CN110078898A - A kind of heat-conductive resin composition - Google Patents
A kind of heat-conductive resin composition Download PDFInfo
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- CN110078898A CN110078898A CN201910439939.0A CN201910439939A CN110078898A CN 110078898 A CN110078898 A CN 110078898A CN 201910439939 A CN201910439939 A CN 201910439939A CN 110078898 A CN110078898 A CN 110078898A
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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
- B32B15/04—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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- 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
- C08G59/4007—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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- 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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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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
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- 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
- 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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- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
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- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
This application discloses a kind of heat-conductive resin compositions, liquid crystal unit is introduced to curing agent, utilize the rigid flat structure of liquid crystal unit, still retain regular orderly liquid crystalline phase after making epoxy resin cure, a large amount of regular orderly liquid crystalline phases can be improved the thermal conductivity of heat-conductive resin composition in system, electronic package material using the preparation of the application heat-conductive resin composition has good thermal conductivity energy, and then meets requirement of the electronics industry to heat-radiating substrate thermal diffusivity.In addition, the preparation process of the heat-conductive resin composition of the application is simple, facilitate production, is easy to be widely used to promote.
Description
Technical field
This application involves Epoxy Resin Technology field more particularly to a kind of heat-conductive resin compositions.
Background technique
Have heat resistance, moisture-proof etc. excellent with the composition epoxy resin of epoxy resin and its curing agent as an essential component
It is anisotropic can, therefore, coating, adhesive, composite resin matrix, in terms of be widely used, especially
It is that great effect has been played in electronic component and integrated antenna package, 95% or more electronic component and integrated electricity on the market
The package substrate on road is all made of composition epoxy resin and is prepared.Current electronic market, high performance components in electronic product
It is more and more, meanwhile, the integration density of component is also higher and higher, for the cooling requirements for meeting electronic product, need to further mention
The thermal conductivity of high package substrate.
Currently, the thermal conductivity common method for improving package substrate is to add heat filling into composition epoxy resin, mention
The thermal conductivity of high epoxy resin composition, and then improve the thermal conductivity of substrate.Fig. 1 is heat-conductive composite material thermal conductivity with filling body
The relational graph of fraction variation, as shown in Figure 1, substrate thermal conductivity obviously rises as heat filling additive amount rises.But
When heat filling additive amount be greater than its critical size concentration after, resin just can not complete wetting wrap up filler, this will cause base
There is obvious cavity in intralamellar part, and reliability sharply declines, thus, it just can not be by mentioning after heat filling reaches certain additive amount
High filler additive amount improves substrate thermal conductivity.
It would therefore be highly desirable to a kind of heat-conductive resin composition with Thermal conductivity.
Summary of the invention
The application provides a kind of heat-conductive resin composition, when solving existing epoxy resin for Electronic Packaging, dissipates
Hot the problem of being unsatisfactory for industry requirement.
This application provides a kind of heat-conductive resin compositions, comprising:
Component 1: epoxy resin；
Component 2: curing agent,
Wherein, the curing agent includes the compound that the following general formula (1) indicates:
In the general formula (1), R1, R2, R3, R4, R5, R6, R7, R8Independently of one another-H or-CH3；
R includes structure position shown in following (a)-(e), and n indicates the integer of 1-4, as n=1, R is (a), (b),
(c), (d), any one in (e)；As n > 1, R is independently of one another (a), (b), (c), (d), any one in (e)
Kind,
Optionally, shown curing agent accounts for epoxy resin and the mass fraction of curing agent total amount is greater than 20%.
Optionally, the epoxy resin includes at least one polyfunctional epoxy resin, and polyfunctional epoxy resin includes adjacent first
Epoxy novolac, the DCPD that epoxy novolac, phenol novolac epoxy, bisphenol A-type epoxy novolac, trifunctional epoxy novolac, DOPO are modified
Phenol novolac epoxy, XYLOK epoxy novolac, biphenyl type epoxy novolac, triglycidyl group triisocyanate, triglycidyl group
Para-aminophenol, four glycidyl group diaminodiphenylmethane, four glycidyl amine of diamino-diphenyl ether, 1,1,2,2- tetra-
Four glycidol ether of (p-hydroxybenzene) ethane.
Optionally, the epoxy resin is the mixture of polyfunctional epoxy resin and bifunctional epoxy resin, wherein double officials
Can epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol f type epoxy resin, brominated epoxy resin,
Ethylene glycol diglycidylether, tetramethyl biphenyl diphenol diglycidyl ether, 2,5 di tert butyl hydroquinone 2-glycidyl
Ether, 2,2 '--5,5 '-di-t-butyls -4,4 of dimethyl '-diglycidyl diphenylsulfide, tetramethyl Bisphenol F two are shunk sweet
One of oily ether is a variety of.
Optionally, the curing agent further includes one of DICY, DDS and PN or a variety of.
Optionally, the heat-conductive resin composition further includes component 3: curing accelerator, and the curing accelerator includes uncle
One of complex compound of amine type accelerator, imidazoles promotor and borontrifluoride boron amide is a variety of.
Optionally, the heat-conductive resin composition further includes component 4: heat filling, the heat filling include aluminium nitride,
One in boron nitride, aluminium oxide, magnesia, crystalline sillica, aluminium hydroxide, magnesium hydroxide, calcirm-fluoride and talcum powder
Kind is a variety of.
Optionally, the heat-conductive resin composition further includes dispersing agent, coupling agent, antisettling agent or solvent.
Optionally, the partial size D of the heat filling50Between 0.1-100 μm.
The application also provide prepreg based on above-mentioned resin combination preparation, laminate, copper-clad plate, metal substrate,
Circuit board.
This application provides a kind of heat-conductive resin compositions, and liquid crystal unit is introduced to curing agent, utilizes liquid crystal unit
Rigid flat structure makes still to retain regular orderly liquid crystalline phase after epoxy resin cure, a large amount of regular orderly in system
Liquid crystalline phase can be improved the thermal conductivity of heat-conductive resin composition, the Electronic Packaging material prepared using the application heat-conductive resin composition
Material has good thermal conductivity energy, and then meets requirement of the electronics industry to heat-radiating substrate thermal diffusivity.In addition, the thermally conductive tree of the application
The preparation process of oil/fat composition is simple, facilitates production, is easy to be widely used to promote.
Detailed description of the invention
In order to illustrate more clearly of the technical solution of the application, letter will be made to attached drawing needed in the embodiment below
Singly introduce, it should be apparent that, for those of ordinary skills, without creative efforts, also
Other drawings may be obtained according to these drawings without any creative labor.
Fig. 1 is the relational graph that heat-conductive composite material thermal conductivity changes with packing volume mark.
Specific embodiment
The application provides a kind of heat-conductive resin composition with Thermal conductivity, which specifically wraps
It includes:
Component 1: epoxy resin；
Component 2: curing agent,
Wherein, the curing agent includes the compound that the following general formula (1) indicates:
In the general formula (1), n indicates the integer of 1-4, R1, R2, R3, R4, R5, R6, R7, R8Independently of one another-H or-
CH3；
R includes structure position shown in following (a)-(e),
R includes structure position shown in following (a)-(e), specifically, R is (a), (b), (c), (d), (e) as n=1
In any one；As n > 1, R is independently of one another (a), (b), (c), (d), any one in (e).
In this example, to make the liquid crystal unit for having enough in resin system, in favor of forming liquid crystalline phase, thus it is described solid
The mass fraction of agent should be greater than the 20% of curing agent and epoxy resin gross mass.
In this example, to make solidfied material have certain crosslink density and heat resistance, epoxy resin includes at least one more officials
Energy epoxy resin, polyfunctional epoxy resin includes o-cresol formaldehyde epoxy, phenol novolac epoxy, bisphenol A-type epoxy novolac, trifunctional
Epoxy novolac, the DCPD phenol novolac epoxy, XYLOK epoxy novolac, biphenyl type epoxy novolac, three that epoxy novolac, DOPO are modified
Glycidyl triisocyanate, triglycidyl group para-aminophenol, four glycidyl group diaminodiphenylmethane, diamino
Four glycidyl amine of diphenyl ether, four glycidol ether of 1,1,2,2- tetra- (p-hydroxybenzene) ethane.
In this example, to make solidfied material have better toughness, epoxy resin is polyfunctional epoxy resin and bifunctional ring
The mixture of oxygen resin, bifunctional epoxy resin can reduce the crosslink density of solidfied material.Wherein, bifunctional epoxy resin includes
Bisphenol A type epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol f type epoxy resin, brominated epoxy resin, ethylene glycol two shrink sweet
Oily ether, tetramethyl biphenyl diphenol diglycidyl ether, 2,5 di tert butyl hydroquinone diglycidyl ether, 2,2 '-dimethyl-
One of 5,5 '--4,4 '-diglycidyl diphenylsulfides of di-t-butyl, tetramethyl Bisphenol F diglycidyl ether are more
Kind.
In this example, for the caking property and heat resistance for improving heat-conductive resin composition, curing agent further includes dicyandiamide
(DICY), one of 4,4 ' diaminodiphenylsulfones (DDS) and o-cresol-formaldehyde resin (PN) or a variety of.
In this example, to reduce solidification temperature, shortens curing time, improve curing degree, heat-conductive resin composition also wraps
Component 3: curing accelerator is included, curing accelerator includes the network of tertiary amines promotor, imidazoles promotor and borontrifluoride boron amide
Close one of object or a variety of.
For the thermal conductivity for further increasing solidfied material, heat-conductive resin composition further includes component 4: heat filling, described to lead
Hot filler includes aluminium nitride, boron nitride, aluminium oxide, magnesia, crystalline sillica, aluminium hydroxide, magnesium hydroxide, calcirm-fluoride
And one of talcum powder or a variety of.Wherein, filler of the heat filling used preferably through surface treatment, surface treating agent
It is preferred that silane coupling agent, titante coupling agent.The partial size of heat filling is between 0.1-100 μm, certainly, also may be selected two or
More than two partial size grades are compounded, to improve bulk density.
To enable filler to better disperse, and there is better interface binding power with resin, and there is better technique
Property, in this example, heat-conductive resin composition further includes dispersing agent, coupling agent, antisettling agent or solvent.Currently, dispersing agent, idol
Connection agent, antisettling agent, the type of solvent are more, and those skilled in the art can select suitable dispersing agent, idol according to actual needs
Join agent, antisettling agent, solvent, specific kind will not be described in detail herein.
There is good heating conduction to be explicitly shown the heat-conductive resin composition of the application, can be used conveniently to prepare into metal
The packaging parts such as substrate, prepreg, laminate will be specifically described below by test data.
Table 1 is the constituent table of resin combination in comparative example and embodiment.
Table 1
The composition in table 1 will be illustrated below:
Phenol novolac epoxy is multi-functional epoxy, and epoxide equivalent is 170~200g/eq, 40~60 DEG C of softening point；
Bisphenol type epoxy is difunctional epoxide, and epoxide equivalent is 430~460g/eq；
AG-80, i.e. four glycidyl group diaminodiphenylmethane are multi-functional epoxy, epoxide equivalent 135g/eq；
PN, i.e. linear phenolic resin, 105~110g/mol of hydroxyl equivalent, 104~110 DEG C of softening point；
Aluminium oxide, diameter D50For 5 μ.
The structure of curing agent A are as follows:
Wherein, R isIts
Hydroxyl equivalent 376g/mol, specific synthesis process are as follows: take the bisphenol F type epoxy 85g and 4,4- of 160~180g/eq of epoxide equivalent
'-biphenyl diphenol 93g co-dissolve adds the methylimidazole of 0.05g in ethylene glycol monomethyl ether, and 120~125 DEG C of reaction 2h are
Available, phenolic hydroxyl equivalent surveys 376g/mol.
The structure of curing agent B are as follows:
Wherein, R isIts
Hydroxyl equivalent 388g/mol, specific synthesis process are as follows: take the bisphenol type epoxy 90g and 4,4- of 175~185g/eq of epoxide equivalent
0.02g 4 bromide is added in ethylene glycol monomethyl ether in '-biphenyl diphenol 93g co-dissolve, and 70~80 DEG C of reaction 3h can be obtained
It arrives, phenolic hydroxyl equivalent surveys 386g/mol.
The structure of curing agent C are as follows:
Wherein, R isIts
Hydroxyl equivalent 573g/mol, specific synthesis process are as follows: take epoxide equivalent 350-400g/eq tetrabromobisphenol A type ring oxygen 185g and
In DMF, 150~160 DEG C of reaction 3h can be obtained 4,4- '-biphenyl diphenol 93g co-dissolves, and phenolic hydroxyl equivalent surveys 573g/
mol。
The structure of curing agent D are as follows:
Wherein, R isIts hydroxyl equivalent 376g/
Mol, specific synthesis process are as follows: take the ethylene glycol diglycidylether 65g and 3 of 125~135g/eq of epoxide equivalent, 3,5,5- tetra-
Methyl -4,4- '-biphenyl diphenol 123g co-dissolve is in ethylene glycol monomethyl ether, addition 0.03g 4 bromide, and 100~110 DEG C
Reaction 2h can be obtained, and phenolic hydroxyl equivalent surveys 376g/mol.
The structure of curing agent E are as follows:
Wherein, R is
Its hydroxyl equivalent 560g/mol, specific synthesis process are as follows: take the phosphorous epoxy of DOPO-HQ type of epoxide equivalent 360-400g/eq
In DMF, 120~130 DEG C of reaction 2h can be obtained 190g and 4,4- '-biphenyl diphenol 93g co-dissolve, and phenolic hydroxyl equivalent is real
Survey 560g/mol.
The structure of curing agent F are as follows:
Wherein, R isIts
Hydroxyl equivalent 440g/mol, specific synthesis process are as follows: take the bisphenol type epoxy 90g and 3 of 175~185g/eq of epoxide equivalent, 3,
5,5- tetramethyl -4,4- '-biphenyl diphenol 123g co-dissolves are in DMF, and 120~130 DEG C of reaction 4h can be obtained, phenolic hydroxyl group
Equivalent surveys 439g/mol.
Copper-clad plate is prepared using the resin combination of comparative example and embodiment in table 1, preparation process includes:
Firstly, prepare glue: preparing material according to the proportion of each material in comparative example and embodiment table, with solvent by ring
Oxygen resin, curing agent, promotor dissolve and are uniformly mixed to arrive packless glue.When having filler in proportion, prepare first
Then auxiliary agent is added in packless glue, filler is added after mixing, and ball milling dispersion obtains the glue containing filler.
Then, it prepares bonding sheet: impregnating 7628 glass cloth with glue, certain temperature carries out drying semi-solid preparation, bonded
Piece.
Finally, preparation copper-clad plate: 4 bonding sheet overlappings are covered with copper foil up and down, can be obtained by hot-press solidifying and cover copper
Plate, condition of cure are 180 DEG C, 30min.
The copper-clad plate prepared using the resin combination of comparative example and embodiment is tested for the property, wherein thermal conductivity
It is tested according to ASTM D5470 method, other performances are tested according to IPC TM-650 method, and table 2 is the performance test results.
Table 2
It is and right according to the performance test results in table 2 it is found that comparative example 1 and embodiment 1,3~11 are without addition filler
Ratio 1 is compared, and the resin combination of embodiment 1,3~11 has higher thermal conductivity, and comparative example 2, embodiment 2 are right respectively
The filler of equivalent is added on the basis of ratio 1, embodiment 1, thermal conductivity can all rise after adding filler.
In addition, the heat-conductive resin composition using the application can prepare other products.For example, the application also provides a kind of tree
Rouge solidfied material, heat-conductive resin composition by mentioned earlier solidify；The application also provides a kind of metal substrate, insulating layer
Heat-conductive resin composition by mentioned earlier solidifies；The application also provides a kind of prepreg, is impregnated by reinforcing material above
The heat-conductive resin composition forms；The application also provides a kind of laminate, and prepreg by mentioned earlier solidifies.
This application provides a kind of heat-conductive resin compositions, liquid crystal unit are introduced to curing agent, the liquid crystal in the application
The general structure of primitive are as follows:Its
In, R1, R2, R3, R4, R5, R6, R7, R8Independently of one another-H or-CH3.The kind heat-conductive resin composition of the application utilizes liquid
The rigid flat structure of brilliant primitive still retains regular orderly liquid crystalline phase, big gauge in system after making epoxy resin cure
Whole orderly liquid crystalline phase can be improved the thermal conductivity of heat-conductive resin composition, the electricity prepared using the application heat-conductive resin composition
Sub- encapsulating material has good thermal conductivity energy, and then meets requirement of the electronics industry to heat-radiating substrate thermal diffusivity.In addition, the application
Heat-conductive resin composition preparation process it is simple, facilitate production, be easy to be widely used to promote.
Above-described the application embodiment does not constitute the restriction to the application protection scope.
Claims (10)
1. a kind of heat-conductive resin composition characterized by comprising
Component 1: epoxy resin；
Component 2: curing agent,
Wherein, the curing agent includes the compound that the following general formula (1) indicates:
In the general formula (1), R1, R2, R3, R4, R5, R6, R7, R8Independently of one another-H or-CH3；
R includes structure position shown in following (a)-(e), and n indicates the integer of 1-4, as n=1, R is (a), (b), (c),
(d), any one in (e)；As n > 1, R is independently of one another (a), (b), (c), (d), any one in (e),
2. heat-conductive resin composition according to claim 1, which is characterized in that shown curing agent accounts for epoxy resin and solidification
The mass fraction of agent total amount is greater than 20%.
3. heat-conductive resin composition according to claim 1, which is characterized in that the epoxy resin includes at least one more
Functional epoxy resins, polyfunctional epoxy resin include o-cresol formaldehyde epoxy, phenol novolac epoxy, bisphenol A-type epoxy novolac, three officials
Epoxy novolac that can be epoxy novolac, DOPO modified, DCPD phenol novolac epoxy, XYLOK epoxy novolac, biphenyl type epoxy novolac,
Triglycidyl group triisocyanate, triglycidyl group para-aminophenol, four glycidyl group diaminodiphenylmethane, diamino
Four glycidyl amine of base diphenyl ether, four glycidol ether of 1,1,2,2- tetra- (p-hydroxybenzene) ethane.
4. heat-conductive resin composition according to claim 1, which is characterized in that the epoxy resin is multi-functional epoxy tree
The mixture of rouge and bifunctional epoxy resin, wherein bifunctional epoxy resin includes bisphenol A type epoxy resin, hydrogenated bisphenol A ring
Oxygen resin, bisphenol f type epoxy resin, brominated epoxy resin, ethylene glycol diglycidylether, tetramethyl biphenyl diphenol two shrink sweet
Oily ether, 2,5 di tert butyl hydroquinone diglycidyl ether, 2,2 '--5,5 '-di-t-butyls -4,4 of dimethyl '-two shrinks are sweet
One of oleyl diphenyl thioether, tetramethyl Bisphenol F diglycidyl ether are a variety of.
5. heat-conductive resin composition according to claim 1, which is characterized in that the curing agent further include DICY, DDS with
And one of PN or a variety of.
6. heat-conductive resin composition according to claim 1, which is characterized in that the heat-conductive resin composition further includes group
Part 3: curing accelerator, the curing accelerator include the network of tertiary amines promotor, imidazoles promotor and borontrifluoride boron amide
Close one of object or a variety of.
7. heat-conductive resin composition according to claim 1, which is characterized in that the heat-conductive resin composition further includes group
Part 4: heat filling, the heat filling include aluminium nitride, boron nitride, aluminium oxide, magnesia, crystalline sillica, hydrogen-oxygen
Change one of aluminium, magnesium hydroxide, calcirm-fluoride and talcum powder or a variety of.
8. heat-conductive resin composition according to claim 1, which is characterized in that the heat-conductive resin composition further includes point
Powder, coupling agent, antisettling agent or solvent.
9. heat-conductive resin composition according to claim 7, which is characterized in that the partial size D of the heat filling50Between
0.1-100μm。
10. prepreg, laminate, copper-clad plate, gold based on the described in any item resin combination preparations of the claims 1-9
Belong to substrate, circuit board.
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| CN115725053A (en) * | 2022-11-24 | 2023-03-03 | 深圳市郎搏万先进材料有限公司 | Epoxy resin composition, reinforced fiber prepreg and reinforced fiber composite material |
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