KR101898234B1 - Resin composition, article prepared by using the same and method of preparing the same - Google Patents

Abstract

Disclosed is a resin composition comprising a thermally conductive particle, a boron nitride nanotube, and a matrix resin, an article made therefrom, and a method of manufacturing the same.

Description

Resin compositions, articles made therefrom, and methods of making the same United States

A resin composition, an article made therefrom, and a method of manufacturing the same.

Due to the highly integrated, miniaturized, multifunctional and lightweight electronic products, a lot of heat can be generated inside the electronic products. If the heat generated in the electronic device inside the electronic product is not properly discharged to the outside of the electronic product, the function of the electronic product may be deteriorated and the service life may be shortened.

Therefore, it is necessary to develop a material capable of providing a heat-radiating material having an electrical insulating property suitable for use in an electronic device, and at the same time having an improved thermal conductivity.

Embodiments of the present invention provide resin compositions, articles made therefrom, and methods of making the same. Specifically, the present invention provides a resin composition having improved thermal conductivity and electrical insulation, an article made therefrom, and a method of manufacturing the same.

According to one embodiment of the present invention, there is provided a resin composition comprising thermally conductive particles, a boron nitride nanotube, and a matrix resin.

According to another embodiment of the present invention, an article made from the resin composition is provided.

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: providing a resin composition comprising thermally conductive particles, a boron nitride nanotube, and a matrix resin; And

And heating or curing the resin composition to form an article.

An article made of a resin composition according to one embodiment of the present invention has improved thermal conductivity. In addition, it can have excellent properties to be employed as a heat insulating material in various electronic products.

1 is a cross-sectional view schematically showing the structure of an article made of a resin composition according to an embodiment of the present invention.
FIGS. 2 and 3 are scanning electron microscope (SEM) photographs of the boron nitride nanotubes used in the examples.
FIG. 4 is a transmission electron microscope (TEM) photograph of the boron nitride nanotubes used in Examples. FIG.
FIG. 5 is a diagram showing an X-ray diffraction (XRD) pattern of boron nitride nanotubes used in Examples. FIG.
6 is a SEM photograph of the hexagonal boron nitride particles used in Examples.
FIG. 7 is a photograph showing an actual picture of a circular disc specimen according to the first embodiment. FIG.
8 is a photograph showing a real image of a rectangular beam-shaped specimen according to the first embodiment.
FIG. 9 is a photograph showing an actual picture of a square plate type specimen according to the first embodiment. FIG.
FIGS. 10 and 11 are SEM photographs showing the fracture surfaces of the specimen according to Example 1. FIG.
12 and 13 are SEM photographs showing the fracture surfaces of the specimen according to Comparative Example 1. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. The effects and features of the present invention and methods of achieving them will be apparent with reference to the embodiments described in detail below with reference to the drawings. However, the present invention is not limited to the embodiments described below, but may be implemented in various forms.

In the present specification, the singular form includes plural forms unless otherwise specified in the specification.

As used herein, the terms "comprises" or "having" or "having" mean that a feature or element described in the specification is meant to be present, and that excluding one or more other features or components from the possibility of being added no.

In the present specification, the term "aspect ratio of thermally conductive particles" means a value obtained by dividing the average longest axis length of the thermally conductive particles by the average shortest axis length of the thermally conductive particles.

In the present specification, the term "average aspect ratio of boron nitride nanotubes" means the average length of boron nitride nanotubes divided by the average diameter of boron nitride nanotubes.

In the present specification, the term "boron nitride nanotubes" refers to tubular ash composed of boron nitride, ideally a hexagonal ring arranged in parallel along the tube axis. However, the hexagonal rings may not be parallel to the tube axis but may be arranged in a twisted arrangement. It may also include modifications such as boron nitride doped with other materials.

Resin composition

The resin composition according to one embodiment of the present invention may include thermally conductive particles, boron nitride nanotubes, and matrix resin.

Although not intending to be limited by any particular theory, a resin composition that does not contain boron nitride nanotubes tends to form a heat conduction path only in a specific direction in which thermally conductive particles are oriented. In particular, the greater the aspect ratio of the thermally conductive particles, the more the heat conduction path can deviate in a certain direction. This tends to lower the thermal conductivity of the article in certain other directions. Specifically, when it is assumed that an article made of a resin composition containing only boron nitride nanotubes and containing only thermally conductive particles is in a film form, the thermal conductivity in the horizontal direction parallel to the widest plane of the film may be relatively high have. On the other hand, the thermal conductivity in the vertical direction orthogonal to the widest surface of the film tends to be very low.

Further, although it is not intended to be limited by a particular theory, it may be difficult to produce a resin composition containing only a boron nitride nanotube as an article having uniform specifications. Specifically, the boron nitride nanotubes may not be intermixed with each other and may not be uniformly dispersed in the resin composition, and an article made from such a resin composition may be obtained only in a part of the article having a desired specification (for example, a desired thermal conductivity) .

However, the resin composition according to one embodiment of the present invention necessarily includes thermally conductive particles and boron nitride nanotubes, so that the heat transfer channel can be formed in various directions (for example, vertical and horizontal directions) And the thermal conductivity can be improved.

Specifically, since an article made of a resin composition according to an embodiment of the present invention including thermally conductive particles and boron nitride nanotubes efficiently forms heat transfer channels in a vertical direction, thermal conduction in a horizontal direction and a vertical direction The temperature can be very high at the same time. The article made of the resin composition according to one embodiment of the present invention including the thermally conductive particles and the boron nitride nanotube can be greatly improved in thermal conductivity particularly in the vertical direction. In FIG. 1, only vertical heat transfer channels are exemplarily described. However, in the article made of the resin composition according to one embodiment of the present invention, there is also a horizontal heat transfer channel.

The shape of the thermally conductive particle is not limited, and may be various shapes such as a spherical shape, a plate shape, a cubic shape, and the like.

The average particle diameter of the thermally conductive particles may be 0.1 m to 150 m. For example, the average particle diameter of the thermally conductive particles may be 1 μm or more, 3 μm or more, or 10 μm or more, but is not limited thereto. As another example, the average particle size of the thermally conductive particles may be 120 μm or less, 100 μm or less, 90 μm or less, 80 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less . When the average particle diameter of the thermally conductive particles satisfies the above range, the resin composition can be homogeneously dispersed in the resin composition, and the resin composition can have an appropriate viscosity for forming the article, This can be smooth.

The average aspect ratio of the thermally conductive particles may be 1 to 300. For example, the average aspect ratio of the thermally conductive particles may be 3 or more, 5 or more, 7 or more, or 10 or more, but is not limited thereto. Or, as another example, the average aspect ratio of the thermally conductive particles may be 200 or less, or 100 or less, but is not limited thereto. When the average aspect ratio of the thermally conductive particles satisfies the above range, the content of thermally conductive particles that can be contained in the resin composition can be increased, and therefore, an article having improved thermal conductivity can be provided.

According to one embodiment, the thermally conductive particles may comprise a metal nitride, a metal oxide, a metal oxynitride, a metal carbide, or any combination thereof.

For example, the thermally conductive particles may include, but are not limited to, a Group 2 element, a Group 13 element, a Group 14 element, or a combination thereof, nitrides, oxides, oxynitrides, or carbides. The Group 2 element may be selected from beryllium, magnesium, and calcium, but is not limited thereto. The Group 13 element may be selected from boron, aluminum and gallium, but is not limited thereto. The Group 14 element may be selected from among silicon, germanium and tin, but is not limited thereto.

As another example, the thermally conductive particles may include aluminum nitride, aluminum oxide, aluminum oxynitride, boron nitride, boron oxide, boron oxynitride, silicon oxide, silicon carbide, beryllium oxide or combinations thereof , But is not limited thereto.

As another example, the thermally conductive particles may include, but are not limited to, aluminum nitride, boron nitride, or combinations thereof.

As another example, the thermally conductive particles may include, but are not limited to, boron nitride. Since boron nitride has high thermal conductivity, high mechanical stability and / or high chemical stability, articles made from resin compositions containing boron nitride can have high thermal conductivity, high mechanical stability and / or high chemical stability have.

According to another embodiment, the thermally conductive particles may be hexagonal boron nitride particles, but are not limited thereto. Specifically, the average particle size of the hexagonal boron nitride particles may be 0.1 to 150 μm, and the average aspect ratio of the hexagonal boron nitride particles may be 10 to 300, but is not limited thereto.

The average diameter of the boron nitride nanotubes may be between 2 nm and 1 [mu] m. For example, the average diameter of the boron nitride nanotubes may be 5 nm or more, 7 nm or more, or 10 nm or more, but is not limited thereto. Alternatively, as another example, the average diameter of the boron nitride nanotubes may be 800 nm or less, 500 nm or less, or 200 nm or less, but is not limited thereto. When the average diameter of the boron nitride nanotubes satisfies the above range, the resin composition can be homogeneously dispersed in the resin composition, and the resin composition can have a viscosity suitable for forming the article, and the article produced from the resin composition Thin and smooth surface.

The average length of the boron nitride nanotubes may be between 0.5 μm and 1,000 μm. For example, the average length of the boron nitride nanotubes may be 100 μm or less, 50 μm or less, or 10 μm or less, but is not limited thereto. Or, as another example, the average length of the boron nitride nanowires may be at least 500 μm, at least 700 μm, or at least 900 μm, but is not limited thereto. If the average length of the boron nitride nanotubes satisfies the above range, the heat conduction channel can be appropriately formed in the article made of the resin composition, and the thermal conductivity of the article can be improved.

The average aspect ratio of the boron nitride nanotubes may range from 5 to 100,000. For example, the average aspect ratio of the boron nitride nanotubes may be 10 to 10,000, but is not limited thereto. If the average aspect ratio of the boron nitride nanotubes satisfies the above range, the heat conduction channel can be appropriately formed in the article made of the resin composition, and the thermal conductivity of the article can be improved.

The type of the matrix resin is not limited as long as the thermally conductive particles and the boron nitride nanotubes can be uniformly dispersed and fixed.

For example, the matrix resin may be a thermoplastic resin or a thermosetting resin, but is not limited thereto.

Specifically, the matrix resin may be a nylon resin, a polyethylene resin, a polypropylene resin, a polybutylene resin, a polyester resin, a polyurethane resin, a polyacrylic resin, a styrene butadiene resin, a vinyl resin, a polycarbonate resin, An epoxy resin, an amino resin, and a phenol resin, and a resin selected from the group consisting of an epoxy resin, an epoxy resin, an epoxy resin, an epoxy resin, a phenol resin, a polyetherketone resin, But the present invention is not limited thereto.

As another example, the matrix resin may be a thermosetting resin, but is not limited thereto. The resin composition containing the thermosetting resin may be more preferable than the resin composition containing the thermoplastic resin because the thermally conductive particles and the boron nitride nanotube are relatively easily dispersed and have excellent mechanical properties.

Specifically, the matrix resin may be an epoxy resin, but is not limited thereto. The resin composition containing an epoxy resin may have high properties such as heat resistance, moisture resistance, durability, and chemical resistance.

More specifically, the matrix resin is at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, aliphatic epoxy resin and glycidyl amine epoxy resin But is not limited thereto.

More specifically, the matrix resin may be a phenol novolak epoxy resin having a number average molecular weight of 300 or more and / or a phenol novolak epoxy resin having an epoxy equivalent weight of 170 or more, but is not limited thereto.

The resin composition may include not less than 10 wt% and not more than 69 wt% of the thermally conductive particles, based on the total weight of the resin composition. For example, the resin composition may include not less than 30 wt% and not more than 50 wt% of the thermally conductive particles, based on the total weight of the resin composition. When the content of the thermally conductive particles satisfies the above-mentioned range, it is possible to provide an article having excellent thermal conductivity.

The resin composition may include more than 0 wt% to 20 wt% of the boron nitride nanotube, based on the total weight of the resin composition. For example, the resin composition may include 0.5 to 20% by weight, or 1 to 20% by weight, based on the total weight of the resin composition, of the boron nitride nanotubes, It is not. When the content of the boron nitride nanotubes satisfies the above-described range, it is possible to provide an article having excellent thermal conductivity.

The resin composition may include 20% by weight to 70% by weight of the matrix resin, based on the total weight of the resin composition. For example, the resin composition may include 25 wt% to 70 wt%, or 30 wt% to 50 wt% of the matrix resin based on the total weight of the resin composition, but is not limited thereto. When the content of the matrix resin satisfies the above-mentioned range, it is possible to provide an article having excellent mechanical, physical and / or chemical properties.

The resin composition may include 1 to 20% by weight of the boron nitride nanotube, based on the total weight of the thermally conductive particles. For example, the resin composition may include, but is not limited to, from 1.5 wt% to 4.5 wt% of the boron nitride nanotube, based on the total weight of the thermally conductive particles. When the content ratio of the thermally conductive particle and the boron nitride nanotube satisfies the above-mentioned ratio, the heat transfer channel is effectively formed, and therefore, an article having excellent thermal conductivity can be provided.

The resin composition may further include additives according to its uses and / or manufacturing methods, but is not limited thereto. For example, the resin composition may further include at least one additive selected from a dispersant, a crosslinking agent, a filler, a viscosity modifier, an impact modifier, a curing agent, a curing accelerator, a defoaming agent, a wetting agent, But is not limited thereto.

The dispersant may include, for example, at least one selected from ketones, esters, and glycol ethers, but is not limited thereto. Specifically, the dispersing agent is selected from the group consisting of acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, methyl But are not limited to, at least one selected from cellosolve, ethyl cellosolve, cellosolve acetate and butyl cellosolve. More specifically, the dispersing agent may be methyl ethyl ketone, but is not limited thereto. The sum of the content of the dispersant and the content of the thermally conductive particles and the boron nitride nanotubes may be 1: 1 to 1: 4, but is not limited thereto.

The crosslinking agent may include, but is not limited to, at least one selected from boric acid, glutaraldehyde, melamine, peroxyester compounds and alcohol compounds.

Examples of the impact modifier include natural rubber, fluoroelastomer, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene-propylene-diene monomer rubber (EPDM), acrylate rubber, hydrogenated nitrile rubber (HNBR) Styrene block copolymer (SBS), styrene-butadiene rubber (SBR), styrene- (ethylene-butene) -styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer ), Styrene- (ethylene-propylene) -styrene block copolymer (SEPS), acrylonitrile-butadiene-styrene copolymer (including ABS, bulk ABS and high-rubber graft ABS) But are not limited to, at least one selected from the group consisting of rhenitrile-ethylene-propylene-diene-styrene copolymer (AES) and methyl methacrylate-butadiene-styrene block copolymer (MBS).

The curing agent may include, for example, at least one selected from amines, imidazoles, guanines, acid anhydrides, dicyandiamides and polyamines, but is not limited thereto. Specifically, the curing agent is selected from the group consisting of 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-phenylimidazole, bis (2- Methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, phthalic anhydride, tetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, But are not limited to, at least one selected from phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and nadic methyl anhydride. More specifically, the curing agent may be nadic methyl anhydride, but is not limited thereto.

The curing accelerator may include, for example, at least one selected from phenols, carboxylic acids, amides, sulfonamides, and amines, but is not limited thereto. Specifically, the curing accelerator may include at least one selected from phenol, cresol, nonylphenol, benzylmethylamine, benzyldimethylamine, and DMP-30, but is not limited thereto. More specifically, the curing accelerator may be benzyldimethylamine, but is not limited thereto.

When the additive is present in the resin composition, the content of the additive may be 25% by weight or less based on the total weight of the resin composition, but is not limited thereto. For example, the content of the additive may be 20% by weight or less, more specifically, 10% by weight or less based on the total weight of the resin composition, but is not limited thereto.

The resin composition may be prepared by mixing thermally conductive particles, boron nitride nanotubes, and matrix resin. The mixing may be melt mixing or solution mixing.

Optionally, the thermally conductive particles and / or the boron nitride nanotubes may be subjected to a pretreatment step prior to being mixed into the matrix resin.

The pretreatment may include dispersing the thermally conductive particles and / or the boron nitride nanotubes in a solvent to obtain a dispersion liquid; Applying ultrasound to the dispersion; And removing the solvent.

After the thermally conductive particles and / or the boron nitride nanotubes are dispersed in a solvent, application of ultrasonic waves may help the thermally conductive particles and / or the boron nitride nanotubes to be evenly dispersed in the matrix resin.

The solvent used in the pretreatment step is not limited as long as it is a solvent compatible with the thermally conductive particles and / or the boron nitride nanotubes. For example, the solvent may be an alcohol, and more specifically ethanol, but is not limited thereto.

The intensity of ultrasound applied in the pre-treatment step is not limited as long as the thermally conductive particles and / or the boron nitride nanotubes can be dispersed in a solvent. However, it is preferable that the ultrasonic wave has a high output. For example, the output of the ultrasonic wave may be 200 W, but the present invention is not limited thereto.

The matrix resin may be premixed with additives, such as curing agents, curing accelerators and / or dispersants, and may be present in the form of a premixture. At this time, the matrix resin, the curing agent, the curing accelerator and / or the dispersing agent may be mechanically stirred using a blade to exist in the form of a homogeneous premixture.

Alternatively, the resin composition may further include a step in which the thermally conductive particles, the boron nitride nanotubes, and the matrix resin are mixed and then degassed. By performing degassing, trace amounts of solvents, additives, and the like that may be present in the resin composition can be removed, and at the same time, pores that may be present in the resin composition can be removed. By removing the pores, the appearance characteristics of the article made of the resin composition can be improved. The step of degassing can preferably proceed in a substantially vacuum state, but is not limited thereto.

article

An article according to an embodiment of the present invention can be produced from the resin composition. 1 is a cross-sectional view schematically showing the structure of an article made of a resin composition according to an embodiment of the present invention.

An article 100 according to an embodiment of the present invention includes thermally conductive particles 110, boron nitride nanotubes 120, and a matrix 130.

The article according to an embodiment of the present invention necessarily includes thermally conductive particles and boron nitride nanotubes so that heat transfer channels can be oriented in various directions (e.g., various directions including vertical and horizontal) Can be improved. Specifically, the heat conduction channel in the article according to an embodiment of the present invention is efficiently formed even in the vertical direction, so that the thermal conductivity in the vertical direction can be very high.

The shape of the article is not limited and can be a shape of a particle, a film, a sheet, a plate, a block, a tube, or the like.

The article may include, but is not limited to, a heat dissipation member of an electronic component, a substrate of an electronic product, a housing of a light emitting diode (LED), a sealing member of a battery, an epoxy molding compound .

For example, the article may be a thermally conductive film, and at least one surface of the thermally conductive film may further include a substrate, an adhesive film, a paste, and / or a release film to form a heat radiation material.

The thermal conductivity of the article may be greater than 3.0 W / mK when measured according to ASTM E1461, but is not limited thereto. When the thermal conductivity of the article satisfies the above-described range, it may be sufficient to release heat generated from various electronic elements inside the electronic product to the outside of the electronic product.

The breakdown voltage of the article may be at least 10.0 kV / mm when measured according to ASTM D149, but is not limited thereto. When the insulation breakdown voltage of the article satisfies the above-described range, the article can maintain electrical insulation even when heat generated in various electronic elements inside the electronic article is released to the outside of the electronic article. Therefore, when the dielectric breakdown voltage of the article satisfies the above-described range, the article can provide sufficient electrical insulation for use in a housing of an electronic product or the like.

The flexural modulus of the article may be at least 20 GPa as measured according to ASTM D790, but is not limited thereto. When the flexural modulus of the article satisfies the above-described range, durability of various electronic elements inside the electronic product can be maintained for a long time.

Method of manufacturing article

The article comprising: providing a resin composition comprising thermally conductive particles, a boron nitride nanotube, and a matrix resin; And

And then heating or curing the resin composition to form an article.

Optionally, before the resin composition is provided, it may further comprise a pre-treatment step of the thermally conductive particles and / or the boron nitride nanotubes described above.

Further, optionally, the above-described vacuum degassing step may be further included before the resin composition is provided.

The heating or curing may be carried out, for example, at a temperature of 150 DEG C or higher and a pressure of 15,000 pounds or more. For example, the curing may be performed under a temperature condition of 200 DEG C or less, but is not limited thereto. For example, the curing may be performed under pressure conditions of 30,000 pounds or less, but is not limited thereto.

The resin composition may be provided by spraying or coating the resin composition on a substrate, but is not limited thereto. Optionally, heat treatment, light irradiation, and the like may be further performed to pattern the article and / or remove the dispersant and the like contained in the resin composition.

Hereinafter, the resin composition according to one embodiment of the present invention and the articles produced therefrom will be described in more detail with reference to comparative examples and examples. However, the present invention is not limited to the following Comparative Examples and Examples.

[Example]

material

(1) Boron nitride nanotubes

The boron nitride nanotubes used in the following examples were prepared with reference to Materials 2014 , 7 , 5789-5801.

SEM photographs of boron nitride nanotubes used in the following examples are shown in Figures 2 and 3. Transmission electron microscopy (TEM) photographs of the boron nitride nanotubes used in the following examples are shown in FIG. An X-ray diffraction (XRD) pattern of the boron nitride nanotubes used in the following Examples is shown in FIG.

(2) Hexavalent boron nitride particles

The hexagonal boron nitride particles used in the following examples were BBI03PB obtained from high purity chemistry. SEM photographs of the hexagonal boron nitride particles used in the following Examples are shown in Fig.

(3) phenol novolac epoxy

The phenol novolac epoxy used in the following examples is the trade name YDPN-631, available from Kukdo Chemical.

Example  One

(1) Pretreatment step: Boron Nitride  Preparation of Nanotube Powder

0.5 g of boron nitride nanotube powder was mixed with 50 mL of ethanol and dispersed for 30 minutes in an ultrasonic horn having a power of 200 W. The dried boron nitride nanotube powder was dried at 50 ° C. in a vacuum drier .

(2) Preparation of preliminary mixture

5 g of phenol novolac epoxy, 4.4 g of nadic methyl anhydride and 0.05 g of benzyldimethylamine were added to the reaction vessel and mechanically stirred with a blade to prepare a homogeneously mixed premix.

(3) Production of resin composition

To the preliminarily prepared preliminary mixture, a boron nitride nanotube (BNNT) powder prepared through a hexagonal boron nitride (h-BN) powder pretreatment step was added. At this time, the weight ratio of the hexagonal boron nitride, the boron nitride nanotube, and the preliminary mixture was 49: 1: 50. To this was added methyl ethyl ketone in an amount of 4.725 g and then mechanically stirred using a blade to obtain a homogeneously mixed slurry. The thus-obtained slurry was vacuum degassed for 5 minutes while maintaining the temperature at 80 캜 to obtain a dried mixture in which methyl ethyl ketone and pores contained in the slurry were removed.

(4) Production of articles

1) Preparation of circular disk specimen

The dried mixture was molded into a stainless steel mold and cured by applying a pressure of 15,000 pounds at 150 DEG C for 4 hours in a hot press to prepare a circular disk specimen having a thickness of 1.0 mm and a diameter of 1.2 cm. A real photograph of the obtained specimen of the circular disk is shown in Fig.

2) Manufacture of rectangular beam-shaped specimens

The dried mixture was molded into a stainless steel mold and then cured by applying a pressure of 15,000 pounds at 150 DEG C for 4 hours in a hot press to form a rectangular beam having a width of 1.27 cm and a length of 12.7 cm and a thickness of 3.4 mm - type specimens were prepared. A real photograph of the obtained rectangular beam-shaped specimen is shown in Fig.

3) Preparation of plate type specimen

The dried mixture was molded into a stainless steel mold and then cured by applying a pressure of 15,000 pounds at 150 DEG C for 4 hours in a hot press to form a square plate having a width of 5 cm and a length of 5 cm and a thickness of 0.5 cm Shaped specimens were prepared. A photograph of the obtained square plate specimen is shown in Fig.

Examples 2 to 6 and Comparative Examples 1 to 2

A specimen corresponding to each shape was prepared in the same manner as in Example 1, except that the weight ratio of the hexaboride boron nitride, the boron nitride nanotube, and the preliminary mixture was changed as shown in Table 1 below.

The weight ratio of h-BN, BNNT and premix Example 1 49: 1: 50 Example 2 48.5: 1.5: 50 Example 3 48: 2: 50 Example 4 69: 1: 30 Example 5 68.5: 1.5: 30 Example 6 68: 2: 30 Comparative Example 1 50: 0: 50 Comparative Example 2 70: 0: 30

Evaluation example 1: SEM photograph

SEM photographs of the circular disk specimens of Example 1 are shown in Figs. 10 and 11. Fig. 12 and 13 show SEM photographs of the fractured section of the circular disk specimen of Comparative Example 1. In addition,

10 and 11, it can be seen that in the specimen of Example 1, the boron nitride nanotubes connect the hexagonal boron nitride particles.

Evaluation example  2: Thermal conductivity evaluation

The thermal conductivities of the circular disk specimens (1 mm thick and 1.2 cm diameter circular disks) of Examples 1 to 6 and Comparative Examples 1 and 2 were measured using a Flash Diffusivity Analyzer, DXF-900 Xenon flash device obtained from TA Instrument It was measured according to ASTM E1461 standard. Three specimens corresponding to the respective examples were evaluated, and the average values thereof are shown in Table 2 below.

The weight ratio of h-BN, BNNT and premix Thermal conductivity
(W / mK) Example 1 49: 1: 50 3.40 Example 2 48.5: 1.5: 50 3.51 Example 3 48: 2: 50 3.62 Example 4 69: 1: 30 6.72 Example 5 68.5: 1.5: 30 6.96 Example 6 68: 2: 30 7.94 Comparative Example 1 50: 0: 50 2.08 Comparative Example 2 70: 0: 30 5.03

It can be seen from Table 2 that the specimens of Examples 1 to 6 have significantly improved thermal conductivity as compared with the specimens of Comparative Examples 1 and 2.

Additionally, the superiority of the results of the embodiments of the present invention can be confirmed by comparing the thermal conductivity of the article disclosed in the article with the thermal conductivity of the article according to embodiments of the present invention. Specifically, in "Study on thermal conductive BN / novolac resin composites (Thermochimica Acta, 523, 111, 2011, Li et al.)", Novolac epoxy composites containing 50 wt% and 70 wt% boron nitride, Respectively, with thermal conductivity of 0.37 W / mK and 0.47 W / mK, respectively. In addition, "thermal conduction of epoxy resin composites filled with combustuion synthesized h-4BN particles (Molecules, 21, 670, 2016, Chung et al.) Contained 46.2 wt.% And 82.4 wt.% Of surface treated boron nitride A novolac epoxy composite has been reported to exhibit a thermal conductivity of 1.8 W / mK and 2.7 W / mK, respectively. In the "Fabrication of thermally conductive composite woth surface modified boron nitride by epoxy wetting method (Ceramic International, 40, 5181, 2014, Kim et al.)" Using epoxy wetting method, 70 wt% boron nitride And that the composite material has a thermal conductivity of 2.8 W / mK. In contrast, it can be seen that the article according to an embodiment of the present invention has improved thermal conductivity by about three times. .

As an example of evaluating the thermal conductivity by dispersing only boron nitride nanotubes in a polymeric resin, a composite material was prepared and evaluated as a "hybrid of high thermal conductivity via BNNTs / epoxy / organic-hybrid composite systems (J Mater Sci: Mater Electron, 5217, 2016, Yung et al.) Reported that composites containing 1 wt%, 3 wt%, and 5 wt% boron nitride nanotubes, respectively, were 0.2 W / mK, 0.3 W / mK, and 0.45 W / mK Of the thermal conductivity. This is a very low value compared to the thermal conductivity seen in the article according to an embodiment of the present invention. Yung et al.'S composite (specifically, a composite containing only boron nitride nanotubes) has an unacceptable level of thermal conductivity Quot; Moreover, the resin composition containing 5% by weight or more of boron nitride nanotubes is very difficult to manufacture in view of the fact that the boron nitride nanotubes are very difficult to be dispersed. Therefore, it can be seen that the resin composition containing only the boron nitride nanotubes is very difficult to commercialize.

Evaluation example  3: Flexural modulus evaluation

The flexural moduli of the rectangular beam-like specimens of Examples 1 and 4 and Comparative Examples 1 and 2 (rectangular beam-shaped specimens having a width of 1.27 cm, a length of 12.7 cm and a length of 3.4 mm) were obtained from WithLab Measured according to ASTM D790 standard using Universal Testing Machine, WL2100A / B. Five specimens corresponding to the respective examples were evaluated, and the average value thereof was shown in Table 3 below.

The weight ratio of h-BN, BNNT and premix Flexural modulus
(GPa) Example 1 49: 1: 50 26.5 Example 4 69: 1: 30 25.7 Comparative Example 1 50: 0: 50 17.1 Comparative Example 2 70: 0: 30 15.9

It can be seen from Table 3 that the specimens of Examples 1 and 4 containing 1.0 weight ratio of boron nitride nanotubes had a significantly improved flexural modulus as compared to the specimens of Comparative Examples 1 and 2 which did not contain boron nitride nanotubes .

While not wishing to be bound by any particular theory, this is believed to be the result of the boron nitride nanotubes connecting between the hexagonal boron nitride particles to increase the bond strength in the matrix.

From the flexural modulus results, it was confirmed that an article made of a resin composition according to an embodiment of the present invention has sufficient mechanical durability to withstand long-term heat release and temperature change in an electronic device inside the electronic product.

Evaluation example  4: Evaluation of dielectric breakdown voltage

The dielectric breakdown voltages of the plate specimens of Examples 1 and 4 and Comparative Examples 1 and 2 (5 cm width, 5 cm length and 0.5 cm thickness plate) were measured using a Dielectric Breakdown Tester from Haefely Hitronics , 710-56A-B according to ASTM D-149 standard. Five specimens corresponding to each example were evaluated, and their average values are shown in Table 4 below.

The weight ratio of h-BN, BNNT and premix Dielectric breakdown voltage
(kV / mm) Example 1 49: 1: 50 16 Example 4 69: 1: 30 14 Comparative Example 1 50: 0: 50 16 Comparative Example 2 70: 0: 30 14

It can be seen from Table 4 that the specimens of Examples 1 and 4 containing 1.0 weight ratio of boron nitride nanotubes had breakdown voltages equal or similar to those of Comparative Examples 1 and 2 without boron nitride nanotubes .

From the results of the dielectric breakdown voltage, it was confirmed that the article made of the resin composition according to one embodiment of the present invention had sufficient electrical insulation property for heat dissipation in the electronic device inside the electronic product.

100: Goods
110: thermally conductive particle
120: boron nitride nanotubes
130: Matrix

Claims (18)

A resin composition capable of producing an article having a thermal conductivity of 3.0 W / mK or more, a breakdown voltage of 10.0 kV / mm or more, and a flexural modulus of 20 GPa or more, The composition comprises
A thermally conductive particle having an average aspect ratio of 1 to 300, a boron nitride nanotube, and a matrix resin,
The average diameter of the boron nitride nanotubes is 2 nm to 1 占 퐉,
The average length of the boron nitride nanotubes is 0.5 μm to 1,000 μm,
The average aspect ratio of the boron nitride nanotubes is 5 to 100,000,
Based on the total weight of the resin composition,
10% to 69% by weight of the thermally conductive particles;
More than 0 wt% to 20 wt% of the boron nitride nanotubes; And
From 20% by weight to 70% by weight of the matrix resin,
Based on the total weight of the thermally conductive particles, from 1.5 wt% to 4.5 wt% of the boron nitride nanotubes,
Wherein the thermally conductive particles comprise aluminum nitride, aluminum oxide, aluminum oxynitride, boron nitride, boron oxide, boron oxynitride, silicon oxide, silicon carbide, beryllium oxide or combinations thereof. The method according to claim 1,
Wherein the thermally conductive particles have an average particle diameter of 0.1 占 퐉 to 150 占 퐉. The method according to claim 1,
Wherein the thermally conductive particles comprise boron nitride. The method according to claim 1,
Wherein the thermally conductive particles are hexagonal boron nitride particles. 5. The method of claim 4,
The average particle diameter of the hexagonal boron nitride particles is 0.1 mu m to 150 mu m,
Wherein the hexagonal boron nitride particles have an average aspect ratio of from 10 to 300. The method according to claim 1,
Wherein the matrix resin is a thermoplastic resin or a thermosetting resin. The method according to claim 1,
The matrix resin may be selected from the group consisting of nylon resin, polyethylene resin, polypropylene resin, polybutylene resin, polyester resin, polyurethane resin, polyacrylic resin, styrene butadiene resin, vinyl resin, polycarbonate resin, polysulfone resin, , At least one selected from the group consisting of polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetate resin, polystyrene resin, styrene divinyl benzene resin, fluororesin, acrylic resin, silicone resin, epoxy resin, amino resin and phenol resin , Resin composition. The method according to claim 1,
Wherein the matrix resin is an epoxy resin. The method according to claim 1,
Further comprising an additive. An article made from the resin composition of any one of claims 1 to 9. 11. The method of claim 10,
The thermal conductivity of the article is at least 3.0 W / mK;
The breakdown voltage of the article is at least 10.0 kV / mm;
Wherein the article has a flexural modulus of at least 20 GPa. A resin composition capable of producing an article having a thermal conductivity of 3.0 W / mK or more, a breakdown voltage of 10.0 kV / mm or more, and a flexural modulus of 20 GPa or more, wherein the resin composition comprises thermally conductive particles having an average aspect ratio of 1 to 300 Providing a resin composition comprising a boron nitride nanotube and a matrix resin; And
And heating or curing the resin composition to form an article,
The average diameter of the boron nitride nanotubes is 2 nm to 1 占 퐉,
The average length of the boron nitride nanotubes is 0.5 μm to 1,000 μm,
The average aspect ratio of the boron nitride nanotubes is 5 to 100,000,
Based on the total weight of the resin composition,
10% to 69% by weight of the thermally conductive particles;
More than 0 wt% to 20 wt% of the boron nitride nanotubes; And
From 20% by weight to 70% by weight of the matrix resin,
Based on the total weight of the thermally conductive particles, from 1.5 wt% to 4.5 wt% of the boron nitride nanotubes,
Wherein the thermally conductive particles comprise aluminum nitride, aluminum oxide, aluminum oxynitride, boron nitride, boron oxide, boron oxynitride, silicon oxide, silicon carbide, beryllium oxide or combinations thereof. 13. The method of claim 12,
Before the step of providing the resin composition,
Further comprising the step of pretreating said thermally conductive particles and / or said boron nitride nanotubes;
The pretreatment may include dispersing the thermally conductive particles and / or the boron nitride nanotubes in a solvent to obtain a dispersion;
Applying ultrasound to the dispersion; And
And removing the solvent.
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