CN112226041A - High-thermal-conductivity epoxy resin composition and preparation method thereof - Google Patents
High-thermal-conductivity epoxy resin composition and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/40—Macromolecules 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
- C08G59/62—Alcohols or phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The high heat conducting epoxy resin composition contains epoxy resin, high heat conducting stuffing of alumina in the average grain size of 0.01-20 microns and maximum grain size smaller than 100 microns in the content of 90-94 wt% of the epoxy resin composition, surface treating agent and curing agent. The invention uses the alumina high heat conduction filler and the surface treatment agent, and can obtain the high heat conduction type epoxy resin composition with 90-94% of filler content and 5.5W/m.K of heat conduction coefficient, the surface treatment agent can increase the caking property of the filler and the whole resin system, improve the bending strength of the resin composition, and improve the operability and reliability of the epoxy resin composition.
Description
Technical Field
The invention relates to an epoxy resin composition, in particular to a high-thermal-conductivity epoxy resin composition and a preparation method thereof.
Background
With the rapid development of electronic information technology, increasingly higher requirements are placed on miniaturization, portability and the like of electronic products. The rapid increase of the integration level of the chip inevitably leads to the increase of the heat productivity and the continuous rise of the working temperature of the circuit. If the heat dissipation is poor, the chip is easy to fail. The development of the epoxy resin composition with high thermal conductivity coefficient is helpful for solving the heat dissipation problem of the intelligent chip with high integration level or high integration level and high power density, and ensures that the chip can stably work in a normal range. For high-integration high-power-density intelligent chips such as energy modules, the thermal conductivity of the chips is required to be 3W/m.K-5W/m.K or even higher.
Compared with silicon dioxide, the high-thermal-conductivity filler aluminum oxide has the problems of low filler content, low bending strength, high storage modulus and the like; especially bending strength and filler content, are the main challenges that restrict the high thermal conductivity of alumina fillers and apply to the field of epoxy molding compounds to prepare compositions with higher thermal conductivity coefficient.
The prior art has been studied in this regard mainly: chinese patent CN102911479A discloses an epoxy resin composition suitable for a fully encapsulated device, which can obtain an epoxy molding compound with a thermal conductivity coefficient of 2.2W/m.K by adding crystalline silica micropowder; chinese patent CN105440588B discloses a high-thermal-conductivity molding type epoxy underfill and a preparation method thereof, and the composition can obtain a composition with the highest thermal conductivity coefficient of 3.3W/m.K by adding a spherical thermal-conductivity filler; chinese patent CN111073217A discloses a high thermal conductivity low stress epoxy molding compound for semiconductor encapsulation, which can be obtained by designing the particle size and shape of the thermal conductive filler and filling epoxy resin with different types and sizes of thermal conductive fillers with different shapes, and has a thermal conductivity of 3.5W/m.k or more.
However, most of the current research results show that the filler content of the obtained high thermal conductive epoxy resin composition is below 90%, and the bending strength of the high thermal conductive epoxy resin composition is not mentioned.
Disclosure of Invention
The invention aims to solve the technical problem of providing an epoxy resin composition with high thermal conductivity against the defects of the prior art.
The invention also provides a preparation method of the high-thermal conductivity epoxy resin composition, aiming at the defects of the prior art.
The technical problem to be solved by the invention is realized by the following technical scheme, and the invention is a high-heat-conductivity epoxy resin composition which is characterized by comprising epoxy resin, high-heat-conductivity filler, surface treating agent and curing agent,
the high heat conduction filler contains alumina, the average grain diameter of the alumina is 0.01-20um, the maximum grain diameter is less than 100um, the content of the alumina accounts for 90-94 percent of the total content of the epoxy resin composition, and the content of the alumina is preferably 93 percent;
the surface treating agent and the high-heat-conductivity filler can be mixed in advance, the mixing time is more than or equal to 15min, the mixing temperature is 25-200 ℃, further, the mixing time is preferably 30-60 min, and the mixing temperature is preferably 120-200 ℃.
Preferably, the surface treating agent is polyphosphoric acid and acrylic acid copolymer resin shown as a formula (4), the content of the polyphosphoric acid and acrylic acid copolymer resin accounts for 0.01-5% of the content of the high-heat-conducting filler, the content of the polyphosphoric acid and acrylic acid copolymer resin is further preferably 0.1-3%, and the structural formula is shown as
Wherein m is an integer of 20-40, and n is an integer of 40-80.
Preferably, the content of the epoxy resin accounts for 1-10 percent of the total content of the epoxy resin composition, preferably 1-5 percent of the total content of the epoxy resin composition, the epoxy resin comprises the epoxy resin shown in the formula (1) or the formula (2), the content of the epoxy resin accounts for at least 50 percent of the total content of the epoxy resin,
formula (1), wherein R ═ H or CH3；
Formula (2), n is an integer of 1 to 15;
the epoxy resin may contain any known epoxy resin in addition to the epoxy resin having the structure of formula (1)/(2). For example: novolac epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol fluorene epoxy resins, disulfide epoxy resins, hydroquinone epoxy resins, naphthol aralkyl epoxy resins, naphthalene diol epoxy resins, oxazolidone ring-containing epoxy resins, and the like, but are not limited thereto. The epoxy resin may be used alone or in combination of 2 or more.
Preferably, the content of the curing agent accounts for 1-10% of the total content of the epoxy resin composition, preferably 1-5%, the curing agent is solid at normal temperature, the curing agent comprises the phenolic resin shown in the formula (3), the content of the phenolic resin at least accounts for 50% of the total content of the curing agent, and the structural formula of the phenolic resin is shown in the specification
Formula (3), wherein n is 0 to 10;
the phenolic resin can contain other phenolic resin curing agents besides the phenolic resin with the structure of the formula (3) on the premise of not influencing the effect of the invention. For example; phenol aralkyl resins, biphenyl type phenol aralkyl resins, tea phenol aralkyl resins, and the like, which are synthesized from phenols such as phenol, cresol, resorcinol, catechol, bisphenol, phenylphenol, and aminophenol, or tea phenols, and dimethoxyp-xylene or bismethoxymethylbiphenyl, and modified phenol resins such as polyvinyl acetal modified phenol resins, epoxy modified phenol resins, silicone modified phenol resins, borophenol resins, xylene modified phenol resins, diphenyl ether formaldehyde resins, and aralkyl ether formaldehyde resins, but the present invention is not limited thereto. The phenolic resin may be used alone, or 2 or more.
Preferably, the ratio of the epoxy equivalent in the epoxy resin to the hydroxyl equivalent in the curing agent is 0.5 to 2.0, and more preferably 0.7 to 1.8.
Preferably, the composition also comprises an accelerator, wherein the accelerator is one or a mixture of more of imidazole, phosphorus or amine catalysts, and the content of the accelerator accounts for 0.01-2% of the total content of the epoxy resin composition, and is preferably 0.01-0.5%;
the accelerator is not particularly limited, and any known curing agent accelerator for epoxy resin compositions can be used. Can be one or more of imidazole, phosphorus or amine catalysts. Commonly used imidazoles including 2-methylimidazole, 2-phenylimidazole, 2-methyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-undecylimidazole and the like; phosphorus compounds including triphenyl phosphorus, tributyl phosphorus, adducts of triphenyl phosphorus and benzoquinone, tetraphenylphosphonium tetraphenyl borate, triphenyl phosphorus triphenylborane, and the like; a tertiary amine compound; a quaternary ammonium salt; an organic metal salt; diazadizacycloalkanes, etc., and these compounds and their derivatives may be used alone or in combination.
Preferably, the average particle size of the alumina high-thermal-conductivity filler is 0.1-20um, the maximum particle size is less than 75um, and further preferably, the maximum particle size is less than 55 um; the shape of the high thermal conductive filler can be angular, spherical, preferably spherical (including sphere-like).
The invention also provides a preparation method of the high-heat-conductivity epoxy resin composition, which is characterized in that a surface treating agent and a high-heat-conductivity filler are mixed in advance, the mixing time is more than or equal to 15min, the mixing temperature is 25min-200 ℃, after mixing, the mixture is cooled to room temperature, then other components are added for stirring and mixing, and after uniform mixing, kneading, calendaring, cooling and crushing are carried out, so that the powdery epoxy resin composition with certain particle size distribution is obtained.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the high-thermal conductivity epoxy resin composition with 90-94% of filler content and 5.5W/m.K thermal conductivity can be obtained by utilizing the alumina high-thermal conductivity filler and matching with the surface treatment agent, and the surface treatment agent can increase the cohesiveness of the filler and the whole resin system, improve the bending strength of the resin composition and improve the operability and reliability of the epoxy resin composition;
secondly, by adding the epoxy resin with the structure of formula (1) or formula (2) and the curing agent with the structure of formula (3), the stress of the whole resin system can be effectively reduced, and a low-viscosity resin system is provided; by matching with the high-thermal-conductivity filler and the surface treating agent, the high-reliability epoxy resin composition with high thermal conductivity, high bending strength, low storage modulus and good cohesiveness can be obtained.
The epoxy resin composition provided by the invention overcomes the problem of low bending strength of aluminum oxide as a high-thermal-conductivity filler, and meanwhile, the composition is low in storage modulus, good in operability and high in reliability, can be used for high-end products such as energy modules with high packaging integration level and complex structures, and has excellent comprehensive performance.
Detailed Description
The embodiments of the present invention are further described to enable those skilled in the art to further understand the present invention without limiting the right of the present invention.
Example 1 a highly thermally conductive epoxy resin composition, which comprises an epoxy resin, a curing agent, an accelerator, a highly thermally conductive filler, and a surface treatment agent; the epoxy resin is a mixture of epoxy resins with structures shown in formulas (1) and (2), wherein the epoxy resins with the structures shown in formulas (1) and (2) account for half of the total amount of the epoxy resins; the curing agent is phenolic resin with a structure shown in a formula (3); the accelerant is one or more of imidazole, phosphorus or amine catalysts; the high heat conduction filler is alumina, the average grain diameter of the high heat conduction filler is 0.1-20um, and the maximum grain diameter is less than 75 um;
the epoxy resin accounts for 5 percent of the total weight of the epoxy resin composition, the curing agent accounts for 1 percent of the total weight of the epoxy resin composition, the accelerating agent accounts for 0.01 percent of the total weight of the epoxy resin composition, the high heat-conducting filler accounts for 93 percent of the total weight of the epoxy resin composition, the surface treating agent accounts for 1.5 percent of the weight of the high heat-conducting filler, and the balance is other component raw materials, wherein the other component raw materials mentioned in the embodiment and the following embodiments refer to other components which can also contain other components such as a coloring agent, a release agent, a coupling agent, a stress releasing agent, an ion catching agent and a flame retardant in addition to the;
the preparation method comprises adding the high-thermal-conductivity filler into a high-speed stirrer, adding the surface treatment agent into the high-speed stirrer in a stirring state, and mixing and stirring at 120 ℃ for 15min to uniformly disperse the surface treatment agent on the surface of the high-thermal-conductivity filler; cooling to room temperature, adding other components such as epoxy resin, curing agent and the like, stirring and mixing uniformly, kneading and rolling through an extruder, a calender roll or a kneader, cooling and crushing to obtain the powdery epoxy resin composition with certain particle size distribution.
Embodiment 2, a high thermal conductive epoxy resin composition, wherein the epoxy resin in the composition is a mixture of epoxy resin having a structure represented by formula (1) and epoxy resin CNE195LL, wherein the epoxy resin represented by formula (1) accounts for 50% of the total weight of the epoxy resin, the epoxy resin CNE195LL accounts for 50% of the total weight of the epoxy resin, and the epoxy resin CNE195LL is epoxy resin of vinblastic resin; the types of the other components are the same as those in the embodiment 1, and the high-heat-conductivity filler is the mixture of alumina and silica;
the epoxy resin accounts for 1 percent of the total weight of the epoxy resin composition, the curing agent accounts for 3 percent of the total weight of the epoxy resin composition, the accelerating agent accounts for 0.3 percent of the total weight of the epoxy resin composition, the alumina accounts for 90 percent of the total weight of the epoxy resin composition, the surface treating agent accounts for 0.5 percent of the weight of the high-heat-conducting filler, and the rest is silicon dioxide and other component raw materials;
the preparation method comprises adding the high-thermal-conductivity filler into a high-speed stirrer, adding the surface treatment agent into the high-speed stirrer in a stirring state, and mixing and stirring at 200 ℃ for 30min to uniformly disperse the surface treatment agent on the surface of the high-thermal-conductivity filler; cooling to room temperature, adding other components such as epoxy resin, curing agent and the like, stirring and mixing uniformly, kneading and rolling through an extruder, a calender roll or a kneader, cooling and crushing to obtain the powdery epoxy resin composition with certain particle size distribution.
Example 3, a highly thermally conductive epoxy resin composition, in which an epoxy resin having a structure represented by formula (2) below and an epoxy resin CNE195LL were mixed, wherein the epoxy resin represented by formula (2) below accounted for 75% by weight of the total epoxy resin, the epoxy resin CNE195LL accounted for 25% by weight of the total epoxy resin, and the epoxy resin CNE195LL was an epoxy resin of vinblastic resin; the kinds of the remaining components were the same as in example 1;
the epoxy resin accounts for 3 percent of the total weight of the epoxy resin composition, the curing agent accounts for 2 percent of the total weight of the epoxy resin composition, the accelerating agent accounts for 0.5 percent of the total weight of the epoxy resin composition, the high heat-conducting filler accounts for 90 percent of the total weight of the epoxy resin composition, the surface treating agent accounts for 1.0 percent of the weight of the high heat-conducting filler, and the balance is raw materials of other components;
the preparation method comprises adding the high-thermal-conductivity filler into a high-speed stirrer, adding the surface treatment agent into the high-speed stirrer in a stirring state, and mixing and stirring at 25 ℃ for 60min to uniformly disperse the surface treatment agent on the surface of the high-thermal-conductivity filler; then adding other components such as epoxy resin, curing agent and the like, stirring and mixing uniformly, kneading and rolling the mixture by an extruder, a calender roll or a kneader, and then cooling and crushing the mixture to obtain the powdery epoxy resin composition with certain particle size distribution.
Example 4 is a highly thermally conductive epoxy resin composition, wherein the curing agent is a mixture of a phenolic resin represented by formula (3) and a curing agent HF-1M, and the curing agent HF-1M is a phenolic resin of japan Minghe, wherein the phenolic resin represented by formula (3) accounts for 50% of the total weight of the curing agent, the curing agent HF-1M accounts for 50% of the total weight of the curing agent, the types and amounts of the remaining components are the same as those of example 1, and the preparation method is the same as that of example 1.
Example 5 a highly thermally conductive epoxy resin composition, the kind of each component in the composition is the same as that of example 1; wherein the content of the first and second substances,
the epoxy resin accounts for 4% of the total weight of the epoxy resin composition, the curing agent accounts for 1% of the total weight of the epoxy resin composition, the accelerator accounts for 0.5% of the total weight of the epoxy resin composition, the high thermal conductive filler accounts for 93% of the total weight of the epoxy resin composition, the surface treatment agent accounts for 1.5% of the weight of the high thermal conductive filler, and the balance is raw materials of other components, so that the consistency of experimental conditions is ensured, and the other components adopted in the embodiment are the same as those in the following embodiments;
the preparation method comprises adding the high-thermal-conductivity filler into a high-speed stirrer, adding the surface treatment agent into the high-speed stirrer in a stirring state, and mixing and stirring at 120 ℃ for 30min to uniformly disperse the surface treatment agent on the surface of the high-thermal-conductivity filler; then adding other components such as epoxy resin, curing agent and the like, stirring and mixing uniformly, kneading and rolling the mixture by an extruder, a calender roll or a kneader, and then cooling and crushing the mixture to obtain the powdery epoxy resin composition with certain particle size distribution.
Embodiment 6 is a highly thermally conductive epoxy resin composition, which comprises an epoxy resin, a curing agent, an accelerator, a highly thermally conductive filler, and a surface treatment agent; the kinds of the above-mentioned respective compositions are the same as those in example 5;
the epoxy resin accounts for 2 percent of the total weight of the epoxy resin composition, the curing agent accounts for 3 percent of the total weight of the epoxy resin composition, the accelerating agent accounts for 0.3 percent of the total weight of the epoxy resin composition, the high heat-conducting filler accounts for 94 percent of the total weight of the epoxy resin composition, the surface treating agent accounts for 0.7 percent of the weight of the high heat-conducting filler, and the balance is raw materials of other components;
the preparation method was the same as in example 5.
Embodiment 7 is a highly thermally conductive epoxy resin composition, which comprises an epoxy resin, a curing agent, an accelerator, a highly thermally conductive filler, and a surface treatment agent; the types of the curing agent and the high thermal conductive filler are the same as those of the embodiment 5; the epoxy resin is the mixture of epoxy resins with structures shown in formula (1) and formula (2);
the epoxy resin shown in the formula (1) accounts for 1.7 percent of the total weight of the epoxy resin composition, the epoxy resin shown in the formula (2) accounts for 3 percent of the total weight of the epoxy resin composition, the curing agent accounts for 5 percent of the total weight of the epoxy resin composition, the accelerating agent accounts for 0.3 percent of the total weight of the epoxy resin composition, the high thermal conductive filler accounts for 90 percent of the total weight of the epoxy resin composition, the surface treating agent accounts for 0.01 percent of the weight of the high thermal conductive filler, and the balance is other component raw materials; the preparation method was the same as in example 5.
Embodiment 8 is a highly thermally conductive epoxy resin composition, which comprises an epoxy resin, a curing agent, an accelerator, a highly thermally conductive filler, and a surface treatment agent; the types of the curing agent, the high thermal conductive filler and the accelerator are the same as those in example 5; the epoxy resin is the epoxy resin with the structure shown in the formula (1);
the epoxy resin shown in the formula (1) accounts for 4% of the total weight of the epoxy resin composition, the curing agent accounts for 1% of the total weight of the epoxy resin composition, the accelerator accounts for 0.3% of the total weight of the epoxy resin composition, the high thermal conductive filler accounts for 92% of the total weight of the epoxy resin composition, the surface treating agent accounts for 2.5% of the weight of the high thermal conductive filler, and the balance is raw materials of other components; the preparation method was the same as in example 5.
Example 9, examples 1-8, wherein the ratio of the epoxy equivalent weight in the epoxy resin to the hydroxyl equivalent weight in the curing agent is 0.5.
Example 10, the high thermal conductivity epoxy resin composition of examples 1-8, wherein the ratio of the epoxy equivalent to the hydroxyl equivalent in the curing agent is 0.7.
Example 11, the highly thermally conductive epoxy resin composition of examples 1 to 8, wherein the ratio of the epoxy equivalent to the hydroxyl equivalent in the curing agent is 1.8.
The highly thermally conductive epoxy resin composition of example 12, examples 1-8, wherein the epoxy resin has an equivalent ratio of epoxy equivalent to hydroxyl equivalent in the curing agent of 2.0.
The epoxy resin composition of example 13, examples 1-12, wherein the high thermal conductive filler is spherical alumina filler with an average particle size of 0.1-20um and a maximum particle size of less than 55 um.
Comparative example 1, a high thermal conductive epoxy resin composition, the composition of high thermal conductive filler selected from silica filler, the rest is the same as example 5, preparation method is also the same as example 5.
Comparative example 2, a highly thermal conductive epoxy resin composition, in which the epoxy resin is a mixture of epoxy resin represented by formula (2) and epoxy resin CNE195LL, wherein the epoxy resin represented by formula (2) accounts for 25% of the total weight of the epoxy resin, the epoxy resin CNE195LL accounts for 75% of the total weight of the epoxy resin, the epoxy resin CNE195LL is epoxy resin of vinblastic resin, the rest is the same as example 5, and the preparation method is the same as example 5.
Comparative example 3, a highly thermally conductive epoxy resin composition, in which the curing agent is a mixture of a phenolic resin represented by formula (3) and a curing agent HF-1M, wherein the phenolic resin represented by formula (3) accounts for 20% of the total weight of the curing agent, the curing agent HF-1M accounts for 80% of the total weight of the curing agent, the curing agent HF-1M is a phenolic resin of Nippon Ming & Shih, the rest is the same as example 5, and the preparation method is the same as example 5.
Comparative example 4, a highly heat conductive epoxy resin composition, which was otherwise the same as example 5 except that no surface treatment agent was added, and the preparation method was the same as example 5.
Comparative example 5, a highly thermally conductive epoxy resin composition having the same components as in example 5; the preparation method is that the surface treating agent and the high heat conduction filler are not mixed in advance, but the components are directly mixed to prepare the epoxy resin composition.
The following test experiments were conducted on the epoxy resin compositions prepared using the components and methods described in examples 5 to 8 and comparative examples 1 to 5, and the following table shows the components and weight percentages of the products described in examples 5 to 8 and comparative examples 1 to 5,
the relevant experimental methods adopted by the products of the above examples are as follows:
(1) gel time
The gelation time(s) was determined as set forth in item 5.3 of SJ/T11197-1999 epoxy Molding Compound.
(2) Length of flow
The flow distance (cm) was determined as the 5.2 spiral flow length of SJ/T11197-1999 epoxy Molding Compound.
(3) Coefficient of thermal conductivity
Thermal conductivity was measured as described in item 5.7 of the SJ/T11197-1999 epoxy Molding Compound.
(4) Bending strength
The flexural strength was tested according to the 5.5 th test for flexural strength, flexural modulus of the epoxy Molding Compound SJ/T11197-1999.
(5) High temperature storage modulus
The storage modulus (MPa) of the block at 175 ℃ was measured by a dynamic thermomechanical analyzer (DMA).
(6) Operability test
Preparing the epoxy resin composition powder into a cake material with a certain specification according to the requirements of customers, and molding and packaging the energy module under the conditions that the die assembly pressure is 300kN, the injection pressure is 10MPa and the curing time is 300 s. If the packaging is finished, no air holes, sand holes, adhesive films and the like exist. The operability is OK, otherwise NG.
(7) Reliability test
Preparing the epoxy resin composition powder into a cake material with a certain specification according to the requirements of customers, and molding and packaging the energy module under the conditions that the die assembly pressure is 300kN, the injection pressure is 10MPa and the curing time is 300 s. After packaging is finished, curing is carried out for 4h at 125 ℃, three-level assessment is carried out according to JEDEC standard, the cured sample is subjected to advanced C-SAM scanning, the layering condition is observed, then drying is carried out for 24h at 125 ℃, moisture absorption is carried out for 40h at the relative humidity of 60 ℃/60%, reflow soldering is carried out for three times at 260 ℃, and after cooling, C-SAM scanning is carried out again, and the layering condition is observed. And if the two conditions are not layered, the reliability is judged to be OK, and if not, the reliability is judged to be NG.
The results of the tests on the products of examples 5-8 and comparative examples 1-5 are shown in the following table:
from the above test results, it is clear that the high thermal conductive epoxy resin compositions of 5W/mK, 5.5W/mK, 4W/mK, and 4.5W/mK, which are obtained in examples 5, 6, 7, and 8, respectively, have high flexural strength, low storage modulus, and reliability Ok;
comparative example 1 the same as example 5 except that no high thermal conductive filler was used, the epoxy resin composition obtained had a low thermal conductivity.
Compared with the example 5, the comparative example 2 has lower content of the epoxy resin with the structure of the formula (2), and the reliability of the obtained high-thermal-conductivity epoxy resin composition is poor.
Compared with the example 5, the content of the phenolic resin with the structure shown in the formula (3) in the comparative example 3 is lower, and the reliability of the obtained high-thermal-conductivity epoxy resin composition is poor.
Comparative example 4 compared to example 5, without the surface treatment agent, the obtained highly thermally conductive epoxy resin composition had low flexural strength, high storage modulus at 175 ℃, and poor operability and reliability.
Comparative example 5 in comparison with example 5, in the process of preparing the epoxy resin composition, the surface treatment agent and the high thermal conductive filler were not mixed in advance, and the obtained high thermal conductive epoxy resin composition was low in bending strength and poor in workability and reliability.
As can be seen from the above examples, the high thermal conductivity type epoxy resin composition of the present invention has better comprehensive properties such as thermal conductivity, bending strength, storage modulus, operability, reliability, etc. than the prior art.
The above embodiments are only for more clearly illustrating the technical solutions of the present invention, and the scope of the present invention includes but is not limited to the above embodiments, and any suitable changes or substitutions that are consistent with the claims of the present invention and are made by those skilled in the art shown should fall within the scope of the present invention.
Claims (10)
1. A high thermal conductive epoxy resin composition, characterized in that: the composition comprises epoxy resin, high heat conduction filler, surface treating agent and curing agent,
the high heat-conducting filler contains alumina, and the content of the alumina accounts for 90-94% of the total content of the epoxy resin composition.
2. A highly thermally conductive epoxy resin composition according to claim 1, wherein: the surface treating agent is polyphosphoric acid and acrylic acid copolymer resin shown as a formula (4), the content of the polyphosphoric acid and the acrylic acid copolymer resin accounts for 0.01-5% of the content of the high-heat-conducting filler, and the structural formula is
Wherein m is an integer of 20-40, and n is an integer of 40-80.
3. The highly thermally conductive epoxy resin composition according to claim 1 or 2, characterized in that: the content of the epoxy resin accounts for 1 to 10 percent of the total content of the epoxy resin composition, the epoxy resin comprises the epoxy resin shown in a formula (1) or a formula (2), and the content of the epoxy resin accounts for at least 50 percent of the total content of the epoxy resin,
formula (1), wherein R ═ H or CH3；
In the formula (2), n is an integer of 1 to 15.
4. A highly thermally conductive epoxy resin composition according to claim 3, wherein: the content of the curing agent accounts for 1-10% of the total content of the epoxy resin composition, the curing agent comprises phenolic resin shown in formula (3), the content of the phenolic resin at least accounts for 50% of the total content of the curing agent, and the structural formula is shown in the specification
Formula (3), wherein n is 0 to 10.
5. The highly thermally conductive epoxy resin composition according to claim 4, wherein: the ratio of epoxy equivalent in the epoxy resin to hydroxyl equivalent in the curing agent is 0.5-2.0.
6. The highly thermally conductive epoxy resin composition according to claim 5, wherein: the ratio of the epoxy equivalent in the epoxy resin to the hydroxyl equivalent in the curing agent is 0.7-1.8.
7. A highly thermally conductive epoxy resin composition according to claim 1, wherein: the composition also comprises an accelerant which is one or a mixture of more of imidazole, phosphorus or amine catalysts, and the content of the accelerant accounts for 0.01-2% of the total content of the epoxy resin composition.
8. A highly thermally conductive epoxy resin composition according to claim 1, wherein: the average grain diameter of the alumina high-thermal-conductivity filler is selected from 0.1-20um, the maximum grain diameter is less than 100um, and the maximum grain diameter is further preferably less than 75 um.
9. A highly thermally conductive epoxy resin composition according to claim 1, wherein: the high heat conduction filler is angular or spherical.
10. A method for preparing the highly thermally conductive epoxy resin composition according to any one of claims 1 to 9, wherein: the method comprises the steps of mixing a surface treating agent and a high-thermal-conductivity filler in advance for 15min or more at a mixing temperature of 25-200 ℃, cooling to room temperature after mixing, adding other components, stirring and mixing, kneading, calendering, cooling and crushing after uniformly mixing to obtain the powdery epoxy resin composition with a certain particle size distribution.
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