KR20200016699A - An electromagnetic wave shielding composition comprising carbon group non-oxide nanoparticles - Google Patents

Abstract

One embodiment of the present invention provides an electromagnetic wave shielding composition comprising a binder resin and two-component or three-component carbon group non-oxide nanoparticles having an average particle size of 5 to 300 nm. The present invention is advantageous in terms of productivity and economic feasibility due to a simple manufacturing process.

Description

Electromagnetic shielding composition comprising carbon group non-oxide nanoparticles {AN ELECTROMAGNETIC WAVE SHIELDING COMPOSITION COMPRISING CARBON GROUP NON-OXIDE NANOPARTICLES}

The present invention relates to an electromagnetic wave shielding composition comprising carbon group non-oxide nanoparticles, and more particularly to an electromagnetic wave shielding composition comprising a multi-component carbon group non-oxide nanoparticles.

Recently, due to the rapid development and mass distribution of computers, electronic products, and communication devices, the generation of electromagnetic waves is increasing, and various problems are raised, such as the occurrence of interference between electronic products due to the rapid generation of noise caused by electromagnetic waves in various frequency ranges. have. In particular, electronic devices are applied to various safety devices and convenience devices for the safety of drivers and pedestrians in a vehicle, and the consumer's interest in the functions is maximized, resulting in low power and high integration of electronic components and circuits. In addition, high reliability is required in many aspects, such as suppressing electromagnetic interference between electronic components due to multifunctionalization, electromagnetic shielding, and immunity.

In order to effectively suppress electromagnetic interference between conventional electronic products, the best method has been to surround electromagnetic products with metal housings to shield electromagnetic waves or to construct expensive electromagnetic shielding networks. However, in the case of wrapping an electronic product with a metal, an expensive mold manufacturing cost is required, as well as a weight of the metal itself, which is disadvantageous in terms of weight reduction of a vehicle for improving fuel efficiency.

Therefore, research is being actively conducted to use functional polymer plastic instead of metal as an electromagnetic shielding material to wrap electronic products, and a polymer composite material in which a filler having electrical conductivity or magnetic is added to the polymer to functionalize the conventional polymer plastic is reviewed. It is becoming. In addition, in general, a technique for shielding electromagnetic waves, reflection shielding using a metal material, absorption shielding using a conductive material is used.

In the case of the polymer composite according to the prior art, the magnetic shield is contained in the polymer to secure the absorption shielding performance in the low frequency region, or the conductive nano material is contained in the polymer to secure the reflective shielding performance in the high frequency region. Patent Publication No. 2011-53058 discloses a technique for providing an electromagnetic shielding function using a composite material made of a polymer and a low melting point metal material.

The polymer composite containing the conductive filler according to the prior art is produced by the most common extrusion and injection molding, which is the most economical production method can be obtained a lighter weight and a reduction in manufacturing cost compared to the electromagnetic shielding material made of a metal material. However, the conventional polymer composite as described above has a disadvantage in that it is difficult to uniformly disperse and distribute the conductive filler in the polymer during the manufacturing process by extrusion and injection. In order to solve this difficulty of dispersion, various methods such as surface treatment of conductive fillers and addition of a compatibilizer to increase the compatibility between the filler and the polymer have been proposed. However, this causes problems in manufacturing process complexity and increase in manufacturing cost. There is this.

In addition, since the polymer composite according to the prior art includes a conductive filler, the shielding function due to conductivity is mainly used, and thus the electromagnetic shielding function in the low frequency region is limited, and when the crack or gap of the material occurs, the space is There is a fear of becoming a moving path. Therefore, in order to shield broadband electromagnetic waves, it is necessary to use a polymer composite compounded by uniformly using magnetic particles and conductive particles as a housing material of an electronic component. In this case, a cost problem occurs.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is to provide an electromagnetic shielding composition which is excellent in the electromagnetic shielding performance and the manufacturing process is economically advantageous.

One aspect of the present invention provides an electromagnetic wave shielding composition comprising an average particle size of 5 ~ 300nm and carbon group non-oxide nanoparticles represented by the following formula (1), and a binder resin.

<Formula 1>

AxBy

Where

A, B are each C, Si, Ge, or B,

x and y are the mole fractions of A and B, respectively,

x is 0.01-0.99 and x + y = 1.

Another aspect of the present invention provides an electromagnetic wave shielding composition comprising an average particle size of 5 to 300nm and carbon group non-oxide nanoparticles represented by the following Chemical Formula 2, and a binder resin.

<Formula 2>

AxByCz

Where

A, B, C are each C, Si, Ge, or B,

x, y, z are the mole fractions of A, B, and C, respectively

x and y are each 0.01-0.9, and x + y + z = 1.

As used herein, the term "carbon-group non-oxide nanoparticle" means a particle including at least one carbon-group (Group 13) element of C, Si, and Ge, and heterogeneous carbon-group elements are alloyed or at least one It may be understood as a concept including particles in which boron (B) is alloyed with a carbon group element of.

As used herein, the term "non-oxide nanoparticle" means a particle substantially free of an oxygen element (O), the oxide layer (oxide) generated on the surface of the non-oxide nanoparticles by a naturally occurring oxidation reaction It can be understood as a concept including a layer).

In the electromagnetic shielding composition, the carbon group non-oxide nanoparticles may be included in the form of a diluted solution at a concentration of 1 to 1,000 ppm, and the content of the solution may be 1 to 20 parts by weight based on 100 parts by weight of the binder resin. .

The binder resin may be low density polyethylene (LDPE), high density polyethylene (HDPE), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), copolymer of ethylene and propylene (EPM), polyurethane (polyurethane), polyurea (poly urea), silicone resin (silicon resin), epoxy resin (epoxy resin) and may be one selected from the group consisting of two or more thereof, preferably, may be a silicone resin, It is not limited to this.

The silicone resin has excellent resilience, chemical resistance, heat resistance, flame retardancy, weather resistance, chemical resistance, hot water resistance, oil resistance, insulation, non-toxicity, strength, low temperature elasticity, and the like, and when the composition containing the silicone resin is used as an electromagnetic shielding material. Since the tensile strength, elongation, friction fastness and the like is excellent, there is an advantage that the coated portion is not peeled off arbitrarily. In addition, the silicone resin is not only harmful to the human body, but also has the advantage of long life of the shielding material.

The silicone resin may be, for example, one selected from the group consisting of dimethylsiloxane, polydimethylsiloxane, polyether modified polydimethylsiloxane, oligosiloxane, and mixtures of two or more thereof.

In one embodiment, the electromagnetic wave shielding composition is an alkaline earth metal compound, tourmaline, tin (Sn), antimony (Sb), tellurium (Te), iodine (I), xenon (Xe), cesium (Cs), Barium (Ba), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Tolium (Tm), Ytterbium (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), polonium (Po), asstatin (At), radon (Rn), Francium (Fr), Radium (Ra), Actinium (Ac), Thorium (Th), Protactinium (Pa), Uranium (U), Neptunium (Np), Plutonium (Pu), Americium (Am), Curium (Cm) , Berkelium (Bk), Californium (Cf), Einitanium (Es), Fermium (Fm), Mendelebium (Md), Nobelium (No), Lawrencium (Lr), Rutherfordium (Rf), Dubnium (Db), Siboum (Sg), borium (Bh), hassium (Hs), mite It may further comprise one selected from the group consisting of a cerium (Mt) and a mixture of two or more thereof.

In one embodiment, the electromagnetic shielding material composition is carbon nanotubes (CNT), carbon nanoparticles (CNP), graphene nanoplates (GNP), carbon fibers (CF), carbon black (CB) and a mixture of two or more thereof It may further comprise one selected from the group consisting of.

In one embodiment, the carbon group non-oxide nanoparticles may be surface-modified by one selected from the group consisting of alkoxy groups, hydroxyl groups, amino groups and combinations thereof.

The electromagnetic wave shielding composition according to an aspect of the present invention is excellent in electromagnetic shielding performance by controlling the particle size of the carbon group non-oxide nanoparticles to a certain range and including a binder resin, and is advantageous in terms of productivity and economic efficiency due to the simple manufacturing process. .

It is to be understood that the effects of the present invention are not limited to the above effects, and include all effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout the specification, when a part is "connected" to another part, it includes not only "directly connected" but also "indirectly connected" with another member in between. . In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

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

Example 1 Preparation of an Electromagnetic Wave Shielding Material Composition Comprising SiB Nanoparticles

Silicon-boron alloy nanoparticles may be prepared according to Scheme 1 below.

<Scheme 1>

2SiH ₄ + 2B ₂ H ₆ + N ₂ SiB ₄ + 8H ₂ + N ₂

Monosilane gas (SiH ₄ ), diborane gas (B ₂ H ₆ ), and nitrogen are mixed and injected into the reaction chamber to irradiate a CO ₂ laser beam. At this time, the diborane gas acts as a catalyst gas and a source gas, and the energy absorbed at 10.6 탆 wavelength is efficiently transferred to the silane gas, and the Si-H bond of the silane gas is well broken so that the silicon-boron alloy nanoparticles (SiB _x -NPs) are generated.

In addition, since diborigox is decomposed into boron and hydrogen atoms, boron forms an alloy with silicon nanoparticles, and serves to prevent oxidation of silicon. Silane gas as the source gas is 90% or more of the total volume (volume of the raw material gas and the catalyst gas combined), and the catalyst gas is adjusted to the range of 10% or less of the total volume. In addition, the carrier gas nitrogen does not exceed 400 parts by volume relative to the silane gas as the raw material gas. The flow rate of gas is in sccm. Process pressure inside the reaction chamber is prepared by setting in the range of 100 ~ 400 Torr. In this range, silicon-boron alloy nanoparticles (SiB _x -NPs) having a size of 5 to 300 nm are prepared.

division Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Raw material gas (sccm) 300 500 700 1000 1500 Catalyst gas (sccm) 15 36 60 80 105 Carrier Gas (sccm) 400 400 400 500 500 Process pressure (Torr) 350-200 350-200 250-100 250-100 200-100 Particle Size (nm) 20-30 20-30 20-30 20-30 20-30 B content (wt%) 2.5 6 9.6 12.5 16 Si content (wt%) 97.5 94 90.4 87.5 84 Atomic ratio 1:15 1: 6 1: 4 1: 3 1: 2 SiBx SiB ₁₅ SiB ₆ SiB ₄ SiB ₃ SiB ₂

Subsequently, 80 wt% of dimethylsiloxane as a liquid silicone resin, 10 wt% of a solution in which SiB _x -NPs having an average particle diameter of 20 to 30 nm and 1 to 1,000 ppm of dispersed solution, and 10 wt% of a silicone resin curing agent were added to a stirrer and mixed. To prepare an electromagnetic wave shielding material composition. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles. Example 1-5

100 mg of SiB ₄ -NPs prepared in Example 1-3 was dispersed in 25 ml of methanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiB ₄ -NPs with methoxy groups.

Example 1-6

100 mg of SiB ₄ -NPs prepared in Example 1-3 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiB ₄ -NPs with ethoxy groups.

Example 1-7

100 mg of SiB ₄ -NPs prepared in Example 1-3 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiB ₄ -NPs with isopropoxy.

Experimental Example 1

After applying the electromagnetic wave shielding composition of Example 1-3 to the substrate to a thickness of 0.5 ~ 1.5mm constant and semi-dried, it was placed on the belt of the drying unit and heated to 120 ~ 180 ℃ for about 3-5 minutes to dry completely . Cool air was blown to the completely dried substrate by using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 1-1 to 1-5).

Samples having different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 100 to 120 kvp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 1-1 Preparation Example 1-2 Preparation Example 1-3 Preparation Example 1-4 Preparation Example 1-5 SiB ₄ -NPs (concentration) 1 ppm 10 ppm 100 ppm 500 ppm 1,000 ppm SiB ₄ -NPs (wt%) 10 10 10 10 10 Silicone resin (wt%) 80 80 80 80 80 Curing agent (% by weight) 10 10 10 10 10 Thickness (mm) 1.5 1.5 One 0.8 0.5 Voltage (kvp) 100 100 100 120 120 Shielding rate (%) 80.5 85.2 99.5 98.9 99.1

Example 2 Preparation of Electromagnetic Wave Shielding Material Composition Comprising SiC Nanoparticles

Silicon-carbon alloy nanoparticles may be prepared according to Scheme 2 below.

<Scheme 2>

2SiH ₄ + C ₂ H ₂ → 2SiC + 5H ₂

Example 2-1

Monosilane gas (SiH ₄ ), acetylene gas (C ₂ H ₂ ), and nitrogen are mixed and injected into the reaction chamber to irradiate a CO ₂ laser beam. Acetylene gas is decomposed into carbon and hydrogen atoms, and carbon forms alloys with silicon nanoparticles, and serves to prevent oxidation of silicon. Silane gas and acetylene gas which are raw material gases are injected in the volume ratio of 2: 1, respectively. In addition, the carrier gas nitrogen does not exceed 400 parts by volume relative to the silane gas as the raw material gas. The flow rate of gas is in sccm. Process pressure inside the reaction chamber is prepared by setting in the range of 100 ~ 500 Torr. In this range, silicon-carbon alloy nanoparticles (SiC-NPs) having a size of 10 to 30 nm are manufactured.

Thereafter, as a liquid silicone resin, 80% by weight of dimethylsiloxane, 10 to 30% by weight of a solution containing 1 to 1,000 ppm of SiC-NPs having an average particle diameter of 10 to 30 nm, and 10% by weight of a silicone resin curing agent were added to a stirrer and mixed. An electromagnetic wave shielding composition was prepared. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles.

Example 2-2

100 mg of SiC-NPs prepared in Example 2-1 was dispersed in 25 ml of methanol, and ultrasonic waves were irradiated for 5 minutes to prepare surface-modified SiC-NPs with methoxy groups.

Example 2-3

100 mg of SiC-NPs prepared in Example 2-1 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiC-NPs with ethoxy groups.

Example 2-4

100 mg of SiC-NPs prepared in Example 2-1 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiC-NPs with isopropoxy.

Experimental Example 2

The electromagnetic wave shielding composition of Example 2-1 was applied to a substrate with a constant thickness of 0.5 to 1.5 mm, and then semi-dried, placed on a belt of a drying unit, and dried at 120 to 180 ° C. for about 3 to 5 minutes to dry completely. . Cool air was blown to the completely dried substrate using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 2-1 to 2-5).

Samples with different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 50 to 100 kbp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 2-1 Preparation Example 2-2 Preparation Example 2-3 Preparation Example 2-4 Preparation Example 2-5 SiC-NPs (concentration) 1 ppm 10 ppm 100 ppm 500 ppm 1,000 ppm SiC-NPs (wt%) 10 10 10 10 10 Silicone resin (wt%) 80 80 80 80 80 Curing agent (% by weight) 10 10 10 10 10 Thickness (mm) 1.5 1.5 One 0.8 0.5 Voltage (kvp) 50 50 50 100 100 Shielding rate (%) 81.7 89.8 90.1 96 98.8

Example 3 Preparation of an Electromagnetic Wave Shielding Material Composition Comprising SiGeB Nanoparticles

Silicon-germanium-boron alloy nanoparticles can be prepared according to Scheme 3 below.

<Scheme 3>

2SiH ₄ + 2GeH ₄ + B ₂ H ₆ → 2SiGeB + 11H ₂

Example 3-1

100 parts of monosilane (SiH ₄ ), 100 parts of Germane (GeH ₄ ), and 40 to 80 parts of diborane (B ₂ H ₆ ) and nitrogen of carrier gas through the source gas supply nozzle (N ₂ ) The mixed gas containing 400 parts by volume is supplied into the reaction chamber having an internal pressure of 80 to 400 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber through the irradiation part. Irradiation was performed for 3 hours in the form of a continuous wave line beam of 10.6 μm to prepare silicon-germanium-boron alloy nanoparticles (SiGeB-NPs). The particle size of SiGeB-NPs is 10-300 nm.

Thereafter, 80 wt% of dimethylsiloxane as a liquid silicone resin, 10 wt% of a solution in which 1 to 100 ppm of SiGeB-NPs having an average particle diameter of 10 to 30 nm, and 10 wt% of a silicone resin curing agent were added to a stirrer and mixed with electromagnetic waves. The shielding composition was prepared. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles.

Example 3-2

100 mg of SiGeB-NPs prepared in Example 3-1 was dispersed in 25 ml of methanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiGeB-NPs with methoxy groups.

Example 3-3

100 mg of SiGeB-NPs prepared in Example 3-1 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiGeB-NPs with ethoxy groups.

Example 3-4

100 mg of SiGeB-NPs prepared in Example 3-1 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiGeB-NPs with isopropoxy.

Experimental Example 3

The electromagnetic wave shielding composition of Example 3-1 was applied to a substrate with a constant thickness of 0.5 to 1.5 mm, and then semi-dried, and placed on a belt of a drying unit, and dried at 120 to 180 ° C. for about 3 to 5 minutes to dry completely. . Cool air was blown to the completely dried substrate using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 3-1 to 3-3).

Samples with different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 100kvp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 3-1 Preparation Example 3-2 Preparation Example 3-3 SiGeB-NPs (concentration) 1 ppm 10 ppm 100 ppm SiGeB-NPs (wt%) 10 10 10 Silicone resin (wt%) 80 80 80 Curing agent (% by weight) 10 10 10 Thickness (mm) 1.5 1.5 One Voltage (kvp) 100 100 100 Shielding rate (%) 89.8 86.7 99

Example 4 Preparation of Electromagnetic Wave Shielding Material Composition Comprising SiGeC Nanoparticles

Silicon-germanium-carbon alloy nanoparticles can be prepared according to Scheme 4 below.

<Scheme 4>

2SiH ₄ + 2GeH ₄ + C ₂ H ₂ → 2SiGeC + 9H ₂

Example 4-1

100 parts by weight of monosilane (SiH ₄ ), 100 parts by weight of Germane (GeH ₄ ), and 40 to 80 parts by weight of acetylene (C ₂ H ₂ ) and nitrogen (N) ₂ ) The mixed gas mixed with 400 parts by volume is supplied into the reaction chamber having an internal pressure of 80 to 400 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber with a wavelength of 10.6. Irradiation for 3 hours in the form of a line beam of continuous wave (μm) was made of silicon-germanium-carbon alloy nanoparticles (SiGeC-NPs). The particle size of SiGeC-NPs is 5 to 300 nm.

Thereafter, 80 wt% of dimethylsiloxane as a liquid silicone resin, 10 wt% of a solution containing 1 to 100 ppm of SiGeC-NPs having an average particle diameter of 10 to 30 nm, and 10 wt% of a silicone resin curing agent were added to a stirrer and mixed with electromagnetic waves. The shielding composition was prepared. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles.

Example 4-2

100 mg of SiGeC-NPs prepared in Example 4-1 was dispersed in 25 ml of methanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiGeC-NPs with methoxy groups.

Example 4-3

100 mg of SiGeC-NPs prepared in Example 4-1 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiGeC-NPs with ethoxy groups.

Example 4-4

100 mg of SiGeC-NPs prepared in Example 4-1 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified SiGeC-NPs with isopropoxy.

Experimental Example 4

The electromagnetic wave shielding composition of Example 4-1 was applied to a substrate with a thickness of 0.5 to 1.5 mm, and then semi-dried. . Cool air was blown to the completely dried substrate using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 4-1 to 4-3).

Samples with different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 100kvp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 4-1 Preparation Example 4-2 Preparation Example 4-3 SiGeC-NPs (concentration) 1 ppm 10 ppm 100 ppm SiGeC-NPs (wt%) 10 10 10 Silicone resin (wt%) 80 80 80 Curing agent (% by weight) 10 10 10 Thickness (mm) 1.5 1.5 One Voltage (kvp) 100 100 100 Shielding rate (%) 81.8 89.7 98.9

Example 5 Preparation of Electromagnetic Wave Shielding Material Composition Comprising CB Nanoparticles

Carbon-boron alloy nanoparticles can be prepared according to Scheme 5 below.

Scheme 5

C ₂ H ₂ + ₄ B ₂ H ₆ + N _{2 2} B ₄ C + ₁₃ H ₂ + N ₂

Example 5-1

100 parts by volume of acetylene (C ₂ H ₂ ) as the source gas, 40 to 80 parts by volume of diborane (B ₂ H ₆ ) and 400 parts by volume of nitrogen (N ₂ ) as the carrier gas through the source gas supply nozzle The mixed gas mixture is supplied into the reaction chamber having an internal pressure of 100 to 400 torr, and the laser beam generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber through a radiation unit. (Carbon-boron alloy nanoparticles (CB _x -NPs) were prepared _by irradiation for 3 hours in the form of (Line Beam)). The particle size of CB _x -NPs is 10-300 nm.

Thereafter, as a liquid silicone resin, 80 wt% of dimethylsiloxane, 10 wt% of a solution containing 1 to 1,000 ppm of CB _x- NPs having an average particle diameter of 10 to 300 nm, and 10 wt% of a silicone resin curing agent were mixed in a stirrer. To prepare an electromagnetic wave shielding material composition. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles.

Example 5-2

100 mg of CB _x -NPs prepared in Example 5-1 was dispersed in 25 ml of methanol, and ultrasonic waves were irradiated for 5 minutes to prepare CB _x -NPs surface-modified with a methoxy group.

Example 5-3

100 mg of CB _x -NPs prepared in Example 5-1 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare CB _x -NPs surface-modified with an ethoxy group.

Example 5-4

100 mg of CB _x -NPs prepared in Example 5-1 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare CB _x -NPs surface-modified with isopropoxy.

Experimental Example 5

The electromagnetic wave shielding composition of Example 5-1 was uniformly coated on a substrate with a thickness of 0.5 to 1.5 mm and then semi-dried. . Cool air was blown to the completely dried substrate using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 5-1 to 5-5).

Samples having different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 100 to 120 kvp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 5-1 Preparation Example 5-2 Preparation Example 5-3 Preparation Example 5-4 Preparation Example 5-5 CB _x -NPs (concentration) 1 ppm 10 ppm 100 ppm 500 ppm 1,000 ppm CB _x -NPs (% by weight) 10 10 10 10 10 Silicone resin (wt%) 80 80 80 80 80 Curing agent (% by weight) 10 10 10 10 10 Thickness (mm) 1.5 1.5 One 0.8 0.5 Voltage (kvp) 100 100 100 120 120 Shielding rate (%) 79.8 82.6 86.7 93.1 99.8

Example 6: Preparation of electromagnetic shielding material composition comprising GeB nanoparticles

Germanium-boron alloy nanoparticles can be prepared according to Scheme 6 below.

<Scheme 6>

2GeH ₄ + 2B ₂ H ₆ + N ₂ GeB ₄ + 8H ₂ + N ₂

Example 6-1

Through the feed gas supply nozzle, 100 parts of Germane (GeH ₄ ) source gas, 40 ~ 80 parts of diborane (B ₂ H ₆ ) and 400 parts of nitrogen (N ₂ ) carrier gas were mixed. The mixed gas is supplied into the reaction chamber having an internal pressure of 100 to 400 torr, and the laser generated by the CO ₂ laser generator is supplied to the mixed gas supplied into the reaction chamber through a irradiation unit. Germanium-boron alloy nanoparticles (GeB _x -NPs) were prepared _by irradiation in the form of a beam) for 3 hours. The particle size of GeB _x -NPs is 10-300 nm.

Thereafter, 80 wt% of dimethylsiloxane (dimethylsiloxane), 10 wt% of GeB _x -NPs having an average particle diameter of 10 to 300 nm, and 10 wt% of a silicone resin curing agent were mixed in a stirrer as a liquid silicone resin. To prepare an electromagnetic wave shielding material composition. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles.

Example 6-2

100 mg of GeB _x -NPs prepared in Example 6-1 was dispersed in 25 ml of methanol, and ultrasound was irradiated for 5 minutes to prepare GeB _x -NPs surface-modified with methoxy groups.

Example 6-3

100 mg of GeB _x -NPs prepared in Example 6-1 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified GeB _x -NPs with ethoxy groups.

Example 6-4

100 mg of GeB _x -NPs prepared in Example 6-1 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare GeB _x -NPs surface-modified with isopropoxy.

Experimental Example 6

The electromagnetic wave shielding composition of Example 6-1 was applied to a substrate with a constant thickness of 0.5 to 1.5 mm, and then semi-dried, placed on a belt of a drying unit, and dried at 120 to 180 ° C. for about 3 to 5 minutes to dry completely. . Cool air was blown to the completely dried substrate using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 6-1 to 6-5).

Samples having different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 100 to 120 kvp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 6-1 Preparation Example 6-2 Preparation Example 6-3 Preparation Example 6-4 Preparation Example 6-5 GeB _x -NPs (concentration) 1 ppm 10 ppm 100 ppm 500 ppm 1,000 ppm GeB _x -NPs (% by weight) 10 10 10 10 10 Silicone resin (wt%) 80 80 80 80 80 Curing agent (% by weight) 10 10 10 10 10 Thickness (mm) 1.5 1.5 One 0.8 0.5 Voltage (kvp) 100 100 100 120 120 Shielding rate (%) 79.8 82.6 86.7 93.1 98.9

Example 7: Preparation of electromagnetic shielding material composition comprising GeC nanoparticles

Germanium-carbon alloy nanoparticles may be prepared according to Scheme 7 below.

Scheme 7

2GeH ₄ + C ₂ H ₂ → 2GeC + 5H ₂

Example 7-1

Germane gas (GeH ₄ ), acetylene gas (C ₂ H ₂ ) and nitrogen are mixed and injected into the reaction chamber to irradiate a CO ₂ laser beam. Acetylene gas is decomposed into carbon and hydrogen atoms, and carbon forms alloys with silicon nanoparticles, and serves to prevent oxidation of silicon. The raw material gases germane gas and acetylene gas are injected at a volume ratio of 2: 1, respectively. In addition, the carrier gas nitrogen does not exceed 400 parts by volume relative to the silane gas as the raw material gas. The flow rate of gas is in sccm. Process pressure inside the reaction chamber is prepared by setting in the range of 100 ~ 500 Torr. In this range, germanium-carbon alloy nanoparticles (GeC-NPs) having a size of 10 to 30 nm are prepared.

Thereafter, 80 wt% of dimethylsiloxane as a liquid silicone resin, 10 wt% of a solution in which GeC-NPs having an average particle diameter of 10 to 30 nm dispersed in 1 to 1,000 ppm, and 10 wt% of a silicone resin curing agent were mixed in a stirrer. An electromagnetic wave shielding material composition was prepared. In the prepared electromagnetic shielding material composition, since very small bubbles are generated at the interface between the powder and the liquid phase, the bubble removing operation was performed for 1 hour in the vacuum chamber to remove the bubbles.

Example 7-2

100 mg of GeC-NPs prepared in Example 7-1 was dispersed in 25 ml of methanol and ultrasonically irradiated for 5 minutes to prepare surface-modified GeC-NPs with methoxy groups.

Example 7-3

100 mg of GeC-NPs prepared in Example 7-1 was dispersed in 25 ml of ethanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified GeC-NPs with ethoxy groups.

Example 7-4

100 mg of GeC-NPs prepared in Example 7-1 was dispersed in 25 ml of isopropanol, and ultrasonically irradiated for 5 minutes to prepare surface-modified GeC-NPs with isopropoxy.

Experimental Example 7

The electromagnetic wave shielding composition of Example 7-1 was uniformly coated on a substrate with a thickness of 0.5 to 1.5 mm and then semi-dried. . Cool air was blown to the completely dried substrate by using a blower to completely cure, and then removed from the substrate to obtain a film type electromagnetic shielding material (Production Examples 7-1 to 7-5).

Samples with different thicknesses of the electromagnetic wave shielding film were cut into 20 cm x 20 cm, and the shielding rate (%) was measured by irradiating electromagnetic waves with a voltage of 50 to 100 kbp. At this time, the shielding rate of the electromagnetic shielding film was measured 10 times at different positions each time, and the average shielding rate (%) was obtained.

division Preparation Example 7-1 Preparation Example 7-2 Preparation Example 7-3 Preparation Example 7-4 Preparation Example 7-5 GeC-NPs (concentration) 1 ppm 10 ppm 100 ppm 500 ppm 1,000 ppm GeC-NPs (wt%) 10 10 10 10 10 Silicone resin (wt%) 80 80 80 80 80 Curing agent (% by weight) 10 10 10 10 10 Thickness (mm) 1.5 1.5 One 0.8 0.5 Voltage (kvp) 50 50 50 100 100 Shielding rate (%) 77.5 83.6 89.6 94.2 98.3

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the invention is indicated by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the invention.

Claims (5)

Carbon group non-oxide nanoparticles having an average particle size of 5 to 300 nm and represented by the following Chemical Formula 1, and
Electromagnetic shielding material composition comprising a binder resin:
<Formula 1>
AxBy
Where
A, B are each C, Si, Ge, or B,
x and y are the mole fractions of A and B, respectively,
x is 0.01-0.99 and x + y = 1. Carbon group non-oxide nanoparticles having an average particle size of 5 to 300 nm and represented by the following Chemical Formula 2, and
Electromagnetic shielding material composition comprising a binder resin:
<Formula 2>
AxByCz
Where
A, B, C are each C, Si, Ge, or B,
x, y, z are the mole fractions of A, B, and C, respectively
x and y are each 0.01-0.9, and x + y + z = 1. The method according to claim 1 or 2,
The electromagnetic wave shielding composition is alkaline earth metal compound, tourmaline, tin (Sn), antimony (Sb), tellurium (Te), iodine (I), xenon (Xe), cesium (Cs), barium (Ba), lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Tolium (Tm), Ytterbium (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), polonium (Po), asstatin (At), radon (Rn), francium (Fr), radium (Ra), actinium (Ac), thorium (Th), protactinium (Pa), uranium (U), neptunium (Np), plutonium (Pu), americium (Am), querium (Cm), buckleium (Bk), Californium (Cf), Einitanium (Es), Fermium (Fm), Mendelebium (Md), Nobelium (No), Lawrencium (Lr), Rutherfordium (Rf), Dubnium (Db), Siboum (Sg) Bh), hassium (Hs), mitenerium (Mt) and two of them Electromagnetic shielding material composition further comprising one selected from the group consisting of the above mixture. The method according to claim 1 or 2,
The electromagnetic shielding composition is one selected from the group consisting of carbon nanotubes (CNT), carbon nanoparticles (CNP), graphene nanoplates (GNP), carbon fibers (CF), carbon black (CB), and mixtures of two or more thereof. Electromagnetic shielding material composition further comprising. The method according to claim 1 or 2,
Wherein the carbon group non-oxide nanoparticles surface-modified by one selected from the group consisting of alkoxy groups, hydroxyl groups, amino groups and combinations thereof.