CN110078898B - Heat-conducting resin composition - Google Patents
Heat-conducting resin composition Download PDFInfo
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- CN110078898B CN110078898B CN201910439939.0A CN201910439939A CN110078898B CN 110078898 B CN110078898 B CN 110078898B CN 201910439939 A CN201910439939 A CN 201910439939A CN 110078898 B CN110078898 B CN 110078898B
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- 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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- 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
- C08G59/621—Phenols
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- 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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- C09K5/00—Heat-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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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Abstract
The application discloses heat-conducting resin composition introduces the mesogen to the curing agent, utilizes the rigidity platykurtic structure of mesogen, still remains regular orderly liquid crystal phase after making epoxy solidify, and a large amount of regular orderly liquid crystal phase can improve heat conductivity of heat-conducting resin composition in the system, and the electronic packaging material that adopts this application heat-conducting resin composition to prepare has good thermal conductivity, and then satisfies the requirement of electron trade to the heat dissipation base plate thermal diffusivity. In addition, the preparation process of the heat-conducting resin composition is simple, the production is convenient, and the wide popularization and use are easy.
Description
Technical Field
The application relates to the technical field of epoxy resin, in particular to a heat-conducting resin composition.
Background
Epoxy resin compositions containing epoxy resins and curing agents thereof as essential components have excellent properties such as heat resistance and moisture resistance, and therefore, they are widely used in paints, adhesives, composite resin substrates, electronic packaging materials, and the like, and particularly, they play a great role in electronic components and integrated circuit packaging, and 95% or more of the electronic components and integrated circuit packaging substrates on the market are prepared from epoxy resin compositions. In the current electronic market, high-power components and parts are more and more in electronic products, and simultaneously, the integration density of the components and parts is also higher and higher, so that the heat conductivity of a packaging substrate needs to be further improved in order to meet the heat dissipation requirement of the electronic products.
At present, a common method for improving the thermal conductivity of the package substrate is to add a thermal conductive filler into an epoxy resin composition to improve the thermal conductivity of the epoxy resin composition, thereby improving the thermal conductivity of the substrate. Fig. 1 is a graph showing the relationship between the thermal conductivity of the heat-conductive composite material and the volume fraction of the filler, and as shown in fig. 1, the thermal conductivity of the substrate is obviously increased as the addition amount of the heat-conductive filler is increased. However, when the addition amount of the heat conductive filler is larger than the critical volume concentration, the resin cannot completely wet the packing filler, which causes significant voids in the substrate and a rapid decrease in reliability, and thus, when the addition amount of the heat conductive filler reaches a certain amount, the heat conductivity of the substrate cannot be improved by increasing the addition amount of the filler.
Therefore, a thermally conductive resin composition having good thermal conductivity is desired.
Disclosure of Invention
The application provides a heat-conducting resin composition, which solves the problem that the heat dissipation performance of the existing epoxy resin does not meet the industrial requirements when the epoxy resin is used for electronic packaging.
The present application provides a thermally conductive resin composition comprising:
component 1: an epoxy resin;
and (2) component: a curing agent for curing the epoxy resin composition,
wherein the curing agent comprises a compound represented by the following general formula (1):
in the general formula (1), R1，R2，R3，R4，R5，R6，R7，R8Independently of one another are-H or-CH3；
R includes structural moieties represented by the following (a) to (e), n represents an integer of 1 to 4, and when n is 1, R is any one of (a), (b), (c), (d), and (e); when n > 1, R is any one of (a), (b), (c), (d) and (e) independently,
optionally, the mass fraction of the curing agent in the total amount of the epoxy resin and the curing agent is more than 20%.
Optionally, the epoxy resin comprises at least one multifunctional epoxy resin comprising o-cresol novolac, phenol novolac, bisphenol a novolac, trifunctional novolac, DOPO modified novolac, DCPD phenol novolac, XYLOK novolac, biphenyl novolac, triglycidyl triisocyanate, triglycidyl p-aminophenol, tetraglycidyl diaminodiphenylmethane, diaminodiphenyl ether tetraglycidyl amine, 1,2, 2-tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether.
Optionally, the epoxy resin is a mixture of a multifunctional epoxy resin and a difunctional epoxy resin, wherein the difunctional epoxy resin comprises one or more of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, brominated epoxy resin, ethylene glycol diglycidyl ether, tetramethylbiphenol diglycidyl ether, 2, 5-di-tert-butylhydroquinone diglycidyl ether, 2 ' -dimethyl-5, 5 ' -di-tert-butyl-4, 4 ' -diglycidyl diphenyl sulfide, and tetramethylbisphenol F diglycidyl ether.
Optionally, the curing agent further comprises one or more of DICY, DDS, and PN.
Optionally, the thermally conductive resin composition further comprises component 3: and the curing accelerator comprises one or more of tertiary amine accelerators, imidazole accelerators and boron trifluoride amine complexes.
Optionally, the thermally conductive resin composition further comprises component 4: a thermally conductive filler comprising one or more of aluminum nitride, boron nitride, aluminum oxide, magnesium oxide, crystalline silica, aluminum hydroxide, magnesium hydroxide, calcium fluoride, and talc.
Optionally, the thermally conductive resin composition further includes a dispersant, a coupling agent, an anti-settling agent, or a solvent.
Optionally, the particle size D of the thermally conductive filler50Between 0.1 and 100 μm.
The application also provides a prepreg, a laminated board, a copper-clad plate, a metal substrate and a circuit board which are prepared based on the resin composition.
The application provides a heat-conducting resin composition, introduces the mesogen to the curing agent, utilizes the rigidity platykurtic structure of mesogen, still remains regular and orderly liquid crystal phase after making epoxy solidify, and a large amount of regular and orderly liquid crystal phase can improve heat conductivity of heat-conducting resin composition in the system, and the electronic packaging material that adopts this application heat-conducting resin composition to prepare has good thermal conductivity, and then satisfies the requirement of electron trade to the heat dissipation base plate thermal diffusivity. In addition, the preparation process of the heat-conducting resin composition is simple, the production is convenient, and the wide popularization and use are easy.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph of thermal conductivity of a thermally conductive composite as a function of filler volume fraction.
Detailed Description
The present application provides a thermally conductive resin composition having good thermal conductivity, specifically comprising:
component 1: an epoxy resin;
and (2) component: a curing agent for curing the epoxy resin composition,
wherein the curing agent comprises a compound represented by the following general formula (1):
in the general formula (1), n represents an integer of 1 to 4, R1，R2，R3，R4，R5，R6，R7，R8Independently of one another are-H or-CH3；
R includes structural sites represented by the following (a) to (e),
r includes structural sites represented by the following (a) to (e), and specifically, when n is 1, R is any one of (a), (b), (c), (d), and (e); when n > 1, R is any one of (a), (b), (c), (d) and (e) independently of each other.
In this example, the mass fraction of the curing agent should be greater than 20% of the total mass of the curing agent and the epoxy resin in order to have enough mesogens in the resin system to facilitate the formation of a liquid crystal phase.
In this example, in order to provide a cured product with a certain crosslinking density and heat resistance, the epoxy resin includes at least one multifunctional epoxy resin, and the multifunctional epoxy resin includes o-cresol novolac, phenol novolac, bisphenol a novolac, trifunctional novolac, DOPO-modified novolac, DCPD phenol novolac, XYLOK novolac, biphenyl novolac, triglycidyl triisocyanate, triglycidyl p-aminophenol, tetraglycidyl diaminodiphenylmethane, diaminodiphenyl ether tetraglycidyl amine, 1,2, 2-tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether.
In this example, the epoxy resin is a mixture of a multifunctional epoxy resin and a bifunctional epoxy resin, and the bifunctional epoxy resin can reduce the crosslinking density of the cured product, in order to provide the cured product with better toughness. Wherein the bifunctional epoxy resin comprises one or more of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, brominated epoxy resin, ethylene glycol diglycidyl ether, tetramethylbiphenol diglycidyl ether, 2, 5-di-tert-butylhydroquinone diglycidyl ether, 2 ' -dimethyl-5, 5 ' -di-tert-butyl-4, 4 ' -diglycidyl diphenyl sulfide and tetramethylbisphenol F diglycidyl ether.
In this example, in order to improve the adhesion and heat resistance of the thermally conductive resin composition, the curing agent further includes one or more of Dicyandiamide (DICY), 4' diaminodiphenyl sulfone (DDS), and o-cresol formaldehyde resin (PN).
In this embodiment, in order to lower the curing temperature, shorten the curing time, and improve the curing degree, the thermally conductive resin composition further includes component 3: the curing accelerator comprises one or more of tertiary amine accelerators, imidazole accelerators and boron trifluoride amine complexes.
In order to further improve the thermal conductivity of the cured product, the heat-conducting resin composition also comprises a component 4: a thermally conductive filler comprising one or more of aluminum nitride, boron nitride, aluminum oxide, magnesium oxide, crystalline silica, aluminum hydroxide, magnesium hydroxide, calcium fluoride, and talc. Among them, the heat conductive filler used is preferably a filler subjected to surface treatment, and the surface treatment agent is preferably a silane coupling agent or a titanate coupling agent. The grain diameter of the heat-conducting filler is between 0.1 and 100 mu m, and certainly, two or more grain diameter grades can be selected for compounding, so that the bulk density is improved.
In order to enable better dispersion of the filler, better interfacial bonding with the resin, and better manufacturability, the thermally conductive resin composition in this example further includes a dispersant, a coupling agent, an anti-settling agent, or a solvent. At present, there are many kinds of dispersants, coupling agents, anti-settling agents, and solvents, and those skilled in the art can select suitable dispersants, coupling agents, anti-settling agents, and solvents according to actual needs, and detailed descriptions of specific varieties will not be provided herein.
In order to clearly show that the heat-conducting resin composition of the present application has good heat-conducting performance and can be suitably used for preparing packaging parts such as metal substrates, prepregs, laminated plates and the like, the following description will be made through experimental data.
Table 1 shows the composition of the resin compositions in comparative examples and examples.
TABLE 1
The composition in table 1 will be described below:
the phenol novolac epoxy is multifunctional epoxy, the epoxy equivalent is 170-200 g/eq, and the softening point is 40-60 ℃;
the bisphenol A epoxy is bifunctional epoxy, and the epoxy equivalent is 430-460 g/eq;
AG-80, tetraglycidyl diaminodiphenylmethane, is a multifunctional epoxy with an epoxy equivalent weight of 135 g/eq;
PN, namely linear phenolic resin, the hydroxyl equivalent weight of which is 105-110 g/mol, and the softening point of which is 104-110 ℃;
alumina of diameter D50Is 5 mu.
The structure of curing agent A is:
wherein R is
The hydroxyl equivalent is 376g/mol, and the specific synthetic process is as follows: 85g of bisphenol F epoxy with the epoxy equivalent of 160-180 g/eq and 93g of 4, 4-biphenol are taken to be dissolved in ethylene glycol monomethyl ether together, and then 0.05g of dimethyl imidazole, 120-125 gReacting for 2h, and actually measuring 376g/mol of phenolic hydroxyl equivalent.
The structure of curing agent B is:
wherein R is
The hydroxyl equivalent of the hydroxyl is 388g/mol, and the specific synthetic process is as follows: 90g of bisphenol A epoxy with the epoxy equivalent of 175-185 g/eq and 93g of 4, 4-biphenol are taken to be dissolved in ethylene glycol monomethyl ether together, 0.02g of tetramethyl ammonium bromide is added, the mixture reacts for 3 hours at 70-80 ℃, and the actual measurement of the phenolic hydroxyl equivalent is 386 g/mol.
The structure of curing agent C is:
wherein R is
The hydroxyl equivalent weight is 573g/mol, and the specific synthetic process is as follows: 185g of tetrabromobisphenol A type epoxy with the epoxy equivalent of 350-400g/eq and 93g of 4, 4-biphenol are dissolved in DMF and react for 3 hours at 150-160 ℃, and the actual measurement of the phenolic hydroxyl equivalent is 573 g/mol.
The structure of curing agent D is:
wherein R is
The hydroxyl equivalent is 376g/mol, and the specific synthetic process is as follows: dissolving 65g of ethylene glycol diglycidyl ether with epoxy equivalent of 125-135 g/eq and 123g of 3,3,5, 5-tetramethyl-4, 4-diphenol in ethylene glycol monomethyl ether, and adding 0.03g of tetramethylThe ammonium bromide is obtained by reacting for 2 hours at 100-110 ℃, and the actual measurement of the equivalent weight of phenolic hydroxyl groups is 376 g/mol.
The structure of curing agent E is:
The structure of curing agent F is:
wherein R is
The hydroxyl equivalent weight is 440g/mol, and the specific synthetic process is as follows: 90g of bisphenol A epoxy with the epoxy equivalent of 175-185 g/eq and 123g of 3,3,5, 5-tetramethyl-4, 4-biphenol are taken to be dissolved in DMF together and react for 4h at 120-130 ℃, and the measured phenolic hydroxyl equivalent is 439 g/mol.
The resin composition of the comparative example and the embodiment in the table 1 is adopted to prepare the copper-clad plate, and the preparation process comprises the following steps:
firstly, preparing a glue solution: preparing materials according to the proportion of the materials in the comparative example and the table in the example, dissolving the epoxy resin, the curing agent and the accelerator by using a solvent, and uniformly mixing to obtain a glue solution without filler. When the filler is mixed, firstly, preparing a filler-free glue solution, then adding the auxiliary agent, uniformly mixing, adding the filler, and performing ball milling dispersion to obtain the filler-containing glue solution.
Then, an adhesive sheet was prepared: and dipping 7628 glass cloth by using glue solution, drying at a certain temperature and semi-curing to obtain the bonding sheet.
And finally, preparing a copper-clad plate: and (3) overlapping 4 bonding sheets, covering copper foils on the upper and lower bonding sheets, and performing hot-pressing curing to obtain the copper-clad plate, wherein the curing condition is 180 ℃ and 30 min.
The copper-clad plates prepared using the resin compositions of comparative example and example were subjected to a performance test in which the thermal conductivity was measured according to ASTM D5470 method and other properties were measured according to IPC TM-650 method, and Table 2 shows the results of the performance test.
TABLE 2
As can be seen from the results of the performance tests in Table 2, the resin compositions of examples 1 and 3 to 11 have higher thermal conductivity than comparative example 1 because no filler is added to comparative example 1 and no filler is added to examples 1 and 3 to 11, and the thermal conductivity of comparative example 2 and example 2 increases after the filler is added to comparative example 1 and example 1.
In addition, other products can be prepared using the thermally conductive resin composition of the present application. For example, the present application also provides a resin cured product obtained by curing the above-described thermally conductive resin composition; the application also provides a metal substrate, wherein the insulating layer is formed by curing the heat-conducting resin composition; the application also provides a prepreg which is formed by impregnating the heat-conducting resin composition described above with a reinforcing material; the application also provides a laminate formed by curing the prepreg described above.
The application provides a heat-conducting resin composition, liquid crystal elements are introduced into a curing agent, and the structural general formula of the liquid crystal elements in the application is as follows:
wherein R is1，R2，R3，R4，R5，R6，R7，R8Independently of one another are-H or-CH3. The heat-conducting resin composition of the present applicationThe rigid flat structure of the liquid crystal element is utilized, the regular and ordered liquid crystal phase is still kept after the epoxy resin is cured, the thermal conductivity of the heat-conducting resin composition can be improved by a large amount of regular and ordered liquid crystal phases in the system, and the electronic packaging material prepared by the heat-conducting resin composition has good thermal conductivity, so that the requirement of the electronic industry on the heat dissipation of the heat dissipation substrate is met. In addition, the preparation process of the heat-conducting resin composition is simple, the production is convenient, and the wide popularization and use are easy.
The above-described embodiments of the present application do not limit the scope of the present application.
Claims (9)
1. A thermally conductive resin composition, comprising:
component 1: an epoxy resin;
and (2) component: a curing agent, wherein the mass fraction of the curing agent in the total amount of the epoxy resin and the curing agent is more than 20 percent,
wherein the curing agent comprises a compound represented by the following general formula (1):
in the general formula (1), R1，R2，R3，R4，R5，R6，R7，R8Independently of one another are-H or-CH3；
R includes structural moieties represented by the following (a) to (e), n represents an integer of 1 to 4, and when n is 1, R is any one of (a), (b), (c), (d), and (e); when n > 1, R is any one of (a), (b), (c), (d) and (e) independently,
2. the thermally conductive resin composition of claim 1, wherein the epoxy resin comprises at least one multifunctional epoxy resin comprising o-cresol novolac, phenol novolac, bisphenol a novolac, trifunctional novolac, DOPO-modified novolac, DCPD phenol novolac, XYLOK novolac, biphenyl novolac, triglycidyl triisocyanate, triglycidyl p-aminophenol, tetraglycidyl diaminodiphenylmethane, diaminodiphenyl ether tetraglycidyl amine, 1,2, 2-tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether.
3. The heat conductive resin composition of claim 1, wherein the epoxy resin is a mixture of a multifunctional epoxy resin and a difunctional epoxy resin, wherein the difunctional epoxy resin comprises one or more of bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, bisphenol F epoxy resin, brominated epoxy resin, ethylene glycol diglycidyl ether, tetramethylbiphenol diglycidyl ether, 2, 5-di-tert-butylhydroquinone diglycidyl ether, and 2,2 ' -dimethyl-5, 5 ' -di-tert-butyl-4, 4 ' -diglycidyl diphenyl sulfide.
4. The thermally conductive resin composition according to claim 1, wherein the curing agent further comprises one or more of DICY, DDS, and PN.
5. The heat conductive resin composition according to claim 1, further comprising component 3: and the curing accelerator comprises one or more of tertiary amine accelerators, imidazole accelerators and boron trifluoride amine complexes.
6. The heat conductive resin composition according to claim 1, further comprising component 4: a thermally conductive filler comprising one or more of aluminum nitride, boron nitride, aluminum oxide, magnesium oxide, crystalline silica, aluminum hydroxide, magnesium hydroxide, calcium fluoride, and talc.
7. The heat conductive resin composition of claim 1, further comprising a dispersant, a coupling agent, an anti-settling agent, or a solvent.
8. The heat-conductive resin composition according to claim 6, wherein the particle diameter D of the heat-conductive filler50Between 0.1 and 100 μm.
9. A prepreg, a laminated board, a copper clad laminate, a metal substrate, a circuit board prepared based on the heat conductive resin composition according to any one of claims 1 to 8.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910439939.0A CN110078898B (en) | 2019-05-24 | 2019-05-24 | Heat-conducting resin composition |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647648A (en) * | 1985-08-26 | 1987-03-03 | The Dow Chemical Company | Polyhydroxyethers from hydroxybiphenyls |
| US4786668A (en) * | 1986-06-09 | 1988-11-22 | Shell Oil Company | Resin materials |
| CN101234975A (en) * | 2008-03-05 | 2008-08-06 | 东华大学 | Method for preparing 3,3'-di(4-cyanophenoxy)diphenyl |
| JP2010090182A (en) * | 2008-10-03 | 2010-04-22 | Shin Kobe Electric Mach Co Ltd | Flame-retardant epoxy resin composition, prepreg, laminate sheet, and wiring board |
| CN102504202A (en) * | 2011-10-10 | 2012-06-20 | 中科院广州化学有限公司 | Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof |
| CN105440588A (en) * | 2015-12-24 | 2016-03-30 | 江苏中鹏新材料股份有限公司 | High-thermal-conductivitymolded underfill as well as preparation method and application thereof |
-
2019
- 2019-05-24 CN CN201910439939.0A patent/CN110078898B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647648A (en) * | 1985-08-26 | 1987-03-03 | The Dow Chemical Company | Polyhydroxyethers from hydroxybiphenyls |
| US4786668A (en) * | 1986-06-09 | 1988-11-22 | Shell Oil Company | Resin materials |
| CN101234975A (en) * | 2008-03-05 | 2008-08-06 | 东华大学 | Method for preparing 3,3'-di(4-cyanophenoxy)diphenyl |
| JP2010090182A (en) * | 2008-10-03 | 2010-04-22 | Shin Kobe Electric Mach Co Ltd | Flame-retardant epoxy resin composition, prepreg, laminate sheet, and wiring board |
| CN102504202A (en) * | 2011-10-10 | 2012-06-20 | 中科院广州化学有限公司 | Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof |
| CN105440588A (en) * | 2015-12-24 | 2016-03-30 | 江苏中鹏新材料股份有限公司 | High-thermal-conductivitymolded underfill as well as preparation method and application thereof |
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