubes are scattered due to low apparent density of carbon nanotube powders in polymer composite materials and human health hazards.

In order to utilize nanomaterials such as carbon nanotubes, a carbon nano powder is generally mixed with polymer pellets. In this case, when the carbon nanomaterial powder is put into an extruder together with the polymer pellets, the carbon nanomaterial powder and the polymer Layer separation due to the large density difference of the pellets and the dispersion of the carbon nanomaterial due to the phenomenon are still obstacles to the mass use of carbon nanomaterials. In addition, from the standpoint of the carbon nanomaterial producer, packing and distribution costs, which are increased due to the very low apparent density of the carbon nanomaterials made of powder, are becoming burdensome.

The following techniques have been disclosed as methods for improving the apparent density of carbon nanomaterials, particularly carbon nanotubes, disclosed in patent documents to date.

According to Korean Patent Registration No. 10-0955295, "a method for manufacturing a solid body including nano-carbon", a nano-carbon solid body including nano-carbon, metal (including oxide and ion) and resin is disclosed. However, the nanocarbon solids prepared by this method contain metals and resins in order to increase the bonding force for solid-state molding. Therefore, when applied to a polymer composite material, a polymer used as a matrix, a metal contained in a nano- There is a serious problem that the polymer may not be used in a composite material due to its reactivity or compatibility and the expression of important physical properties of the nano-carbon may be deteriorated. In addition, there are various steps of mixing, separating, molding and drying nano- A manufacturing process is required.

Also, in Korean Patent Laid-Open Publication No. 2011-0065704 entitled " Method for producing nano-carbon solid body, nano-carbon solid body, nano-carbon dispersion and method for producing nano-carbon material ", nano-carbon cutting step, nano- Dispersing the nanocarbon with a dispersing machine, dispersing the nanocarbon in a disperser, adding a coagulant to the dispersed nanocarbon solution to form a nanocarbon sludge, removing the liquid component from the nanocarbon sludge, pulverizing or crushing the nanocarbon, A nano-carbon solidification step in which a nano-carbon solidification step in which a nano-carbon powder is made into a carbon powder and a nano-carbon powder is molded in a predetermined shape and then dried to produce a solid body. However, this method does not include the metal and resin in the nano-carbon solid body, but the dispersant and coagulant used in the manufacturing process remain in the nano-carbon solid body, which may cause unexpected side effects when used in the production of polymer composite material, This method also has a disadvantage in that it requires several steps of manufacturing process.

In Korean Patent Laid-Open Publication No. 2010-0038094, entitled " Carbon nanotube granules and a method for producing the same, ", Mitsunosaki Kogyo Co., Ltd., using carbon nanotubes as an interface between a gas and a liquid, Wherein the weight ratio of the carbon nanotube to the solvent is 1: 3 or more. 2. The method of manufacturing a carbon nanotube assembly according to claim 1, wherein the weight ratio of the carbon nanotube to the solvent is 1: 3 or more. However, the high density of the carbon nanotubes by such a method has the disadvantage that the particles can not completely solve the scattering problem due to the presence of the fine carbon nanotube powder in the granules, and the mixing, degassing, and drying processes are required in the manufacturing process, There are disadvantages.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, that is, when a polymer composite material is used in a polymer composite material due to the presence of a metal and a resin or a dispersant added during solidification of the carbon nanomaterial powder, undesirable additives are introduced, And problems of scattering due to low apparent density of carbon nanomaterial powder and human health hazards thereof and problems of layer separation due to large density difference of carbon nanomaterial powder and polymer pellets when the polymer pellets are introduced into an extruder As a result of extensive studies to solve the problems, it has been found that a simple process can solve such a conventional serious problem if the carbon nanomaterial is solidified under specific conditions, thus completing the present invention.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a carbon nanomaterial solid body having a specific size and a high apparent density, which are free from solvents and additives and excellent in packing and distribution conditions.

Another object of the present invention is to provide a carbon material solid body in which physical properties of a carbon nanomaterial powder are maintained as it is when applied to a polymer composite material, thereby maximizing utilization of the carbon nanomaterial.

Another object of the present invention is to provide a method for producing a carbon nanomaterial solid which solidifies a carbon nanomaterial powder by a simple and economical process.

It is another object of the present invention to provide a method of solidifying carbon nanomaterial powder without adding a solvent or an additive.

In order to solve the problems of the present invention as described above, the present invention provides a method for producing a polyurethane foam, which does not contain a solvent or an additive and has a solid size of 2 to 10 mm and a thickness of 1 to 6 mm, Shape, etc., and provides a carbon nanomaterial solid body having an apparent density of 0.05 to 0.60 g / mL.

The present invention also provides a method for manufacturing a carbon nanomaterial solid body, which comprises injecting a carbon nanomaterial powder into a rotary tablet press without mixing a solvent or an additive, and applying pressure to form a solid body.

Also, the present invention provides a method for producing a carbon nanomaterial / polymer composite material using a solid carbon nanomaterial having a solid size of 2 to 10 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / ml to provide.

Also, the present invention provides a carbon nanofiber / polymer composite material manufactured using a solid carbon nanomaterial having a solid size of 2 to 10 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / ml .

Since the carbon nanofiber solid body according to the present invention does not contain any additive such as solvent, metal, resin, dispersant and the like at all, there is no problem such that the additive is introduced into the polymer composite material, In addition, it exhibits the same effect as when the powder is used as it is in the production of a composite material with a polymer, and has an excellent effect of not causing a problem of separation of layers and degradation of physical properties with polymer pellets.

In addition, when the solidification method of the present invention is used, since the carbon nanostructure powder is solidified by using only a tablet machine without using any solvent or additive at all, the manufacturing process is very simple.

Further, by using the solid body produced according to the present invention, scattering problems caused by the use of the carbon nanomaterial powder and the packaging and distribution conditions of the powder are dramatically improved, thereby providing economical and hygienic effects in manufacturing and supplying products .

Therefore, the results of the present invention show a decisive effect that economically and most effectively maximizes the use of the carbon nanomaterial powder.

1 is a schematic view showing a typical form of a carbon nanomaterial solid body produced by the method of the present invention.

Hereinafter, the present invention will be described in detail as an embodiment.

The present invention relates to a carbon nanostructure material which does not contain any solvent or additive other than the carbon nanomaterial component and which has a solid size of 2 to 10 mm and a thickness of 1 to 6 mm and a cross section shape selected from oval, And is characterized by a carbon nanomaterial solid having an apparent density of 0.05 to 0.60 g / mL.

The carbon nanomaterial solid of the present invention is produced by solidifying the carbon nanomaterial powder into a solid form using a rotary tablet machine.

Particularly, in the present invention, carbon nanomaterial powder is directly injected into a rotary tablet machine without mixing solvents and additives, and pressure is applied thereto to form a solid body.

The carbon nanomaterial used in the present invention may be in the form of one or a mixture of two or more selected from carbon nanotubes, carbon nanofibers, graphene and graphite nanoplates, preferably carbon nanotubes.

The carbon nanofiber powder may preferably have an average particle diameter of 0.05 to 100 탆, an apparent density of 0.01 to 0.20 g / mL, and a repose angle of 10 째 to 70 째. Particularly, those having an average particle diameter of 0.1 to 85 μm, an apparent density of 0.01 to 0.20 g / mL and a repose angle of 20 ° to 60 ° can be used more preferably. If the powder is out of the condition of the powder, the solid body may not be formed or the molding may be defective during the solidification process.

The rotary tablet machine used in the present invention may be a tablet machine used for manufacturing tablets such as pharmaceuticals or foods.

In the solidification process of the present invention, the pressure applied to the carbon nanomaterial powder is preferably adjusted within a range of from 100 to 700 kg / cm ² , and more preferably from 300 to 500 kg / cm ² . If the pressure is too low, the solids may easily break, and if it is too strong, solidification is easy. However, when the carbon nanomaterial solid is used for the production of the polymer composite material due to excessive pressure, the physical properties of the carbon nanomaterial may be deteriorated.

In the solidification process of the present invention, the punch size of the rotary tablet machine and the rotation speed of the turntable are appropriately selected without mixing solvents and additives, and the solid body having a specific size and apparent density is manufactured. The shape of the solid body can be variously shaped as shown in FIG. 1, wherein the solid body shape is preferably 2 to 10 mm in size, 1 to 6 mm in thickness, Ellipsoid, triangle, polygonal shape larger than a rectangle, star shape, and the like, and it is preferable that the carbon nanotube is manufactured from a solid material having a bulk density of 0.05 to 0.60 g / mL, more preferably 2 to 6 mm, Is 2 to 5 mm, and the apparent density is 0.1 to 0.5 g / mL. If the size is too large, layer separation due to the difference in size between the carbon nanomaterial solid and the polymer pellet occurs again. If the size is too small, the productivity is lowered in manufacturing the solid body using the rotary tablet machine, The problem also occurs again. If the thickness is too large, the layer separation by the size difference between the carbon nanomaterial solid and the polymer pellet occurs again. If the thickness is too small, the moldability becomes poor during the production of the solid body, and the solid body is easily broken. The apparent density affects the physical properties of the carbon nanomaterial and the packing and distribution due to the solidification when the polymer is used in the polymer composite material. When it is too large, there is a problem that the physical properties are deteriorated when applied to the polymer composite material. The economical advantage due to the solidification of the carbon nanomaterial is eliminated. In addition, it is preferable that the carbon nanomaterial powder used for solidification is prepared so as to have an angle of repose of 10 ° to 70 ° in terms of solid molding using a rotary tablet machine.

In order to produce such a solid body according to the present invention, the application conditions of the rotary tablet machine are preferably such that the punch size is 1 to 10 mm, preferably 2 to 6 mm, the rotation speed of the turntable is 10 to 60 rpm, The range of 20 to 50 rpm is suitable in terms of the productivity of the solid body using the rotary tablet machine and the characteristics such as the size, thickness, and apparent density of the solid body.

In the solidification process of the carbon nanomaterial powder according to the present invention, a solvent, a resin, or an additive is not required to solidify the carbon nanomaterial powder, and solidification can be achieved by a simple process that is not complicated.

The carbon nanomaterial solid body produced according to the present invention is prepared as described above and does not contain solvents or additives at all. The solid body has a size of 2 to 10 mm, a thickness of 1 to 6 mm, , A triangular shape, a polygonal shape larger than a rectangle, and a star shape, and has a shape of a solid carbon nanomaterial having an apparent density of 0.05 to 0.60 g / mL. Preferably, the angle of repose of the carbon nanomaterial powder used for solidification is 10 ° to 70 °. At this time, the angle of repose has a preferable range in terms of solidification using a rotary tablet machine.

In the meantime, the present invention is characterized in that the solid body has a size of 2 to 10 mm, a thickness of 1 to 6 mm, a shape selected from an ellipse, a triangle, a polygonal shape larger than a quadrangle, a star shape, and an apparent density of 0.05 to 0.60 g / And a method of producing a carbon nanomaterial / polymer composite material using the carbon nanomaterial / polymer composite material.

Examples of the polymer material used herein include thermoplastic resins such as polycarbonate, polyethylene terephthalate, amorphous polyethylene terephthalate, glycol-modified polyethylene terephthalate, cyclohexane-modified polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, Polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, Butadiene-styrene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polychlorotrifluoroethylene, polyurethane, ethylene < RTI ID = 0.0 > The Acrylonitrile-butadiene-styrene, polycarbonate / cyclohexane-modified polyethylene terephthalate, acrylonitrile-butadiene-styrene / polyamide, polybutylene terephthalate There may be used a polymer selected from the group consisting of polyvinylidene fluoride, phthalate / polyethylene terephthalate, polybutylene terephthalate / liquid crystal polymer, polysulfone / modified polyphenylene oxide, polypropylene / polyamide, polycarbonate / The ratio of the shape and the polymer material used can be 100 parts by weight of the polymer and 0.1-20 parts by weight of the carbon nano material pellets.

The carbon nanomaterial solid according to the present invention can contain a larger amount of the carbon nanomaterial in the same volume of the container due to the higher apparent density compared to the powder nanomaterial having a very low apparent density, In the case of putting in a packaging container, there is no problem of scattering of powder, so that it has a superior effect in terms of economical and convenient handling in the packaging and distribution conditions.

Meanwhile, the use of the carbon nanofiber solid body according to the present invention in a polymer composite material is generally performed in the same manner as a carbon nanofiber powder is applied to the production of a polymer composite material in order to improve electrical and mechanical properties And can be utilized.

Particularly, when the carbon nanomaterial solid body according to the present invention is used, when the polymer material and the composite material are produced due to the morphological characteristics of the solid body, the carbon nanomaterial solid body and the polymer pellets are uniformly mixed well Dispersed state, the dispersing effect is excellent and the same shape as that of the polymer material can be obtained, so that the effect of improving the dispersibility in terms of physical properties can be obtained, so that the effect on the physical properties of the composite material can be expected to be superior to that of the powder .

Particularly, since the carbon nanomaterial according to the present invention is solidified, it can not only solve the scattering problem in powder but also has a polymeric material mixed with carbon nanomaterial mainly in the form of pellet. Therefore, in the production of carbon nanomaterial / polymer composite material There is no problem of layer separation due to size difference or density difference generated when the polymer pellets are introduced into the extruder according to the size, thickness and apparent density of the solid body, and pellets are not smoothly injected. The physical properties such as electrical conductivity and mechanical properties of composite materials, which are the most important materials used in polymer composite materials, are very useful in that they do not cause a problem of deterioration as compared with the case of using carbon nanomaterials as powders.

In addition, when used in a polymer composite material, problems of scattering due to low apparent density of the carbon nanomaterial powder and human health hazards thereof, and a large density difference between the carbon nanomaterial powder and the polymer pellet when the polymer pellet is introduced into the extruder, Layer separating phenomenon can be solved.

Hereinafter, the present invention will be described by way of examples. The solid form of the carbon nanomaterial powder according to the present invention and the method for its production are illustrated by the following several examples, but these examples should not be construed as limiting the present invention.

Example 1

A carbon nanotube powder having an average particle diameter of 0.1 μm, an apparent density of 0.06 g / mL and an angle of repose of 23 ° was introduced into a hopper of a rotary tablet machine without using a solvent or an additive, and a rectangular punch having a size of 2 mm was used. After setting the thickness to be 3 mm, a carbon nanotube solid having a size of 2 mm and a thickness of 3 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid obtained was 0.41 g / mL.

Example 2

A carbon nanotube powder having an average particle size of 0.1 μm, an apparent density of 0.06 g / mL and an angle of repose of 23 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a square punch having a size of 3 mm was used to form a solid body After setting the thickness to be 3 mm, a carbon nanotube solid having a size of 3 mm and a thickness of 3 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The bulk density of the prepared carbon nanotube solid was 0.36 g / mL.

Example 3

A carbon nano tube powder having an average particle diameter of 83 μm, an apparent density of 0.02 g / mL and an angle of repose of 58 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a square punch having a size of 4 mm Was set to be 2 mm. Then, a carbon nanotube solid having a size of 4 mm and a thickness of 2 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid produced was 0.12 g / mL.

Example 4

A carbon nanotube powder having an average particle size of 83 μm, an apparent density of 0.02 g / mL and an angle of repose of 58 ° was introduced into a hopper of a rotary tablet machine without mixing solvents or additives, and a rectangular punch having a size of 4 mm was used to form a solid After setting the thickness to 3 mm, a carbon nanotube solid body having a size of 4 mm and a thickness of 3 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid produced was 0.09 g / mL.

Example 5

A carbon nano tube powder having an average particle size of 67 μm, an apparent density of 0.034 g / mL and an angle of repose of 45 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a rectangular punch having a size of 4 mm was used to insert the solid After setting the thickness to be 4 mm, a carbon nanotube solid having a size of 4 mm and a thickness of 4 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid produced was 0.18 g / mL.

Example 6

A carbon nano tube powder having an average particle size of 67 μm, an apparent density of 0.034 g / mL and an angle of repose of 45 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a rectangular punch having a size of 4 mm was used to insert the solid After setting the thickness to 5 mm, a carbon nanotube solid body having a size of 4 mm and a thickness of 5 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid produced was 0.16 g / mL.

Example 7

A carbon nano tube powder having an average particle diameter of 15 μm, an apparent density of 0.042 g / mL and an angle of repose of 31 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a square punch having a size of 5 mm was used to form a solid After setting the thickness to be 4 mm, a carbon nanotube solid having a size of 5 mm and a thickness of 4 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The bulk density of the prepared carbon nanotube solid was 0.24 g / mL.

Example 8

A carbon nano tube powder having an average particle diameter of 15 μm, an apparent density of 0.042 g / mL and an angle of repose of 31 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a square punch having a size of 6 mm was used to mix the solid After setting the thickness to 4 mm, a carbon nanotube solid having a size of 6 mm and a thickness of 4 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The bulk density of the prepared carbon nanotube solid was 0.21 g / mL.

Comparative Example 1 (exceeding the size of the solid body)

A carbon nanotube powder having an average particle diameter of 15 μm, an apparent density of 0.042 g / mL and an angle of repose of 31 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a rectangular punch having a size of 1.5 mm was used to form a solid Was set to a thickness of 4 mm. Then, a carbon nanotube solid having a size of 1.5 mm and a thickness of 4 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The bulk density of the prepared carbon nanotube solid was 0.27 g / mL.

Comparative Example 2 (exceeding the size of the solid body)

A carbon nano tube powder having an average particle diameter of 15 μm, an apparent density of 0.042 g / mL and an angle of repose of 31 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a rectangular punch having a size of 7 mm was used. 4 mm, and then the rotation speed of the turntable of the rotary tablet press was set to 20 rpm to prepare a carbon nanotube solid having a size of 7 mm and a thickness of 4 mm. The apparent density of the carbon nanotube solid produced was 0.19 g / mL.

Comparative Example 3 (exceeding the thickness of the solid body)

A carbon nanotube powder having an average particle size of 83 μm, an apparent density of 0.02 g / mL and an angle of repose of 58 ° was introduced into a hopper of a rotary tablet machine without mixing solvents or additives, and a rectangular punch having a size of 4 mm was used to form a solid After setting the thickness to 0.8 mm, a carbon nanotube solid body having a size of 4 mm and a thickness of 0.8 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid produced was 0.16 g / mL.

Comparative Example 4 (exceeding the thickness of the solid body)

A carbon nano tube powder having an average particle diameter of 83 μm, an apparent density of 0.02 g / mL and an angle of repose of 58 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a square punch having a size of 4 mm Was set to 7 mm, and then the rotation speed of the turntable of the rotary tablet press was set to 20 rpm to prepare a carbon nanotube solid having a size of 4 mm and a thickness of 7 mm. The apparent density of the carbon nanotube solid produced was 0.06 g / mL.

Comparative Example 5 (exceeding the apparent density of the solid body)

A carbon nano tube powder having an average particle size of 83 μm, an apparent density of 0.02 g / mL and an angle of repose of 58 ° was introduced into a hopper of a rotary press machine without mixing solvents or additives, and a square punch having a size of 6 mm was used to insert the solid Was set to be 6 mm. Then, a carbon nanotube solid having a size of 6 mm and a thickness of 6 mm was prepared with the rotation speed of the turntable of the rotary tabletting machine at 20 rpm. The apparent density of the carbon nanotube solid produced was 0.04 g / mL.

Comparative Example 6 (exceeding the apparent density of the solid body)

A carbon nanotube powder having an average particle diameter of 0.1 μm, an apparent density of 0.08 g / mL and an angle of repose of 20 ° was introduced into a hopper of a rotary tablet machine without using a solvent or an additive, and a rectangular punch having a size of 2 mm was used. After setting the thickness to be 1 mm, a carbon nanotube solid having a size of 2 mm and a thickness of 1 mm was prepared by rotating the turntable of the rotary tablet machine at 20 rpm. The apparent density of the carbon nanotube solid obtained was 0.70 g / mL.

Comparative Example 7 (average particle diameter of powder exceeded)

The carbon nanotube powder having an average particle size of 0.04 μm, an apparent density of 0.12 g / mL and an angle of repose of 63 ° was put into a hopper of a rotary press machine and a solid body was manufactured using a rotary tablet machine It was impossible to produce a solid body having a size of 2 to 6 mm in shape, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

Comparative Example 8 (average particle diameter of powder exceeded)

A carbon nanotube powder having an average particle size of 114 μm, an apparent density of 0.017 g / mL and an angle of repose of 43 ° was put into a hopper of a rotary tablet machine and a solid body was manufactured using a rotary tablet machine without mixing solvents or additives, Of 2 to 6 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

Comparative Example 9 (Apparent Density of Powder Exceeded)

The carbon nanotube powder having an average particle size of 90 μm, an apparent density of 0.008 g / mL and an angle of repose of 56 ° was put into a hopper of a rotary press machine and a solid body was manufactured using a rotary tablet machine, Of 2 to 6 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

Comparative Example 10 (Apparent Density of Powder Exceeded)

The carbon nanotube powder having an average particle diameter of 0.08 μm, an apparent density of 0.21 g / mL and an angle of repose of 54 ° was introduced into a hopper of a rotary press machine and a solid body was manufactured using a rotary tablet machine It was impossible to produce a solid body having a size of 2 to 6 mm in shape, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

Comparative Example 11 (exceeding the angle of repose of the powder)

The carbon nanotube powder having an average particle diameter of 95 μm, an apparent density of 0.15 g / mL and an angle of repose of 8 ° was put into a hopper of a rotary tablet machine and a solid body was tried to be manufactured using a rotary tablet machine without mixing with a solvent or an additive. Of 2 to 6 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

Comparative Example 12 (exceeding the angle of repose of the powder)

The carbon nanotube powder having an average particle size of 6 μm, an apparent density of 0.013 g / mL and an angle of repose of 75 ° was put into a hopper of a rotary press machine and the solid body was tried to be manufactured using a rotary tablet machine, Of 2 to 6 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

The results of the production of the solid carbon nanotubes produced according to the examples and the comparative examples are shown in FIG. 1, and the results are shown in the following Table 1 (the result of producing the carbon nanotube solid body of the example) and Table 2 As a result of the production of the carbon nanotube solid body of the comparative example).

Example One 2 3 4 5 6 7 8 use
powder Average particle diameter
(m) 0.1 0.1 83 83 67 67 15 15 Apparent density
(g / mL) 0.06 0.06 0.02 0.02 0.034 0.034 0.042 0.042 Angle of repose (°) 23 23 58 58 45 45 31 31 Solid size
(mm) 2 3 4 4 4 4 5 6 thickness
(mm) 3 3 2 3 4 5 4 4 Apparent density
(g / mL) 0.41 0.36 0.12 0.09 0.18 0.16 0.24 0.21

Comparative Example One 2 3 4 5 6 use
powder Average particle diameter
(m) 15 15 83 83 83 0.1 Apparent density
(g / mL) 0.042 0.042 0.02 0.02 0.02 0.08 Angle of repose (°) 31 31 58 58 58 20 Solid size
(mm) 1.5 7 4 4 6 2 thickness
(mm) 4 4 0.8 7 6 One Apparent density
(g / mL) 0.27 0.19 0.16 0.06 0.04 0.70 Remarks Size range
Excess Thickness range
Excess Apparent density
Out of range

Table 3 below shows the case where the powder condition is exceeded as a result of producing the carbon nanotube solid of the comparative example.

Comparative Example 7 8 9 10 11 12 use
powder Average particle diameter
(m) 0.04 114 90 0.08 95 6 Apparent density
(g / mL) 0.12 0.017 0.008 0.21 0.15 0.013 Angle of repose (°) 63 43 56 54 8 75 Solid size
(mm) Solid
Produce
no Solid
Produce
no Solid
Produce
no Solid
Produce
no Solid
Produce
no Solid
Produce
no thickness
(mm) Apparent density
(g / mL) Remarks Average particle diameter
Out of range Apparent density
Out of range Angle of repose
Out of range

As shown in Tables 1 and 2-3, when the manufacturing method of the present invention is used, a solid body of carbon nanotube powder having various sizes, thicknesses, and bulk densities can be obtained by using one rotary kneader alone It can be manufactured by only the process.

When carbon nanotube powders which do not satisfy the characteristics of an average particle size of 0.05 to 100 μm, an apparent density of 0.01 to 0.20 g / mL and a repose angle of 10 ° to 70 ° as in Comparative Examples 7 to 12 are used, It was confirmed that it is not possible to produce a solid body having a solid size of 2 to 6 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL.

Production Example 1

The mixing amount of the carbon nanotube solid product prepared in Example 1 and the polycarbonate / acrylonitrile-butadiene-styrene copolymer (PC / ABS) compounding product (HAC-8265) 3% by weight. The resulting mixture was thoroughly mixed with a small tumbler mixer for uniform mixing, and extruded at a temperature of 240-290 DEG C in a twin-screw extruder having a diameter of 30 mm and an L / D of 36, And then dried in a circulating hot air dryer maintained at 80 ° C for 4 hours. The injection temperature was changed from 250 to 300 ° C in a 160 ton injection machine and the mold temperature was set to 65 ° C to prepare a polymer composite material specimen.

Production Example 2

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 2 was used.

Production Example 3

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 3 was used.

Production Example 4

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 4 was used.

Production Example 5

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 5 was used.

Production Example 6

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 6 was used.

Preparation Example 7

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 7 was used.

Production Example 8

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Example 8 was used.

Manufacturing Comparative Example 1

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Comparative Example 1 was used.

Manufacturing Comparative Example 2

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Comparative Example 2 was used.

Manufacturing Comparative Example 3

Except that the carbon nanotube solid obtained in Comparative Example 3 was used.

Manufacturing Comparative Example 4

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Comparative Example 4 was used.

Manufacturing Comparative Example 5

The same procedure as in Production Example 1 was carried out except that the carbon nanotube solid obtained in Comparative Example 5 was used.

Manufacturing Comparative Example 6

Except that the carbon nanotube solid obtained in Comparative Example 6 was used.

Manufacturing Comparative Example 7

The carbon nanotube powder having an average particle diameter of 15 μm, an apparent density of 0.042 g / mL and an angle of repose of 31 ° was directly used without using the carbon nanotube solid produced in the above Examples or Comparative Examples, The polymer composite test specimens were prepared by the same method. The content of the carbon nanotube powder used was 3% by weight of the compounding amount, which was the same as that of Preparation Example 1.

Experimental Example

In order to confirm the physical properties of the carbon nanomaterial / polymer composite material prepared in the production examples and the comparative production examples, the test specimens prepared in the production examples and the comparative production examples were subjected to an Izod impact strength test method Was measured by ASTM D256 (1/8 inch). Test specimens having surface resistances of 100 mm width, 50 mm length and 2 mm thickness were injection-molded and measured with TRUSTAT-Worksurface tester, respectively. The results are shown in Table 4 (physical properties of the polymer composite material prepared in the manufacturing examples) and Table 5 (physical properties of the polymer composite material prepared in the manufacturing and comparison examples).

division Manufacturing Example One 2 3 4 5 6 7 8 Carbon nanotube content (% by weight) 3 Thermoplastic resin content (% by weight) 97 IZOD impact 67 67 69 69 68 68 67 66 Surface resistance (Log Ω / □) 4.05 4.07 4.08 4.07 4.05 4.01 4.11 4.15 Carbon nanotube powder scattering ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Carbon nanotube powder layer separation ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

division Manufacturing Comparative Example One 2 3 4 5 6 7 Carbon nanotube content (% by weight) 3 Thermoplastic resin content (% by weight) 97 IZOD impact 65 63 65 64 65 62 67 Surface resistance (Log Ω / □) 4.87 4.73 5.68 4.79 4.95 5.50 4.10 Carbon nanotube powder scattering ◎ ○ ◎ ○ ○ ◎ X Carbon nanotube powder layer separation ◎ △ ◎ ○ △ ◎ X

Table 6 is a legend.

Carbon nanotube powder scattering Carbon nanotube powder layer separation ◎ No scattering ◎ No layer separation ○ Slightly scattered ○ Slightly separated △ Some scattered △ Partially disconnected X Scattered X Layer separation severity

As shown in the Tables 4 and 5, the carbon nanotube powder according to the present invention has a size of 2 to 6 mm, a thickness of 1 to 6 mm, and an apparent density of 0.05 to 0.60 g / mL. The problem of scattering of carbon nanotube powder and the problem of separation of carbon nanomaterial powder and polymer pellet due to a large density difference could be solved when the shape was used for producing carbon nanotube / polymer composite material (Production Examples 1 to 8). Also, it was confirmed that physical properties such as the Izod impact strength and surface resistance of the carbon nanotube / polymer composite thus prepared were maintained or slightly improved as compared with the case of using the carbon nanotube as a powder (Comparative Production Example 7). Here, the case of the production example is rather slightly improved, and it is estimated that the morphological characteristic of the solid according to the present invention is different from the powder and has the specific form. Also, the solid body of the carbon nanotube powder which is not included in the range of the solid body size of 2 to 6 mm, the thickness of 1 to 6 mm and the apparent density of 0.05 to 0.60 g / mL, which is a feature of the present invention, When manufacturing carbon nanotube / polymer composite material (Manufacturing Comparative Examples 1 to 6), problems of scattering of carbon nanotube powder and separation of layers with polymer pellets can not be completely solved, and the Izod impact strength and surface resistance Was found to be lower than that in the case of using carbon nanotubes as a powder (Comparative Production Example 7). Thus, it was confirmed that not only the shape of the solid body but also the size and apparent density of the solid body are important factors.

Claims

It does not contain any solvent or additive. It has a solid size of 2 ~ 10mm and a thickness of 1 ~ 6mm. Its cross section shape is elliptical, triangular, rectangular or more polygonal and star shape. Its apparent density is 0.05 ~ 0.60g / mL carbon nanomaterial solid.

The carbon nanomaterial solid body according to claim 1, wherein the carbon nanomaterial powder used in the production of the solid body has an angle of repose of 10 ° to 70 °.

The carbon nanomaterial solid body according to claim 1 or 2, wherein the carbon nanomaterial is at least one selected from the group consisting of carbon nanotubes, carbon nanofibers, graphene, and graphite nanoplates.

The carbon nanomaterial powder is injected into a rotary tablet press without mixing solvents or additives and the pressure is applied to form a solid body having a size of 2 to 10 mm and a thickness of 1 to 6 mm and having a cross section of an ellipse, , And a solid density of 0.05 to 0.60 g / mL is formed in a solid form.

[Claim 5] The method according to claim 4, wherein the carbon nanomaterial powder has an average particle diameter of 0.05 to 100 mu m, an apparent density of 0.01 to 0.20 g / mL, and a repose angle of 10 to 70 DEG.

The method according to claim 4, wherein the pressure is in the range of 100 to 700 kg / cm ² .

The method of claim 4, wherein the rotary tablet machine uses a punch having a punch size of 1 to 8 mm and a rotating speed of the turntable at 10 to 60 rpm to form the carbon nano material.

The method of claim 4, wherein the rotary tablet machine uses a punch having a punch size of 2 to 6 mm and a rotating speed of the turntable at 10 to 60 rpm to form the carbon nano material.

Claims 1. A thermoplastic resin composition comprising a solid and a thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin is at least one of polycarbonate, polyethylene terephthalate, amorphous polyethylene terephthalate, glycol-modified polyethylene terephthalate, cyclohexane-modified polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, Polyphenylene oxide, polyphenylene ether, polyether ketone, polyether ketone ketone, polyethylene, polypropylene, polyacrylic, polymethyl methacrylate, polysulfone, polyphenylene sulfide, polyether sulfone, sulfonated polybutyl Butadiene-styrene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polychlorotrifluoroethylene, polyurethane, polyvinylidene chloride, polyetherimide, polyetherimide, polyetheramide, polyacetal, acrylonitrile- , Ethylene Acrylonitrile-butadiene-styrene, polycarbonate / cyclohexane-modified polyethylene terephthalate, acrylonitrile-butadiene-styrene / polyamide, polybutylene A polymer selected from the group consisting of terephthalate / polyethylene terephthalate, polybutylene terephthalate / liquid crystal polymer, polysulfone / modified polyphenylene oxide, polypropylene / polyamide, polycarbonate / A method for producing a polymer composite material.

Claims 1. A thermoplastic resin composition comprising a solid and a thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin is at least one of polycarbonate, polyethylene terephthalate, amorphous polyethylene terephthalate, glycol-modified polyethylene terephthalate, cyclohexane-modified polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, Polyphenylene oxide, polyphenylene ether, polyether ketone, polyether ketone ketone, polyethylene, polypropylene, polyacrylic, polymethyl methacrylate, polysulfone, polyphenylene sulfide, polyether sulfone, sulfonated polybutyl Butadiene-styrene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polychlorotrifluoroethylene, polyurethane, polyvinylidene chloride, polyetherimide, polyetherimide, polyetheramide, polyacetal, acrylonitrile- , Ethylene Acrylonitrile-butadiene-styrene, polycarbonate / cyclohexane-modified polyethylene terephthalate, acrylonitrile-butadiene-styrene / polyamide, polybutylene Carbon nanomaterials / polymers composed of polymers selected from terephthalate / polyethylene terephthalate, polybutylene terephthalate / liquid crystal polymers, polysulfone / modified polyphenylene oxide, polypropylene / polyamide, polycarbonate / Composite material.