KR20150140125A - Aluminum powder and graphite composite including a thermally conductive resin composition and dissipative products - Google Patents

Aluminum powder and graphite composite including a thermally conductive resin composition and dissipative products Download PDF

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KR20150140125A
KR20150140125A KR1020140068485A KR20140068485A KR20150140125A KR 20150140125 A KR20150140125 A KR 20150140125A KR 1020140068485 A KR1020140068485 A KR 1020140068485A KR 20140068485 A KR20140068485 A KR 20140068485A KR 20150140125 A KR20150140125 A KR 20150140125A
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epoxy resin
resin
curing agent
heat dissipation
average particle
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오원태
박성엽
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동의대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08Materials not undergoing a change of physical state when used
    • C09K5/14Solid materials, e.g. powdery or granular
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00Constructional details common to different types of electric apparatus
    • H05K7/20Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • H05K7/20436Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
    • H05K7/20445Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
    • H05K7/20472Sheet interfaces
    • H05K7/20481Sheet interfaces characterised by the material composition exhibiting specific thermal properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general

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  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

The present invention relates to a thermoconductive composite resin composition containing aluminum mixed powder and graphite having different average particle sizes and a heat dissipating structure using the same. The present invention can produce a thermally conductive composite material having improved thermal conductivity by adding graphite, which is an additive with excellent thermal conductivity, and aluminum powder having an average particle size of 1 to 8 m, to the polymer resin having a low dielectric constant. In addition, by manufacturing an adhesive using the polymer resin, it is possible to reduce the air gap existing at the interface between the heat generating element module and the metal to reduce the shrinkage rate even after a long period of time, maintain the shape under stress, .

Description

TECHNICAL FIELD The present invention relates to a thermally conductive composite resin composition containing aluminum powder and graphite and a heat dissipation structure using the same.

The present invention relates to a thermoconductive composite resin composition containing aluminum mixed powder and graphite having different average particle sizes and a heat dissipating structure using the same.

Recently, due to the high performance, miniaturization and high performance of electronic devices including LED lighting, the amount of heat generated by the electronic components circuit is increased. As a result, the internal temperature of the device rises and malfunctions of the semiconductor devices, characteristics of the resistor components, Problems are occurring. Accordingly, various technologies have been developed as heat dissipation measures for solving such problems.

Conventionally developed heat dissipation measures include a method of installing a heat sink or a heat sink and a method of inserting a heat transfer material such as a thermal grease, a heat radiation pad, a heat radiation tape or the like between a heat source and a heat sink have.

However, in the conventional heat dissipating method, only the heat generated from the heat source is transferred to the heat sink, and the heat accumulated in the heat sink is not discharged into the air. Furthermore, in order to protect the heat source, the heat sink, and the heat sink of the electronic product, the liquid coating material is coated on the surface thereof. In this case, the coating film interferes with the heat emission of the object, .

On the other hand, the thermal conductivity of general epoxy resin is very low (0.15 ~ 0.3 W / mK) compared to metal and ceramic. For this reason, gas has been combined (formed into a foam) in a polymer matrix and used as a heat insulating material in various fields. However, attention has been focused on high thermal conductivity characteristics of polymer composite materials, focusing on electric insulation, moisture absorption, workability, corrosion resistance and other materials having excellent heat conduction characteristics.

The technology using epoxy resin is widely used in the field of electronic parts. The development of complex polymeric materials such as thermoconductive grease, thermally conductive adhesive, and thermally conductive sheet has been developed in order to lower the contact thermal resistance between the surface where the metal and the ceramic are in contact and the part where the electronic component is attached. The thermally conductive grease helps heat conduction of metal parts such as heat exchangers and the thermally conductive adhesive is mainly used for bonding the cooling fin to the metal as the main body. The heat conductive sheet is sandwiched between the power transistor and the substrate, . In recent years, electronic products such as notebook computers and mobile phones have become more highly integrated and have a tendency to have high output specifications. In addition, as the substrate is becoming smaller and smaller, a large amount of heat is generated during operation of the apparatus. Which is a significant influence on the performance. Therefore, the heat dissipation problem of advanced electronic devices is becoming an important issue in product development for increasing the stability and reliability of the device more and more.

Epoxy resins, which are one of the thermosetting resins used in matrix resins in various industries, are used in various ranges due to their excellent physical properties. In the conventional bisphenol type epoxy resins, diglycidyl ether of bisphenol-A , DGEBA) and diglycidyl ether of bisphenol-F (DGEBF) are commercially available and widely used in a wide range of fields.

However, these resins are limited in their use as high-performance materials due to problems inherent in high brittleness properties and weathering resistance, and it is difficult to use these resins as a structural material. Thus, development of an epoxy resin having new properties, It is an urgent necessity.

Korean Patent Publication No. 10-2013-0122478

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has completed the present invention by developing a novel thermally conductive composite material capable of improving the low thermal conductivity of a polymer resin and having excellent adhesion to metal or ceramic materials.

Accordingly, an object of the present invention is to provide a thermally conductive composite resin composition applicable to a heat dissipation structure.

 Another object of the present invention is to provide a method for producing the thermoconductive composite resin composition.

Another object of the present invention is to provide a heat-dissipating adhesive composition comprising the thermoconductive composite resin composition as an active ingredient.

Another object of the present invention is to provide a heat dissipation structure including the above-mentioned heat-dissipating adhesive composition.

In order to solve the above problems, the present invention provides a resin composition comprising: a polymer resin which is an acrylic resin or an epoxy resin; Curing agent; An aluminum alloy powder having an average particle size of 1 to 8 탆; And a thermally conductive composite resin composition comprising graphite powder as an effective component.

In one embodiment of the present invention, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, alkylphenol novolak epoxy Is selected from the group consisting of a resin, a bisphenol-type epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triglycidylisocyanate epoxy resin and an acyclic epoxy resin.

In one embodiment of the present invention, the acrylic resin comprises a polymer or copolymer of methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and hexyl acrylate . ≪ / RTI >

In one embodiment of the present invention, the curing agent is selected from the group consisting of benzyldimethylamine, triethanolamine, triethylenetetraamine, diethylenetriamine, triethylenamine, dimethylaminoethanol and tri (dimethylaminomethyl) phenol .

In one embodiment of the present invention, the polymer resin and the curing agent are characterized by containing a polymer resin to a curing agent in a weight ratio of 8: 1.

In one embodiment of the present invention, an aluminum alloy powder having an average particle size of 1 to 8 占 퐉; Graphite powder is used in a weight ratio of 20 to 45: 10 to 40.

The present invention also relates to a process for producing a high molecular weight resin, which comprises applying an aluminum alloy powder having an average particle size of 1 to 8 μm to an acrylic resin or an epoxy resin; And graphite powder; And a step of adding a curing agent and a solvent to the dispersed solution, agitating the mixture, and then curing the mixture.

In one embodiment of the present invention, the epoxy resin is bisphenol A-epichlorohydrin, the curing agent is triethylenetetraamine, and the solvent is methyl ethyl ketone (MEK) and toluene (Toluene) .

In one embodiment of the present invention, the acrylic resin comprises a polymer or copolymer of methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and hexyl acrylate . ≪ / RTI >

In one embodiment of the present invention, the curing agent is selected from the group consisting of benzyldimethylamine, triethanolamine, triethylenetetraamine, diethylenetriamine, triethylenamine, dimethylaminoethanol and tri (dimethylaminomethyl) phenol .

The present invention also relates to a polymer resin which is an acrylic resin or an epoxy resin; Curing agent; An aluminum alloy powder having an average particle size of 1 to 8 탆; And a graphite powder as an effective component.

The present invention also provides a heat dissipation structure including an adhesive layer formed by applying the heat dissipation adhesive composition.

In one embodiment of the present invention, the heat dissipation structure is selected from the group consisting of a heat dissipation plate, a heat dissipation film, a heat dissipation adhesive, a heat dissipation grease, and a heat dissipation tape.

The present invention can produce a thermally conductive composite material having improved thermal conductivity by adding graphite, which is an additive with excellent thermal conductivity, and aluminum powder having an average particle size of 1 to 8 m, to the polymer resin having a low dielectric constant.

In addition, by manufacturing an adhesive using the polymer resin, it is possible to reduce the air gap existing at the interface between the heat generating element module and the metal to reduce the shrinkage rate even after a long period of time, maintain the shape under stress, .

1 is FE-SEM images (x1000) of Production Example 8 of the present invention.
Fig. 2 is FE-SEM images (x1000) (pGr / pAl6 content = (a) 10/80, (b) 20/70, (c) of graphite and pAl6 with respect to the epoxy resin and curing agent of the present invention ) 30/60, (d) 40/50).
3 is FE-SEM images (x1000) (pGr / pAl (2 + 6) content = (a) 10/40/40 according to the mixed composition of graphite, pAl2 and pAl6 for the epoxy resin and curing agent of the present invention. , (b) 20/35/35, (c) 30/30/30, (d) 40/25/25).

The present invention relates to a technique for producing a thermally conductive composite resin composition improved in thermal conductivity by adding graphite, aluminum powder having an average particle size of 2 mu m and aluminum powder having an average particle size of 6 mu m to an epoxy resin or an acrylic resin, And a method of applying the same as a heat dissipation material.

Epoxy resins have good metal adhesiveness and development with heat-resistant adhesives is useful. Existing adhesives, despite high initial adhesion to common metals such as aluminum, are somewhat weaker in exposure to moisture and hot environments. In contrast, the epoxy adhesive is environmentally friendly and maintains a constant high adhesive force even at high temperatures. In general, metals are corroded by moisture or air, which also has a considerable influence on heat dissipation properties.

However, adhesives using epoxy resin can reduce not only the effective heat transfer (heat dissipation) but also the corrosion caused by moisture by reducing the air gap existing at the interface between the heating element module and the metal. Epoxy resin can be adhered with high strength even when it is bonded at room temperature. It has a low shrinkage rate even after a long period of time after adhesion between metal and interface, and maintains its shape even under stress.

The present invention relates to a polymer resin which is an acrylic resin or an epoxy resin; Curing agent; An aluminum alloy powder having an average particle size of 1 to 8 占 퐉 and graphite powder as an effective component.

In one embodiment of the present invention, the epoxy resin is an epoxy resin having an average of more than two epoxy groups per molecule of one of the resins having two or more epoxy groups in one molecule. Epoxy resins are thermosetting resins that are excellent in electrical insulation, heat resistance and chemical stability.

Preferably, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, alkylphenol novolac epoxy resin, bisphenol epoxy At least one epoxy compound selected from resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, triglycidyl isocyanates and acyclic epoxy resins can be used, and a bisphenol-A type resin can be most preferably used .

The above epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin may be used in combination with one another such as methyl ethyl ketone (MEK), dimethyl formamide (DMF), methyl cellosolve (MCS), carbitol acetate, carbitol, PGMEA, PGME , Toluene, xylene, NMP, 2-methoxyethanol, etc. may be mixed and dissolved as a solvent.

In one embodiment of the present invention, the acrylic resin may be a polymer or copolymer of methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and hexyl acrylate .

In the present invention, usable polymeric resin curing agents are not particularly limited, and any curing agent conventionally used in epoxy compositions is not relevant. Preferably, the epoxy resin curing agent which can be used in the production of the epoxy resin composition of the present invention may be an amine type, imidazole type, acid anhydride type or a mixture thereof.

The amine-based curing agents usable in the present invention include linear amines, aliphatic amines, modified aliphatic amines, aromatic amines, secondary amines, and tertiary amines, and examples thereof include benzyldimethylamine, triethanolamine, triethylene Tetramine, diethylenetriamine, triethylenamine, dimethylaminoethanol, and tri (dimethylaminomethyl) phenol.

Examples of the imidazole-based curing agent include imidazole, isomimidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidizole, 2,4-dimethyl imidizole, butyl imidizole, 2-methyldimidazole, 2-undecylidimidizole, 1-vinyl-2-methylimidizole, 2-n-heptadecylimidizole, 2- 2-methylimidizole, 1-propyl-2-methylimidizole, 1-cyanoethyl-2-methyl 1-cyanoethyl-2-ethyl-4-methylimidizole, 1-cyanoethyl-2-undecylimidizole, 1-cyanoethyl- 2-methylimidizole, an adduct of imidazole and methylimidizole, an adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidizole, phenylimidazole , Benzylimidizole, 2-methyl-4,5-diphenylimidizole, 2,3,5-triphenylimidizole, 2-styrylimidizole, 1- (dodecylbenzyl) -2- Methyl (2-hydroxy-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl) (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) -4,5-diphenylimidazole, 2- Diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5-diphenylimidazole, 1-benzyl- -Methylimidizole and 2-p-methoxystyrylimidazole, and the like.

Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, And an anhydride-based curing agent. The acid anhydride-based curing agent is preferably used by mixing the curing agents as a catalyst, rather than being used alone.

In one embodiment of the present invention, the polymer resin and the curing agent contain a polymer resin and a curing agent in a weight ratio of 8: 1.

Also, in one embodiment of the present invention, when the aluminum mixed powder is 100% or more of the polymer resin, the mechanical properties of the composite composition are remarkably lowered and the structural stability is weakened. Also, due to the increased specific gravity, it is not effective in reducing the weight of the finished product.

In one embodiment of the present invention, the graphite powder may be natural graphite or artificial graphite alone or a mixture thereof.

 In one embodiment of the present invention, the aluminum alloy powder and the graphite powder are mixed in an amount of 40 to 80% by weight based on the total weight of the polymer resin, the curing agent, the aluminum alloy powder and the graphite powder, The content ratio of the aluminum alloy powder and the graphite powder can be adjusted in the range of 20 to 45:10 to 40 weight ratio, preferably 60 wt% of the aluminum alloy powder and 20 to 30 wt% of the graphite powder. .

A method for producing a thermally conductive composite resin according to the present invention comprises the steps of: adding graphite powder and an aluminum alloy powder having an average particle size of 1 to 8 μm to a polymer resin and dispersing the mixture; And adding a curing agent and a solvent to the dispersed solution, agitating the mixture, and curing the mixture.

In one embodiment of the present invention, the polymer resin is bisphenol A epichlorohydrin, the curing agent is triethylenetetramine, and the solvent includes but is not limited to methyl ethyl ketone (MEK) and toluene (Toluene) Do not.

In one embodiment of the present invention, the solvent is selected from the group consisting of methyl ethyl ketone (MEK), toluene, dimethylformamide (DMF), methylcellosolve (MCS), carbitol acetate, carbitol, PGMEA, Is at least one selected from the group consisting of PGME, toluene, xylene, NMP, and 2-methoxyethanol, preferably MEK / toluene at a v / v of 1/1 to 3/1.

Also, in an embodiment of the present invention, the solvent may be added with MEK / toluene at a v / v of 1/1 to 3/1.

Further, a polymer resin; Curing agent; An aluminum alloy powder having an average particle size of 1 to 8 탆 and graphite powder as an active ingredient can be used as a heat-dissipating adhesive composition. However, when the heat-radiating adhesive composition is used for interfacial bonding of a heat sink, heat Can be easily released into the atmosphere.

In one embodiment of the present invention, when the heat-radiating adhesive composition is applied to a heat sink, the thickness of the heat-radiating adhesive composition may be 10 to 100 탆, but the present invention is not limited thereto.

Also, the heat conductive composite resin composition or the heat radiation adhesive composition of the present invention can be used as a heat dissipation structure, and the heat dissipation structure can be used as a heat dissipation plate, a heat dissipation film, a heat dissipation adhesive, a heat dissipation grease and a heat dissipation tape.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited by the following Examples.

< Example  1>

Epoxy resin composite material composition manufacturing

<1-1> Bisphenol A Epichlorohydrin ( Bisphenol  A epichlrohydrin ) And pAl2 Preparation of epoxy resin composition containing

10-60wt% of pAl2 powder was dispersed evenly in 8g of Bisphenol A epichlrohydrin (MW ≥700 Struers Epofix) for 24h, and then stirred for 24 hours in a 50 ° C oil bath using a mechanical stirrer.

1 g of triethyltetramine (hardener Struers Epofix) was added to the stirred reaction product and slowly stirred so as not to cause air bubbles. Thereafter, the mixture was cured in a 70 ° C oven for 2 hours to prepare an epoxy composite resin composition in which pAl2 was mixed.

In order to facilitate the dispersion of the SiC filler added to the epoxy resin, the epoxy composite resin composition may be prepared by adding a small amount of a solvent (MEK (methyl ethyl ketone) / Toluene = 1/1 to 3/1 v / v) .

The contents of pAl2 used for the preparation of the epoxy composite resin composition in which bisphenol A epichlohydrin and pAl2 were mixed as described above are shown in Table 1 below.

Ingredients and contents for the production of an epoxy composite resin composition in which bisphenol A epichlorohydrin and pAl2 are mixed <Mix composition of pAl2 alloy powder to (epoxy + curing agent) = (8 + 1) g> pAl2 *
(wt.%)
Density (g / cm 3) Thermal conductivity (W / m · K)
25 o C 50 o C Production Example 1 10 1.230 0.307 0.290 Production Example 2 20 1.312 0.405 0.381 Production Example 3 30 1.401 0.487 0.464 Production Example 4 40 1.487 0.627 0.558 Production Example 5 50 1.617 0.755 0.734 Production Example 6 60 1.721 0.903 0.827

* pAl2: Aluminum powder. Average particle size 2 탆

<1-2> Bisphenol A Epichlorohydrin ( Bisphenol  A epichlrohydrin ) And pAl2 / 6 &lt; / RTI &gt;

The epoxy composite resin composition containing bisphenol A epichlohydrin and aluminum powder having an average particle size of 2 占 퐉 and aluminum powder having an average particle size of 6 占 퐉 was prepared in the same manner as in Example 1-1 except that the average particle size Except that an aluminum powder (pAl2) having an average particle size of 2 m and an aluminum powder (pAl6) having an average particle size of 6 m was used, and an aluminum powder having an average particle size of 2 m and an aluminum powder Were used as described in Table 2 below.

In order to facilitate the dispersion of the SiC filler added to the epoxy resin, the epoxy composite resin composition may be prepared by adding a small amount of a solvent (MEK (methyl ethyl ketone) / Toluene = 1/1 to 3/1 v / v) .

Ingredients and Contents for the Preparation of Epoxy Composite Composition Mixed with Bisphenol A Epichlorohydrin and pAl2 / 6 Mixed Composition of pAl2 and pAl6 alloy powder to ((epoxy + curing agent) = (8 + 1) g) pAl2 / 6 **
(wt.%)
Density (g / cm 3) Thermal conductivity (W / m · K)
25 o C 50 o C Production Example 7 25/25 1.712 1.455 1.317 Production Example 8 30/30 1.821 1.955 2.111

** pAl2 / 6: Aluminum mixed powder. Aluminum powders having average particle sizes of 2 탆 and 6 탆 were mixed at a ratio of 1: 1, respectively, and used

The surface of Preparation Example 8 prepared above was observed through FE-SEM photographing, and the results are shown in Fig.

As a result of the analysis, it can be seen that when the aluminum powders having different particle sizes are mixed and used, the thermal conductivity is greatly increased as compared with the case where one kind of aluminum powder is used in the same amount.

&Lt; 1-3 > Preparation of epoxy resin composition containing bisphenol A epichlrohydrin, pGr and pAl6

The epoxy composite resin composition containing bisphenol A epichlohydrin and graphite and aluminum powder (pAl 6) having an average particle size of 6 탆 was prepared in the same manner as in Example 1-1 except that graphite was used instead of pAl2 in Example 1-1, Mu] m, and the graphite used and the aluminum powder having an average particle size of 6 mu m were used as described in Table 3 below.

In order to facilitate the dispersion of the SiC filler added to the epoxy resin, the epoxy composite resin composition may be prepared by adding a small amount of a solvent (MEK (methyl ethyl ketone) / Toluene = 1/1 to 3/1 v / v) .

Ingredients and contents for the production of an epoxy composite resin composition in which bisphenol A epichlorohydrin, pGr and pAl6 are mixed Mixture composition of pGr and pAl6 alloy powder to (epoxy + curing agent) = (8 + 1) g> pGr / pAl6
(wt.%)
Density (g / cm 3) Thermal conductivity (W / m · K)
25 o C 50 o C Production Example 9 30/50 1.409 1.078 1.054 Production Example 10 40/50 1.546 1.120 1.204 Manufacturing example  11 20/60 1.587 2.143 2.108 Manufacturing example  12 30/60 1.605 2.058 2.042 Production Example 13 10/70 1.618 1.781 1.748 Production Example 14 20/70 1.718 1.755 1.745 Manufacturing example  15 10/80 2.032 2.617 2.597

The surface of the epoxy composite resin composition thus prepared was observed through FE-SEM photographing, and the results are shown in Fig.

(B) 20 + 70, (c) 30 + 60, and (d) 40, respectively, in the epoxy composite composition, and the composition ratio of pGr + +50. &Lt; / RTI &gt; Although spherical aluminum particles are mostly present, irregularly shaped particles increase as the content of graphite increases. When the content of the aluminum powder is increased, the thermal conductivity generally increases, but the dispersion stability in the composite composition is somewhat disadvantageously deteriorated, which increases the possibility of non-uniformity of the characteristics. In general, when the content of graphite is about 20-30 wt%, the dispersion stability is improved and the uniformity of characteristics is also improved, so that the thermal conductivity and the dispersion stability of the composite composition are required to be optimized.

<1-4> Bisphenol A Epichlorohydrin ( Bisphenol  A epichlrohydrin ) And pGr , pAl2  And pAl6 Preparation of epoxy resin composition containing

The epoxy composite resin composition containing bisphenol A epichlohydrin and graphite, aluminum powder having an average particle size of 2 mu m and aluminum powder having an average particle size of 6 mu m was prepared in the same manner as in Example 1-1, Graphite, an aluminum powder having an average particle size of 2 mu m, and an aluminum powder having an average particle size of 6 mu m were used, and the graphite used, the aluminum powder having an average particle size of 2 mu m, the aluminum powder having an average particle size of 6 mu m Were used as described in Table 4 below.

In order to facilitate the dispersion of the SiC filler added to the epoxy resin, the epoxy composite resin composition may be prepared by adding a small amount of a solvent (MEK (methyl ethyl ketone) / Toluene = 1/1 to 3/1 v / v) .

PAl2 and pAl6 relative to each component and content <(epoxy + curing agent) = (8 + 1) g for preparing an epoxy composite resin composition in which bisphenol A epichlorohydrin, pGr, pAl2 and pAl6 are mixed Mixture composition> pGr / pAl2 / 6
(wt.%)
Density (g / cm 3) Thermal conductivity (W / m · K)
25 o C 50 o C Production Example 16 30/25/25 1.564 1.888 1.855 Production Example 17 40/25/25 1.587 2.967 3.000 Manufacturing example  18 20/30/30 1.626 1.999 2.026 Production Example 19 30/30/30 1.634 1.661 1.602 Production example 20 10/35/35 1.655 1.894 1.874 Production Example 21 20/35/35 1.758 2.046 1.899 Manufacturing example  22 10/40/40 1.851 2.292 2.242

The surface of the epoxy composite resin composition thus prepared was observed through FE-SEM photographing, and the results are shown in Fig.

As a result, in the epoxy composite composition, the mixed contents of pGr + pAl (2 + 6) were all 90 wt% and the detailed composition ratios were 10 + 40 + 40, 20 + 35 + 35, ) 30 + 30 + 30, and (d) 40 + 25 + 25. As shown in FIG. 3, most of spherical aluminum particles are present, but irregularly shaped particles are increased as the content of graphite increases. In Fig. 3, an aluminum powder having an average particle size of 2 mu m is generally seen. Particularly, when aluminum powders having a small average particle size of 2 μm are mixed, it is difficult to uniformly maintain the dispersion in the composite composition, so that it can be confirmed that the thermal conductivity tends to be relatively low when the content of graphite is small. As shown in FIG. 3, the uniform dispersion characteristics can be confirmed at a content of graphite of 40 wt%, and the thermal conductivity is confirmed to be the highest value.

In addition, as a result of the analysis, it was found that when the Al powder was mixed with two different sizes (2 탆 and 6 탆) in comparison with the results of Examples 1-3, the heat conduction characteristics were superior to those of Example 1-3 have.

<1-5> Acrylic composite resin  Produce

(PMMA), an acrylic composite resin containing graphite and aluminum powder, an acrylic resin and graphite, an aluminum powder (pAl2) having an average particle size of 2 mu m and an aluminum powder having an average particle size of 6 mu m An acrylic composite resin composition containing a powder (pAl6) was prepared by the method of Example 1-3, and the composition of the mixture was used as shown in Table 5.

Composition of acrylic composite resin pGr / pAl
(wt.%)
Thermal conductivity (W / mK)
No press After press 25 o C 50 o C 25 o C 50 o C Production Example 23 20/60 2.202 2.193 2.711 2.701 Production Example 24 30/60 2.098 2.095 2.563 2.559 Production example 25 (40/25/25) * 3.121 3.187 3.409 3.401 Production Example 26 (20/30/30) ** 2.205 2.217 2.801 2.789

* (40/25/25) contains 40wt.% Of pGr, 25wt.% Of pAl2 and pAl6 respectively.

** (20/30/30) contains 20wt.% Of pGr, 30wt.% Of pAl2 and pAl6 respectively.

The acrylic composite resin samples were compressed using a hydraulic press, and the thickness of the samples was reduced to an average of 1/3. Compared with the epoxy resin of the same composition (Production Example 11, Production Example 12, Production Example 17 and Production Example 18, when the thickness of the sample is reduced by the compression, the thermal conductivity is considerably increased. Likewise, it can be seen that the acrylic resin can also be applied to a heat dissipation adhesive, a sheet or the like.

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (13)

A polymer resin which is an acrylic resin or an epoxy resin; Curing agent; An aluminum alloy powder having an average particle size of 1 to 8 탆; And a graphite powder as an active ingredient. The method according to claim 1,
The epoxy resin may be at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, alkylphenol novolak epoxy resin, bisphenol epoxy resin, An epoxy resin, a dicyclopentadiene type epoxy resin, a triglycidyl isocyanate epoxy resin, and an acyclic epoxy resin.
The method according to claim 1,
Wherein the acrylic resin is selected from the group consisting of polymers or copolymers of methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and hexyl acrylate. Composite resin composition.
The method according to claim 1,
Wherein the curing agent is selected from the group consisting of benzyldimethylamine, triethanolamine, triethylenetetraamine, diethylenetriamine, triethylenamine, dimethylaminoethanol and tri (dimethylaminomethyl) phenol. .
The method according to claim 1,
Wherein the polymer resin and the curing agent are contained in a weight ratio of the polymer resin to the curing agent in a ratio of 8: 1.
The method according to claim 1,
An aluminum alloy powder having an average particle size of 1 to 8 탆; Graphite powder is used in a weight ratio of 20 to 45: 10 to 40. The thermoconductive epoxy resin composition of claim 1,
An aluminum alloy powder having an average particle size of 1 to 8 占 퐉 in a polymer resin which is an acrylic resin or an epoxy resin; And graphite powder; And
Adding a curing agent and a solvent to the dispersed solution, stirring the mixture, and curing the mixture.
8. The method of claim 7,
Wherein the epoxy resin is bisphenol A-epichlorohydrin, the curing agent is triethylenetetramine, and the solvent is methyl ethyl ketone (MEK) and toluene (Toluene). &Lt; / RTI &gt;
8. The method of claim 7,
Wherein the acrylic resin is selected from the group consisting of polymers or copolymers of methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and hexyl acrylate. A method for producing a composite resin composition.
8. The method of claim 7,
Wherein the curing agent is selected from the group consisting of benzyldimethylamine, triethanolamine, triethylenetetraamine, diethylenetriamine, triethylenamine, dimethylaminoethanol and tri (dimethylaminomethyl) phenol. &Lt; / RTI &gt;
A polymer resin which is an acrylic resin or an epoxy resin; Curing agent; An aluminum alloy powder having an average particle size of 1 to 8 탆; And a graphite powder as an effective component. A heat dissipation structure comprising an adhesive layer formed by applying the composition of claim 1 or 6. 13. The method of claim 12,
Wherein the heat dissipation structure is selected from the group consisting of a heat dissipation plate, a heat dissipation film, a heat dissipation adhesive, a heat dissipation grease, and a heat dissipation tape.
KR1020140068485A 2014-06-05 2014-06-05 Aluminum powder and graphite composite including a thermally conductive resin composition and dissipative products KR20150140125A (en)

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KR102180206B1 (en) 2019-05-29 2020-11-18 동의대학교 산학협력단 Thermal conductive polymer composites comprising aluminum and carbon material and their application of heat dissipation products
KR102180205B1 (en) 2019-05-29 2020-11-18 동의대학교 산학협력단 Thermal conductive polymer composites comprising alumina and carbon material and their application of heat dissipation products
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KR102180206B1 (en) 2019-05-29 2020-11-18 동의대학교 산학협력단 Thermal conductive polymer composites comprising aluminum and carbon material and their application of heat dissipation products
KR102180205B1 (en) 2019-05-29 2020-11-18 동의대학교 산학협력단 Thermal conductive polymer composites comprising alumina and carbon material and their application of heat dissipation products
KR102186635B1 (en) 2019-05-29 2020-12-03 동의대학교 산학협력단 Thermal conductive polymer composites comprising alumina and calcined carbon material and their application of heat dissipation products
KR20200137794A (en) 2019-05-31 2020-12-09 대흥특수화학(주) Thermal conductive adhesive composition using metal materials and carbon fillers
KR102177818B1 (en) 2019-06-24 2020-11-12 대흥특수화학(주) Thermal conductive adhesive film using carbon fillers
KR20210037037A (en) 2019-09-26 2021-04-06 (주)블루싸이언스 Thermal conductive film comprising thermal conductive polymer composites and method for preparing the same
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