KR20130049520A - A particle having high heat radiation property, method for manufacture thereof, and adhesive composition for packaging electronic components - Google Patents

Abstract

PURPOSE: A high heat-radiating particle is provided to have excellent insulating performance while maintaining high heat conductivity and to form heat conductive paths for connecting heat conductive fillers in an adhesive composition, thereby improving heat-radiating performance. CONSTITUTION: A high heat-radiating particle comprises a carbon-based substrate; and a metal hydroxide material layer formed on the surface of the carbon-based substrate; and one or more coating layers selected from a metal oxide layer, a mixture layer of metal hydroxide and metal oxide. A manufacturing method of the high heat-radiating particle comprises a step of treating a carbon-based substrate with a strong acid; a step of treating the carbon-based substrate with a reducing agent; a step of conducting reaction of the carbon-based substrate and a precursor solution of the metal hydroxide or metal oxide; and a step of heat-treating the reaction product. [Reference numerals] (AA) Strong acid treatment; (BB) Reducing agent treatment; (CC) Metal hydroxide precursor solution or metal oxide precursor solution; (DD) Heat treatment; (EE) Coating layer; (FF) Carbon-based substrate

Description

A particle having high heat radiation property, method for manufacture, and adhesive composition for packaging electronic components

The present invention relates to high heat dissipating particles, a method of manufacturing the same, and an adhesive composition for packaging an electronic component including the same.

The heat-radiation sheet which hardened the resin composition obtained by mix | blending thermally conductive fillers, such as alumina or silica, with the flexible resin and shape | molding on the sheet | seat is, for example, electrical goods, such as a personal computer or a plasma display panel (PDP) It is sandwiched between heat generators, such as electronic components, and heat sinks, such as heat sinks, heat dissipation fins, and metal heat sinks, for use in heat dissipating heat generated by electronic parts.

Recently, due to the integration of electronic components, the thermal integration phenomenon has become more severe. Accordingly, interest in high heat dissipation materials is increasing in order to prevent functional failure of the electronic components due to the thermal integration phenomenon.

Conventionally, heat problems caused by electronic parts have been solved through a heat dissipation sheet manufactured using a resin composition for heat dissipation material including a thermally conductive filler such as alumina or silica, but thermal integration due to electronic parts becomes more severe. Accordingly, there is a demand for development of a high heat dissipation material having more heat dissipation than a conventional heat dissipation material. In addition, since insulating ceramic particles which are conventionally used as high heat-dissipating particles have a high cost, development of particles having low heat and high heat dissipation is urgently required.

An object of this invention is to provide the high heat dissipation particle | grains, its manufacturing method, the adhesive composition for electronic component packaging containing this, and a heat dissipation material.

The present invention as a means for solving the above problems, a carbon-based substrate; And at least one coating layer selected from the group consisting of a metal hydroxide layer, a metal oxide layer, and a mixed layer of metal hydroxide and metal oxide formed on the surface of the carbon-based substrate.

The present invention as another means for solving the above problems, (a) treating the carbon-based substrate with a strong acid; (b) treating the carbon-based substrate obtained through step (a) with a reducing agent; (c) reacting the carbon-based substrate obtained through step (b) with a precursor solution of metal hydroxide or a precursor solution of metal oxide; And (d) heat treating the reaction product obtained through the step (c).

The present invention is another means for solving the above problems, the adhesive resin; Thermally conductive fillers; And it provides an adhesive composition for packaging electronic components comprising the high heat-dissipating particles according to the present invention.

As another means for solving the above problems, the present invention provides a heat dissipation material comprising a cured product of the adhesive composition for electronic component packaging according to the present invention.

High heat-dissipating particles of the present invention is a carbon-based substrate; And at least one coating layer selected from the group consisting of a metal hydroxide layer, a metal oxide layer, and a mixed layer of a metal hydroxide and a metal oxide formed on the surface of the carbon-based substrate, thereby maintaining high thermal conductivity of the carbon-based substrate while maintaining insulation properties. Can have In addition, the adhesive composition for packaging an electronic component of the present invention is an adhesive resin; Thermally conductive fillers; And high heat-dissipating particles according to the present invention, while maintaining insulating properties, the high heat-dissipating particles form a thermally conductive path connecting the thermally conductive fillers in the adhesive composition of the present invention, thereby further improving the heat dissipation effect. have.

1 is a view schematically showing a manufacturing method of high heat-dissipating particles according to an embodiment of the present invention.
2 is a scanning electron micrograph of a heat dissipating material according to one embodiment of the invention.

The present invention is a carbon-based substrate; And at least one coating layer selected from the group consisting of a metal hydroxide layer, a metal oxide layer, and a mixed layer of metal hydroxide and metal oxide formed on the surface of the carbon-based substrate.

Hereinafter, the high heat dissipation particle of this invention is demonstrated concretely.

The high heat-dissipating particles of the present invention include a carbon-based substrate and a coating layer formed on the surface of the carbon-based substrate, wherein the coating layer is selected from the group consisting of a metal hydroxide layer, a metal oxide layer and a mixed layer of metal hydroxide and metal oxide. There may be more than one.

In the present invention, the carbon-based substrate may serve to impart high thermal conductivity to the high heat dissipating particles of the present invention. The kind of the carbon-based substrate is not particularly limited, and any carbon-based material having high thermal conductivity can be used. In the present invention, examples of the carbon-based substrate may include one or more selected from the group consisting of carbon nanotubes, carbon fibers, graphite, and graphene. It is not limited.

In the present invention, the coating layer formed on the surface of the carbon-based substrate may serve to provide insulation to the high heat-dissipating particles of the present invention by blocking the electrical conductivity while maintaining the high thermal conductivity of the carbon-based substrate.

The coating layer may be at least one selected from the group consisting of a metal hydroxide layer including a metal hydroxide, a metal oxide layer including a metal oxide, and a mixed layer including a mixture of a metal hydroxide and a metal oxide.

In the present invention, the metal hydroxide included in the metal hydroxide layer may be at least one selected from the group consisting of aluminum hydroxide (Al (OH) ₃ ), titanium hydroxide (Ti (OH) ₄ ) and mixtures thereof, but is not limited thereto. It doesn't happen.

In the present invention, the metal oxide included in the metal oxide layer may be at least one selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ) and silicon dioxide (SiO ₂ ), but is not limited thereto. It is not.

In the present invention, the metal hydroxide and the metal oxide included in the mixed layer may be hydroxides and oxides of the same metal. For example, in the present invention, the mixed layer may include aluminum hydroxide and aluminum oxide, or may include titanium hydroxide and titanium dioxide, but is not limited thereto.

In the present invention, the thickness of the coating layer is not particularly limited, but may be preferably 10 μm to 200 μm, more preferably 50 μm to 100 μm. When the thickness of the coating layer is less than 10 μm, the adhesion and mechanical properties may be lowered, and when the thickness of the coating layer is greater than 200 μm, the sedimentation phenomenon of the high heat radiation particles may occur.

The invention also comprises the steps of: (a) treating a carbon-based substrate with a strong acid; (b) treating the carbon-based substrate obtained through step (a) with a reducing agent; (c) reacting the carbon-based substrate obtained through step (b) with a precursor solution of metal hydroxide or a precursor solution of metal oxide; And (d) heat treating the reaction product obtained through step (c).

Hereinafter, the manufacturing method of the high heat dissipation particle | grains of this invention is demonstrated concretely.

1 is a view schematically showing a method for producing high heat-dissipating particles according to one embodiment of the present invention.

In order to prepare the high heat-dissipating particles of the present invention, step (a) may be performed first, and step (a) is a step of treating the carbon-based substrate with a strong acid to introduce a carboxyl group to the surface of the carbon-based substrate. Specific contents of the carbon-based substrate are the same as described above.

The kind of the strong acid in step (a) of the present invention is not particularly limited, and any material may be used as long as it is a substance capable of introducing a carboxyl group on the surface of the carbon-based substrate. In the present invention, examples of the strong acid include at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, hydroiodic acid, hydrobromic acid, and mixtures thereof, preferably a mixture of hydrochloric acid and nitric acid and sulfuric acid and A mixture of nitric acid, and the like, but is not limited thereto.

In the present invention, step (a) is specifically 12 hours to 48 hours, preferably 18 hours while putting the carbon-based substrate in the above-mentioned strong acid solution and heated to 40 ℃ to 80 ℃, preferably 50 ℃ to 70 ℃ It may include a step of stirring for 36 hours. Through the step of heating and stirring the strong acid solution containing the carbon-based substrate, a reaction between the surface of the carbon-based substrate and the strong acid can be caused to introduce a carboxyl group to the surface of the carbon-based substrate.

When the heating and stirring temperature is less than 40 ° C, the reaction between the carbon-based substrate and the strong acid may not be sufficiently performed, so that a carboxyl group may not be formed on the surface of the carbon-based substrate. May be caused.

In addition, when the heating and stirring time is less than 12 hours, the reaction between the carbon-based substrate and the strong acid may not be sufficiently performed so that a carboxyl group may not be formed on the surface of the carbon-based substrate, and when it exceeds 48 hours, the surface of the carbon-based substrate Damage may be caused.

In the present invention, step (a) may further include a process of diluting and washing the strong acid solution including the carbon-based substrate after the heating and stirring process.

Dilution of the strong acid solution containing the carbon-based substrate may be performed by dispersing the strong acid solution in distilled water, preferably secondary distilled water. After the dilution process, by washing the strong acid solution several times using tertiary distilled water, the acidity of the strong acid solution containing the carbon-based substrate can be adjusted to pH 7.

In the present invention, step (a) may further include a process of filtering and drying the reaction solution including the carbon-based substrate after the dilution and washing process. Through the filtration and drying process, particles of a carbon-based substrate having a carboxyl group introduced therein may be obtained.

The filtration process may be carried out through a filter, the type of the filter is not particularly limited, as long as it can extract a carbon-based substrate can be used without limitation. In the present invention, for example, a membrane filter may be used, but is not limited thereto.

In the step (a) of the present invention, by drying the carbon-based substrate extracted through the filtration process, a carbon-based substrate having a carboxyl group introduced into the surface can be obtained in the form of particles. The drying means is not particularly limited, and drying means generally used in this field may be used without limitation. In the present invention, for example, it is possible to dry the carbon-based substrate extracted through the filtration process using a forced circulation drying apparatus, but is not limited thereto.

The method for producing high heat dissipating particles of the present invention may include step (b), wherein step (b) is performed to replace the carboxyl group introduced on the surface of the carbon-based substrate through the step (a) with a hydroxyl group, the step Treatment of the carbon-based substrate obtained through (a) with a reducing agent.

The type of the reducing agent in step (b) of the present invention is not particularly limited and may be used without limitation as long as the carboxyl group introduced on the surface of the carbon-based substrate can be substituted with a hydroxyl group. In the present invention, examples of the reducing agent include at least one selected from the group consisting of lithium aluminum hydride (LiAlH ₄ ), sodium borohydride (NaBH ₄ ) and mixtures thereof, preferably lithium aluminum hydride. Rides, but is not limited thereto.

The term "parts by weight" used in the present invention means a weight ratio.

In the present invention, step (b) may include a step of reacting 1 part by weight to 30 parts by weight, preferably 5 parts by weight to 20 parts by weight of a reducing agent based on 100 parts by weight of the carbon-based substrate obtained through step (a). Can be. The carboxyl group introduced to the surface of the carbon-based substrate through the reaction can be reduced and substituted with a hydroxy group. If the content of the reducing agent is less than 1 part by weight, it may be difficult to quantitatively reduce the substitution, and if it is more than 30 parts by weight, the addition reaction due to the remaining reducing agent may proceed.

In the step (b) of the present invention, the process of reacting the carbon-based substrate obtained through step (a) with a reducing agent is performed at a temperature of 20 ° C. to 50 ° C., preferably 25 ° C. to 40 ° C., and most preferably at room temperature for 1 hour. It can be carried out for the above.

In the present invention, step (b) may further include a step of uniformly dispersing the carbon-based substrate obtained through step (a) before the process of reacting the carbon-based substrate obtained through step (a) and the reducing agent. . Uniformly dispersing the carbon-based substrate obtained through step (a) with the reducing agent may induce uniform functional group formation on the surface of the carbon-based substrate.

In the step (b) of the present invention, the dispersion process is not particularly limited, and the carbon-based substrate obtained through step (a) is placed in a dispersion solvent generally used in this field, and a dispersion method generally used in this field is used. It can be performed using. In the present invention, the carbon-based substrate can be uniformly dispersed by, for example, putting the carbon-based substrate obtained through step (a) in anhydrous THF (Tetrahydrofuran) solvent, which is a dispersion solvent, and stirring or / and sonicating. It is not limited to this.

In the present invention, step (b) may further include a step of filtering and drying the reaction solution after the step of reacting the carbon-based substrate and the reducing agent obtained through step (a). Through the filtration and drying process, it is possible to obtain particles of a carbon-based substrate having a hydroxyl group introduced therein.

The filtration process may be carried out through a filter, the type of the filter is not particularly limited, as long as it can extract a carbon-based substrate can be used without limitation. In the present invention, for example, a membrane filter may be used, but is not limited thereto.

In step (b) of the present invention, by drying the carbon-based substrate extracted through the filtration process, it is possible to obtain a carbon-based substrate having a hydroxyl group introduced on the surface in the form of particles. The drying means is not particularly limited, and drying means generally used in this field may be used without limitation. In the present invention, for example, it is possible to dry the carbon-based substrate extracted through the filtration process using an oven of natural drying or 50 ℃, but is not limited thereto.

The method for producing high heat-dissipating particles of the present invention may include step (c), wherein step (c) is a precursor or metal oxide of a hydroxyl group and a metal hydroxide introduced on the surface of the carbon-based substrate obtained through step (b). In order to perform a dehydration condensation reaction of the precursor, the carbon-based substrate obtained through the step (b) is a step of reacting with a precursor solution of a metal hydroxide or a precursor solution of a metal oxide.

The kind of the precursor of the metal hydroxide or the precursor of the metal oxide in step (c) of the present invention is not particularly limited, and any compound that can be bonded through a dehydration condensation reaction with a hydroxyl group introduced on the surface of the carbon-based substrate may be used without limitation. Can be. In the present invention, as an example of the precursor of the metal hydroxide or the precursor of the metal oxide, aluminum isopropoxdie (AIP), tetraethly orthosilicate (TEOS) and titanium (IV) isopropoxide (titanium) (IV) isopropoxide) and one or more selected from the group consisting of, preferably aluminum isopropoxide, but is not limited thereto.

In step (c) of the present invention, the precursor solution of the metal hydroxide or the precursor solution of the metal oxide may be prepared by dispersing the precursor of the metal hydroxide or the precursor of the metal oxide in a dispersion solvent.

The dispersion solvent and the dispersion method are not particularly limited, and those commonly used in the art may be used without limitation. In the present invention, for example, a precursor of a metal hydroxide or a precursor of a metal oxide is placed in a mixture of water and methanol as a dispersion solvent, preferably a mixture having a weight ratio of water and methanol of 4: 1, and stirred or / and sonicated. A precursor solution of a metal hydroxide or a precursor solution of a metal oxide may be prepared, but is not limited thereto.

Step (c) of the present invention may be carried out by reacting the carbon-based substrate obtained through step (b) with a precursor solution of metal hydroxide or a precursor solution of metal oxide at a temperature of 40 ° C. to 80 ° C. for at least 5 hours. If the reaction temperature is less than 40 ℃, the efficiency of the reaction by the dehydration condensation may be lowered, if it exceeds 80 ℃, shape control may not be easy due to rapid dehydration condensation.

In addition, when the reaction time is less than 5 hours, the reaction may not proceed sufficiently so that the dehydration condensation reaction may not occur between the hydroxyl group introduced on the surface of the carbon-based substrate or the precursor of the metal hydroxide or the precursor of the metal oxide. The upper limit of the reaction time is not particularly limited, and can be adjusted, for example, to 7 hours or less, preferably 9 hours or less.

The complexation between the carbon-based substrate and the metal hydroxide or the metal oxide through the dehydration condensation reaction between the hydroxy group on the surface of the carbon-based substrate and the precursor of the metal hydroxide or the precursor of the metal oxide is performed through the chemical surface treatment of the carbon-based substrate. The sol-gel method of allowing the formation of particles on the surface of the metal is different from the conventional process of preparing metal oxide nanoparticles and then complexing them with a carbon-based substrate through chemical covalent bonding.

In the present invention using the sol-gel method, the entire surface of the carbon-based substrate is coated with a metal hydroxide precursor or a metal oxide precursor to form a coating layer on the surface of the carbon-based substrate, but according to the existing process The metal oxide nanoparticles may be present in a partially doped form on the surface of the carbon-based substrate.

In the present invention, the coating layer formed on the surface of the carbon-based substrate can impart high insulation to the high heat-dissipating particles of the present invention by blocking the electrical conductivity while maintaining the high thermal conductivity of the carbon-based substrate, but the existing process and In the case of the heat-dissipating particles manufactured as described above, the metal oxide nanoparticles may not completely block the electrical conductivity of the carbon-based substrate, and thus may have poor insulation.

The method for producing high heat-dissipating particles of the present invention may include step (d), wherein step (d) comprises a metal hydroxide layer, a metal oxide layer, or a metal hydroxide on the surface of the carbon-based substrate obtained through step (c). In order to form a mixed layer of the metal oxide, the reaction product obtained through step (c) is heat treated.

In the present invention, step (d) may include a step of heat treating the reaction product obtained through step (c) at a temperature of 300 ° C. to 500 ° C. for at least 4 hours.

Depending on the heat treatment temperature of the reaction product, a metal hydroxide layer, a mixed layer of metal hydroxide and metal oxide or a metal oxide layer may be formed on the surface of the carbon-based substrate. The higher the heat treatment temperature within the above temperature range, the metal oxide layer tends to be formed. In the present invention, for example, a metal hydroxide layer such as an aluminum hydroxide layer may be formed at a heat treatment temperature of 300 ° C., but a metal oxide layer such as an aluminum oxide layer may be formed at a heat treatment temperature of 500 ° C.

If the heat treatment temperature is less than 300 ° C, not only the metal oxide layer but also the metal hydroxide layer may not be sufficiently formed, and if it exceeds 500 ° C, the structure of the carbon-based material may collapse.

In addition, when the heat treatment time is less than 4 hours, it may be difficult to sufficiently form a metal hydroxide layer, a mixed layer of metal hydroxide and metal oxide or a metal oxide layer on the surface of the carbon-based substrate. The upper limit of the reaction time is not particularly limited and can be adjusted, for example, to 24 hours or less, preferably 12 hours or less.

In the present invention, step (d) may further include a step of removing and washing the solvent of the reaction product solution obtained through step (c) before the heat treatment process. Through the solvent removal and washing process, impurities other than the reaction product may be removed.

The solvent removal process in step (d) of the present invention is not particularly limited, and any solvent can be used without limitation as long as the solvent can be easily removed. In the present invention, for example, a solvent of the reaction product solution may be removed using a rotary evaporator, but is not limited thereto.

In addition, in the step (d) of the present invention, the washing process may be performed using a washing solution, and may be repeated until the remaining impurities are removed.

The kind of the washing solution is not particularly limited, and any type of the washing solution may be used without limitation as long as it can easily remove impurities remaining in the reaction product particles obtained through the solvent removal process, for example, precursors of metal hydroxides or precursors of metal oxides. have. In the present invention, for example, in order to remove impurities remaining in the reaction product particles, washing with secondary distilled water several times, but is not limited thereto.

The present invention also provides an adhesive resin; Thermally conductive fillers; And it relates to an adhesive composition for packaging electronic components comprising high heat-dissipating particles according to the present invention.

The adhesive composition for packaging an electronic component of the present invention may include an adhesive resin, and the adhesive resin may serve to bond the electronic component.

In the present invention, the kind of the adhesive resin is not particularly limited, and if it is excellent in adhesiveness, those commonly used in this field may be used without limitation. In the present invention, examples of the adhesive resin may include at least one selected from the group consisting of an epoxy resin, an acrylic resin, a urethane resin, and a silicone-urethane resin, and preferably an epoxy resin, but is not limited thereto. It doesn't happen.

The adhesive composition for packaging an electronic component of the present invention includes a thermally conductive filler, and the thermally conductive filler may serve to provide heat dissipation by transferring heat generated according to the operation of the electronic component to the outside.

In the present invention, the type of the thermally conductive filler is not particularly limited, and any material having excellent thermal conductivity and insulating property may be used without limitation. In the present invention, examples of the thermally conductive filler include aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), zinc oxide (ZnO), silicon oxide (SiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), and magnesium hydroxide. (Mg (OH) ₂ ), silicon carbide (SiC), aluminum nitride (AlN), boron nitride (BN) and silicon nitride (Si ₃ N ₄ ) One or more selected from the group consisting of, but is not limited thereto. no.

In the adhesive composition of the present invention, the thermally conductive filler may be included in an amount of 10 parts by weight to 100 parts by weight, preferably 30 parts by weight to 80 parts by weight, based on 100 parts by weight of the adhesive resin. When the content of the thermally conductive filler is less than 10 parts by weight, the thermally conductive filler is too small to release heat generated in the electronic component to the outside, and when the content of the thermally conductive filler exceeds 100 parts by weight, the adhesive strength of the adhesive composition may be lowered.

Adhesive composition for packaging electronic components of the present invention comprises the high heat-dissipating particles according to the present invention described above, wherein the high heat-dissipating particles in the adhesive composition of the present invention by forming a thermal conductive path connecting between the thermally conductive fillers, It can play a role of further improving the effect. Details of the high heat-dissipating particles are the same as described above, and will be omitted below.

In the adhesive composition of the present invention, the high heat-dissipating particles may be included in an amount of 0.1 parts by weight to 10 parts by weight, preferably 1 part by weight to 5 parts by weight, based on 100 parts by weight of the adhesive resin. When the content of the high heat-dissipating particles is less than 0.1 part by weight, the heat conduction path may not be sufficiently performed, and thus, the heat dissipation effect may not be improved. It may not be easy.

The adhesive composition for packaging an electronic component of the present invention may further include a multifunctional crosslinking agent in addition to the above components, and may adjust physical properties such as cohesion and adhesive properties of the cured product according to the amount of the multifunctional crosslinking agent used.

The kind of the multifunctional crosslinking agent that can be used in the present invention is not particularly limited, and for example, a general crosslinking agent such as an isocyanate compound, an epoxy compound, an aziridine compound and a metal chelate compound can be used. Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate or naphthalene diisocyanate, One kind or a mixture of two or more kinds of reactants of a polyol (ex. Trimethylol propane); Examples of epoxy compounds include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl ethylenediamine and glycerin diglycidyl ether. One or more selected from the group consisting of; Examples of aziridine compounds include N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxes) Mid), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine), and tri-1-aziridinylphosphine oxide. In addition, examples of the metal chelate-based compound may be a compound in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated with acetyl acetone, ethyl acetoacetate, or the like. It is not limited.

In the adhesive composition of the present invention, the multifunctional crosslinking agent may be included in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the adhesive resin. When the content of the multifunctional crosslinking agent is less than 0.01 part by weight, the cohesive force of the cured product may be lowered and bubbles may occur when measuring the high temperature reliability. When the content of the multifunctional crosslinking agent exceeds 10 parts by weight, the adhesiveness and peeling force of the adhesive may be so high that the adhesive strength and the peeling force may be reduced, and the interlayer foil may be reduced. Durability may be reduced, such as a phenomenon of lifting or lifting.

The present invention also relates to a heat dissipating material comprising a cured product of the adhesive composition for electronic component packaging according to the present invention.

The heat dissipation material of this invention can be obtained by hardening | curing the adhesive composition for electronic component packaging to a desired shape, such as a sheet form, a tape form, a tube form, or a roll form, and the shape, the hardening method, the hardening | curing apparatus, etc. are not specifically limited. The adhesive composition for packaging an electronic component may be cured through a crosslinking reaction between the polyfunctional crosslinking agent and the adhesive resin contained in the composition.

The heat dissipating material of the present invention may be obtained by, for example, inserting an adhesive composition for packaging an electronic component into an injection mold or a batch mold, and curing the resin to a desired shape, and curing the sheet into a sheet by a method such as an extruder or a mold. It may be.

The temperature for curing the adhesive composition for electronic component packaging of the present invention is not particularly limited, but may be preferably 100 ° C to 250 ° C, more preferably 130 ° C to 200 ° C.

When the heat dissipation material of the present invention is molded into a sheet to form a heat dissipation sheet, the heat dissipation sheet may have a thickness of 0.1 mm to 10 mm, preferably 0.5 mm to 5 mm.

The heat dissipating material of the present invention is a cured adhesive composition for electronic components described above, which means that the fluidity of the adhesive composition is greatly reduced, and in addition to the solidified state without completely fluidity, the fluidity remains slightly ( Bird's eye view or putty image).

Moreover, as a usage method of the heat dissipation material of this invention, it is preferable to harden previously the adhesive composition for electronic component packaging, and to use it, interposing between a heat generating body and a heat radiating body, for example. By doing as mentioned above, there exists a tendency for the deformation | transformation of material properties, such as flexibility or durability which arises by the deformation | transformation of the hardening degree of a heat radiating material, to be small.

The thermal conductivity of the heat dissipating material of the present invention may be appropriately designed by the required performance, but preferably 0.3 W / m · K to 3 W / m · K, more preferably 0.5 W / m · K to 3 It may be W / m · K, more preferably 1 W / m · K to 3 W / m · K. The thermal conductivity of the said heat radiating material can be measured, for example with a thermal conductivity meter (LFA 457, NETZCH company make).

The invention also relates to an electronic component package comprising a heat dissipating material according to the invention.

As long as the electronic component package of the present invention includes the heat dissipating material according to the present invention, the configuration, structure, or manufacturing method thereof is not particularly limited, and those commonly used in this field may be employed without limitation.

In the present invention, the electronic component package including the heat dissipation material according to the present invention may be a semiconductor chip package, a printed circuit board (PCB) package, or an LED chip package, but is not limited thereto.

[ Example ]

Hereinafter, the present invention will be described in more detail through examples according to the present invention, but the scope of the present invention is not limited to the examples given below.

< High heat dissipation  Preparation of Particles>

Manufacturing example  One

Treating the carbon-based substrate with a strong acid

0.5 g of carbon nanotube powder as a carbon-based substrate was added to 240 g of a mixed solution of sulfuric acid and nitric acid (sulfuric acid: nitric acid = 3: 1, volume ratio), and stirred for 24 hours while heating to 60 ° C. Subsequently, the strong acid solution in which the carbon nanotube powder is mixed is diluted with 500 g of secondary distilled water and washed with tertiary distilled water several times, thereby increasing the pH of the strong acid solution in which the carbon nanotube powder is mixed. 7 was adjusted. Thereafter, the solution was filtered using a PTFE (polytetrafluoroethylene) membrane filter (manufactured by Advantec Co., Ltd., pore size: 0.2 μm), and then dried using a forced circulation oven, thereby introducing carbon nanotube particles having a carboxyl group introduced thereon. Got.

Treating the carbon-based substrate with a reducing agent

0.5 g of carbon nanotube particles having a carboxyl group introduced into the surface were put in 200 g of anhydrous THF (tetrahydrofuran) solution as a solvent, uniformly dispersed by stirring and sonication, and 0.5 g of lithium aluminum hydride (LiAlH ₄ ) as a reducing agent. Was added to the solution, and the oxidation-reduction reaction was carried out at room temperature for 6 hours. Subsequently, after adding a hydrochloric acid solution to the redox reaction solution, the solution was filtered using a PTFE (polytetrafluoroethylene) membrane filter (manufactured by Advantec, pore size: 0.2 μm), and then using an oven at 50 ° C. And dried to obtain carbon nanotube particles having a hydroxyl group introduced thereon.

Reacting the carbon-based substrate with a precursor solution of a metal hydroxide

0.5 g of carbon nanotube particles having a hydroxyl group introduced on the surface thereof were placed in 200 g of secondary distilled water, and uniformly dispersed by ultrasonication. In addition, 2 g of aluminum isopropoxide (AIP), which is a precursor of aluminum hydroxide, was placed in 300 g of a mixed solution of water and ethanol (water: ethanol = 4: 1, volume ratio), and uniformly dispersed by ultrasonication. Subsequently, the dispersion solution containing the carbon nanotube particles and the dispersion solution containing aluminum isopropoxide are mixed and reacted for 12 hours while heating at 60 ° C. to thereby perform a dehydration condensation reaction between the aluminum isopropoxide and the hydroxyl group. Induced.

Heat treating the reaction product

The solvent was removed from the reaction product solution resulting from the dehydration condensation reaction between the hydroxy group formed on the surface of the carbon nanotube and aluminum isopropoxide using a rotary evaporator (SB-1000, EYELA Co., Ltd.) to obtain reaction product particles. . The reaction product particles were washed several times with secondary distilled water to completely remove the remaining aluminum isopropoxide. Subsequently, the reaction product particles were heat treated at 300 ° C. for 4 hours, thereby preparing carbon nanotube particles having an aluminum hydroxide (Al (OH) ₃ ) layer (thickness: 50 μm) formed on a surface thereof.

<Production of heat dissipation material>

Example  One

50 parts by weight of aluminum oxide (manufactured by Aldrich), which is a thermally conductive filler, and 1 part by weight of the high heat dissipating particles prepared in Preparation Example 1 were blended with respect to 100 parts by weight of an epoxy resin to prepare an adhesive composition for electronic component packaging. This was appropriately diluted with toluene, a solvent, to prepare a coating solution. Subsequently, the prepared coating solution was poured into a PTFE (polytetrafluoroethylene) mold, and cured at 180 ° C. for 3 hours to prepare a sheet-like heat dissipating material (A) having a thickness of 1 mm.

Example  2

A sheet-like heat-dissipating material (B) was prepared in the same manner as in Example 1, except that the content of the high heat-dissipating particles prepared in Preparation Example 1 was changed to 2 parts by weight.

Example  3

A sheet-like heat-dissipating material (C) was prepared in the same manner as in Example 1, except that the content of the high heat-dissipating particles prepared in Preparation Example 1 was changed to 3 parts by weight.

Example  4

A sheet-like heat dissipating material (D) was manufactured in the same manner as in Example 1, except that the content of aluminum oxide (manufactured by Aldrich, Inc.), which is a thermally conductive filler, was changed to 70 parts by weight.

Example  5

A sheet-like heat-dissipating material (E) was prepared in the same manner as in Example 4, except that the content of the high heat-dissipating particles prepared in Preparation Example 1 was changed to 2 parts by weight.

Example  6

A sheet-like heat-dissipating material (F) was manufactured in the same manner as in Example 4, except that the content of the high heat-dissipating particles prepared in Preparation Example 1 was changed to 3 parts by weight.

Example  7

A sheet-like heat-dissipating material (G) was manufactured in the same manner as in Example 1, except that the content of aluminum oxide (manufactured by Aldrich), which is a thermally conductive filler, was changed to 80 parts by weight.

Example  8

A sheet-like heat-dissipating material (H) was manufactured in the same manner as in Example 7, except that the content of the high heat-dissipating particles prepared in Preparation Example 1 was changed to 2 parts by weight.

Example  9

Sheet-like heat dissipating material (I) was prepared in the same manner as in Example 7, except that the content of the high heat dissipating particles prepared in Preparation Example 1 was changed to 3 parts by weight.

Comparative example  One

A sheet-like heat-dissipating material (J) was prepared in the same manner as in Example 1, except that aluminum oxide (Aldrich Co., Ltd.) and the high heat-dissipating particles prepared in Preparation Example 1 were not used. .

Comparative example  2

A sheet-like heat dissipating material (K) was manufactured in the same manner as in Example 1, except that the high heat dissipating particles prepared in Preparation Example 1 were not used.

Comparative example  3

A sheet-like heat dissipating material (L) was manufactured in the same manner as in Example 4, except that the high heat dissipating particles prepared in Preparation Example 1 were not used.

Comparative example  4

A sheet-like heat dissipating material (M) was manufactured in the same manner as in Example 7, except that the high heat dissipating particles prepared in Preparation Example 1 were not used.

The compositions of the heat dissipating materials prepared in Examples 1 to 9 and Comparative Examples 1 to 4 are collectively described in Table 1 below.

division Content of the composition Adhesive resin Thermal conductivity filler High heat dissipation  particle



Example One 100 50 One 2 100 50 2 3 100 50 3 4 100 70 One 5 100 70 2 6 100 70 3 7 100 80 One 8 100 80 2 9 100 80 3
Comparative example One 100 0 0 2 100 50 0 3 100 70 0 4 100 80 0 Content Unit: parts by weight
Adhesive resin: epoxy resin (model name and manufacturer name)
Thermally Conductive Filler: Aluminum Oxide (Model, Manufacturer)
High heat radiation particles: Carbon nanotube particles coated with aluminum hydroxide layer

<Measurement of Physical Properties of Heat-Resistant Materials>

1. Measurement of heat diffusion coefficient

The front surface of the heat-dissipating material prepared in Examples and Comparative Examples was irradiated with a laser and heated, the temperature change was measured using a radiometer on the back side, and then the measured temperature change data was interpreted using curve interpolation. Coefficients were measured.

2. Thermal conductivity measurement

Using the following general formula 1, the thermal conductivity of the heat dissipating material prepared in the above Examples and Comparative Examples was measured.

[Formula 1]

k = α × ρ × Cp

In Formula 1, k denotes thermal conductivity (unit: W / m · K), α denotes thermal diffusion coefficient (unit: mm ² / s), and ρ denotes density (unit: kg / m ³ ). , Cp represents the heat capacity (unit: J / kg K).

After measuring the density and heat capacity of the heat-dissipating material prepared in the above Examples and Comparative Examples, the thermal conductivity was measured by substituting the measured heat diffusion coefficient into the general formula 1 together with the measured density and heat capacity. .

The measurement results of the physical properties of the heat dissipating materials prepared in Examples 1 to 9 and Comparative Examples 1 to 4 are collectively described in Table 2 below.

Thermal diffusion coefficient ( mm ² / s) Thermal Conductivity (W / mK)



Example One 0.427 0.389 2 0.471 0.465 3 0.475 0.532 4 0.436 0.592 5 0.508 0.652 6 0.589 1.2 7 0.615 1.56 8 0.632 1.98 9 0.736 2.7
Comparative example One 0.201 0.213 2 0.307 0.365 3 0.415 0.443 4 0.575 1.313

As shown in Table 2, it can be seen that both the thermal diffusion coefficient and the thermal conductivity are improved as the content of the thermally conductive filler and the high heat dissipation particles increases.

Specifically, looking at Comparative Example 4 and Examples 7 to 9, Comparative Examples 4 and Examples 7 to 9 are all the same content of the thermally conductive filler (aluminum oxide), but the content of the high heat-dissipating particles according to the present invention As a result, the thermal conductivity (2.7) of Example 9, which contains 3 parts by weight of high heat-dissipating particles, is improved by at least two times compared to the thermal conductivity (1.313) of Comparative Example 4, which contains no high-heat-dissipating particles. It can be confirmed.

In addition, referring to Comparative Examples 3 and 4 to 6, Comparative Examples 3 and 4 to 6 are the same in the content of the thermally conductive filler (aluminum oxide), but the content of the high heat-dissipating particles according to the present invention is different As a result, the thermal conductivity (1.2) of Example 6 containing about 3 parts by weight of the high thermal radiation particles was improved by about 2.7 times as compared to the thermal conductivity (0.443) of Comparative Example 3 which did not contain the high thermal radiation particles at all. It can be confirmed.

Therefore, the adhesive composition for packaging an electronic component of the present invention may include thermally conductive fillers and high heat dissipating particles according to the present invention, thereby improving thermal conductivity. In particular, in the adhesive composition for packaging an electronic component of the present invention, the high heat dissipation particles may further improve the heat dissipation effect by connecting the heat conductive filler particles to form a heat conductive path.

<Electron micrograph of heat dissipation material>

The composition of the heat dissipating material prepared in Example 1 was observed using a field emission scanning electron microscope (FE-SEM).

2 is a scanning electron micrograph of a heat dissipating material according to one embodiment of the present invention. As shown in FIG. 2, the highly heat-dissipating particles (arrow-marked portions) of the present invention fill the spaces between the aluminum oxide particles (large particles other than the arrow-marked portions) which are thermally conductive fillers, thereby forming a thermally conductive path. can confirm.

Claims (25)

Carbon-based substrates; And
High heat-dissipating particles comprising at least one coating layer selected from the group consisting of a metal hydroxide layer, a metal oxide layer and a mixed layer of metal hydroxide and metal oxide formed on the surface of the carbon-based substrate. The method of claim 1,
Carbon-based substrate is one or more high heat-dissipating particles selected from the group consisting of carbon nanotubes (carbon nanotube), carbon fiber (carbon fiber), graphite (graphite) and graphene (grapheme). The method of claim 1,
The metal hydroxide comprises at least one selected from the group consisting of aluminum hydroxide (Al (OH) ₃ ), titanium hydroxide (Ti (OH) ₄ ) and mixtures thereof. The method of claim 1,
The metal oxide is one or more high heat-dissipating particles selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ) and silicon dioxide (SiO ₂ ). The method of claim 1,
High heat-dissipating particles having a thickness of 50 μm to 100 μm. (a) treating the carbon-based substrate with a strong acid;
(b) treating the carbon-based substrate obtained through step (a) with a reducing agent;
(c) reacting the carbon-based substrate obtained through step (b) with a precursor solution of metal hydroxide or a precursor solution of metal oxide; And
(d) heat-treating the reaction product obtained through step (c). The method according to claim 6,
The strong acid in step (a) is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, hydroiodic acid, hydrobromic acid and mixtures thereof. The method according to claim 6,
Step (a) is a method of producing high heat-dissipating particles comprising the step of putting a carbon-based substrate in a strong acid solution and stirring for 12 to 48 hours while heating to 40 ℃ to 80 ℃. The method of claim 8,
Step (a) further comprises the step of diluting and washing the strong acid solution containing the carbon-based substrate after the heating and stirring process. The method of claim 9,
Step (a) further comprises the step of filtering and drying the strong acid solution containing the carbon-based substrate after the dilution and washing process. The method according to claim 6,
And the reducing agent in step (b) is at least one selected from the group consisting of lithium aluminum hydride (LiAlH ₄ ), sodium borohydride (NaBH ₄ ) and mixtures thereof. The method according to claim 6,
Step (b) comprises the step of reacting from 1 part by weight to 30 parts by weight of a reducing agent with respect to 100 parts by weight of the carbon-based substrate obtained through step (a). 13. The method of claim 12,
The process of reacting the carbon-based substrate and the reducing agent obtained in step (b) in step (b) is carried out at 20 ℃ to 50 ℃ for at least 1 hour. 13. The method of claim 12,
Step (b) further comprises the step of uniformly dispersing the carbon-based substrate obtained through step (a) before the process of reacting the carbon-based substrate obtained through step (a) with a reducing agent. Way. 13. The method of claim 12,
Step (b) further comprises a step of filtering and drying the reaction solution after the step of reacting the carbon-based substrate and the reducing agent obtained through step (a). The method according to claim 6,
In step (c) the precursor of the metal hydroxide or the precursor of the metal oxide is aluminum isopropoxdie (AIP), tetraethly orthosilicate (TEOS) and titanium (IV) isopropoxide (IV). ) isopropoxide). The method according to claim 6,
Step (c) is carried out by reacting the carbon-based substrate obtained through step (b) with a precursor solution of metal hydroxide or a precursor solution of metal oxide at a temperature of 40 ° C. to 80 ° C. for at least 5 hours. . The method according to claim 6,
Step (d) comprises the step of heat-treating the reaction product obtained through step (c) at a temperature of 300 ℃ to 500 ℃ for at least 4 hours. The method of claim 18,
Step (d) further comprises the step of removing and washing the solvent of the reaction product solution obtained through step (c), prior to the heat treatment process.  Adhesive resin; Thermally conductive fillers; And adhesive composition for packaging electronic components comprising the high heat-dissipating particles according to claim 1. 21. The method of claim 20,
Adhesive resin is an adhesive composition for packaging electronic components at least one selected from the group consisting of epoxy resins, acrylic resins, urethane resins and silicone-urethane resin. 21. The method of claim 20,
Thermally conductive fillers include aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), zinc oxide (ZnO), silicon oxide (SiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ), Silicon carbide (SiC), aluminum nitride (AlN), boron nitride (BN) and silicon nitride (Si ₃ N ₄ ) One or more adhesive composition for packaging electronic components. The method of claim 20,
The thermally conductive filler is an adhesive composition for packaging an electronic component is contained in 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the adhesive resin. 21. The method of claim 20,
High heat-dissipating particles, the adhesive composition for packaging electronic components containing 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the adhesive resin. A heat dissipating material comprising a cured product of the adhesive composition for packaging an electronic component according to claim 20.

Images