CN101974208B - High thermal conductivity resin composition and high thermal conductivity coated metal foil board manufactured by using same - Google Patents
High thermal conductivity resin composition and high thermal conductivity coated metal foil board manufactured by using same Download PDFInfo
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- CN101974208B CN101974208B CN2010102615093A CN201010261509A CN101974208B CN 101974208 B CN101974208 B CN 101974208B CN 2010102615093 A CN2010102615093 A CN 2010102615093A CN 201010261509 A CN201010261509 A CN 201010261509A CN 101974208 B CN101974208 B CN 101974208B
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Abstract
The invention relates to a high thermal conductivity resin composition and a high thermal conductivity coated metal foil board manufactured by using the same. The high thermal conductivity resin composition comprises the following components of: epoxy resin, at least one phenoxy resin or carboxy terminal butadiene acrylonitrile, biphenyl phenolic resin and a high thermal conductivity packing material, wherein the biphenyl phenolic resin has the structure shown in the specification. The high thermal conductivity coated metal foil board manufactured by using the high thermal conductivity resin composition comprises a high thermal conductivity adhesive film and metal foils coated on both sides of the high thermal conductivity adhesive film, wherein the high thermal conductivity adhesive film comprises a carrier film and the high thermal conductivity resin composition coated on the carrier film, and the carrier film is a polyester film or a polyimide film. The high thermal conductivity coated metal foil board comprises a resin composite metal foil and a metal foil or another resin composite metal foil coated on the previous resin composite metal foil, and the resin composite metal foil comprises a metal foil and the high thermal conductivity resin composition coated on the metal foil.
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of highly thermal-conductive resin composition and use the high heat conduction clad with metal foil plate of its making.
Background technology
Along with electronic product to light, thin, short, little, densification, the direction of multifunction develops, the packing density and the integrated level of elements on circuit board are increasingly high, require also more and more urgent to the thermal diffusivity of substrate.Traditional circuit card is textural, because the electronic package quantity and the consumed power that plug on it are less, the heat that electronic package produces can be through the heat radiation of the copper foil layer on the circuit card; Directly heat is dispelled the heat to air, utilize the convection current of air that electronic package is carried out temperature control, current circuit card; Electronic package power is high though no, and quantity is many, and incident problem is that the electric power that is consumed increases; Cause on local power consumption components, producing a large amount of heat; And circuit card can not scatter and disappear away these heats timely, thereby whole aircraft reliability is descended, and under this background, has produced multiple solution.
Wherein a kind of circuit card heat dissipation technology of widely being known is to utilize an insulating radiation tack coat and heat-dissipating metal sheet (like aluminium sheet, copper coin) to carry out pressing, the heat of utilizing the metal better heat radiating effect to be produced with the runaway electron assembly single or multiple lift PC board.This insulating radiation layer also must provide good insulation performance performance, heat dispersion except that metal substrate and copper-foil conducting electricity bonding is provided.This insulation layer can adopt the slim material of common FR-4 (woven fiber glass enhanced epoxy resin), but because the thermal conductivity of FR-4 is not high, be merely 0.25W/M.K, thereby radiating effect is limited.
In general, highly heat-conductive material selects for use the good epoxy resin of binding property as matrix, for epoxide resin material and the solidifying agent that is used thereof; Promotor, heat conductive filler needs its each components contents of adjustment just can reach good effect; Otherwise the easy generation of the heat radiation film of processing is peeled off and thermotolerance is not good, and the generation of the problems referred to above is mainly improper owing to the selection of solidifying agent, for example; Adopt Dyhard RU 100 (DICY) to make solidifying agent,, cause significantly reduction of cross-linked resin composition quilt in the relative unit owing in resin, added a large amount of mineral fillers; Make the heat radiation film thermotolerance of making not high, the thermotolerance of sheet material is poor, and anti-ion transport is poor; Water-intake rate is prone to produce the layering plate bursting than higher simultaneously.If adopt linear phenol type resol or face the bigger curing agent component of fragility such as cresols type resol, can cause made heat radiation film toughness variation, adhesiveproperties is not good, so be not suitable for the making as the heat radiation film.For these reasons, patent CN101613517 has disclosed a kind of novel solidifying agent, and the molecular formula of this solidifying agent is as follows:
This patent adopts the matrix of this solidifying agent cured epoxy resin as highly heat-conductive material; Though though this solidifying agent makes moderate progress for improving thermotolerance and binding property; But the consistency of this solidifying agent and epoxy resin is bad; In use separate out easily, use characteristics is poor, and especially this performance is more outstanding in the filler systems that height is filled.Patent CN101343402 then discloses a kind of method of high heat conduction prepreg; But in the used resin system because lack the flexible composition; So prepared no glass enhanced conductive adhesive film poor in flexibility, especially after filling a large amount of heat conductive fillers, fragility is very big; In use damaged easily cracked, do not have good processibility.And special to open the flat prepared high-heat-conductivity glue film of JP 2003-140047 be to be matrix resin with (methyl) acrylic compounds; Fill heat conductive fillers such as aluminum oxide; Though the glued membrane snappiness of this method preparation is good; But second-order transition temperature is then too low, is-65 ℃, is not suitable for the application of highly heat-conductive copper-clad plate.And phenomenons such as the high-heat-conductivity glue film of existing preparation often exists thermotolerance not high, and snappiness is not enough, and is not strong with the binding property of Copper Foil, and thermal conductivity is on the low side.
Summary of the invention
The object of the present invention is to provide a kind of highly thermal-conductive resin composition; Has excellent high thermal conductivity, good thermotolerance, flame retardant resistance, snappiness and binding property, and processing characteristics; Good snappiness and tensile strength by the high-heat-conductivity glue film of its making can be provided, satisfy high heat conduction demand.
Another object of the present invention is to, a kind of high heat conduction clad with metal foil plate that uses above-mentioned highly thermal-conductive resin composition to make is provided, have high thermal conductivity, good performances such as anti-immersed solder property.
For realizing above-mentioned purpose, the present invention provides a kind of highly thermal-conductive resin composition, comprises the biphenyl type resol with following structure:
This highly thermal-conductive resin composition comprises component and weight percent thereof (calculating by the component total weight percent) as follows: epoxy resin 5-40%, at least a phenoxy resin or nbr carboxyl terminal 5-35%, biphenyl type resol 2-35%, reach high heat conductive filler 10-90%.
Said epoxy resin is at least a epoxy resin shown in the following general structure that has:
R wherein
1Represent Wasserstoffatoms, halogen atom or phenyl, n represents the integer of 0-20, and X is-CH
2-,-O-,-CO-,-SO
2-,-S-,-CH (C
6H
5)-, C (C
6H
5)
2-, CH (CH
3), C (CH
3)
2Or chemical formula
R wherein
2Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents the integer of 0-20;
R wherein
3Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents the integer of 0-20;
R wherein
4Represent Wasserstoffatoms, halogen atom or phenyl, m represents the integer of 0-20;
R wherein
5Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents the integer of 0-20.
Said epoxy resin is the epoxy resin, glycidyl amine type epoxy resin, glycolylurea epoxide resin of the epoxy resin, brominated epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, phenol-phenolic epoxy, ortho-cresol-phenolic aldehyde property epoxy, dihydroxyphenyl propane-phenolic epoxy, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin and cyclopentadiene or two cyclic diolefines and phenols condensation resin, isocyanate-modified epoxy resin, nbr carboxyl terminal modification, through terpene modified epoxy resin, 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin, 10-(2; The 5-dihydroxy phenyl)-9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin or 10-(2; 9-dihydroxyl naphthyl)-9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin one or more.
Said high heat conductive filler is selected from one or more in metal nitride, MOX, carbide or the diamond; Wherein, Metal nitride is aluminium nitride AlN, SP 1 or silicon nitride, and MOX is aluminum oxide, Natural manganese dioxide or beryllium oxide, and carbide is silit or norbide.
Said high heat conductive filler carries out surface treatment through coupling agent, and coupling agent is silane coupling agent or titanic acid ester ester class coupling agent.
Also comprise curing catalyst; This curing catalyst is selected from three second class amine and its esters, quaternary ammonium compound salt compound, 2; 4, one or more in 6-three (dimethylin methylamine) phenol, benzyldimethylamine, imidazoles, three amylic phenol acid amides, list or polyphenolic substance, boron trifluoride and organic title complex, phosphoric acid or the triphenyl phosphite.
Also comprise cyanate ester resin or bismaleimides quasi-polyimide resin, its consumption accounts for the 0-40% of composition solid component total weight percent.
Simultaneously; A kind of high heat conduction clad with metal foil plate that uses above-mentioned highly thermal-conductive resin composition to make also is provided, comprises the high-heat-conductivity glue film and be laminated with in the tinsel of these high-heat-conductivity glue film both sides, said high-heat-conductivity glue film comprises carrier film and is coated on the high thermal grease conduction compsn on this carrier film; Carrier film is polyester film or polyimide film; Thickness is 5-150 μ m, and tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m.
A kind of high heat conduction clad with metal foil plate that uses above-mentioned highly thermal-conductive resin composition to make also is provided; Comprise a resin laminated metal paper tinsel and be laminated with a tinsel or another resin laminated metal paper tinsel on this resin laminated metal paper tinsel; Said resin laminated metal paper tinsel comprises a tinsel, is coated on the highly thermal-conductive resin composition on this tinsel; Wherein tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m.
Beneficial effect of the present invention: highly thermal-conductive resin composition highly thermal-conductive resin composition of the present invention; Having adopted biphenyl type resol is solidifying agent; Make this highly thermal-conductive resin composition have excellent high thermal conductivity, good thermotolerance, flame retardant resistance, snappiness and binding property, and processing characteristics; Good snappiness and tensile strength by the high-heat-conductivity glue film of its making can be provided, satisfy high heat conduction demand.High heat conduction clad with metal foil plate with this highly thermal-conductive resin composition is made has high thermal conductivity, good performances such as anti-immersed solder property.
Embodiment
Highly thermal-conductive resin composition of the present invention comprises component and weight percent thereof (calculating by the component total weight percent) as follows: epoxy resin 5-40%, at least a phenoxy resin or nbr carboxyl terminal 5-35%, biphenyl type resol 2-35%, reach high heat conductive filler 10-90%.
Said epoxy resin is meant the epoxy resin that in 1 molecule resin, has 2 or 2 above epoxide groups, and epoxy resin can be at least a epoxy resin shown in the following general structure that has:
R wherein
1Represent Wasserstoffatoms, halogen atom or phenyl, n represents the integer of 0-20, and X is-CH
2-,-O-,-CO-,-SO
2-,-S-,-CH (C
6H
5)-, C (C
6H
5)
2-, CH (CH
3), C (CH
3)
2Or chemical formula
R wherein
2Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer;
R wherein
3Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer;
R wherein
4Represent Wasserstoffatoms, halogen atom or phenyl, m represents the integer of 0-20;
R wherein
5Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
Said epoxy resin can be the epoxy resin, glycidyl amine type epoxy resin, glycolylurea epoxide resin of the epoxy resin, brominated epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, phenol-phenolic epoxy (being called for short PNE), ortho-cresol-phenolic aldehyde property epoxy (being called for short PNE), dihydroxyphenyl propane-phenolic epoxy (being called for short BNE), Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin and cyclopentadiene or two cyclic diolefines and phenols condensation resin, isocyanate-modified epoxy resin, nbr carboxyl terminal modification, through terpene modified epoxy resin, 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO) modified epoxy, 10-(2; The 5-dihydroxy phenyl)-9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO-HQ) modified epoxy or 10-(2; 9-dihydroxyl naphthyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO-NQ) modified epoxy.Above epoxy resin can use separately or several kinds of mixing are used.According to the present invention, said epoxy resin also can be with one or more mix to use in other resin, for example PPO (ppe), cyanate etc., but be not limited to these.
Said at least a phenoxy resin or nbr carboxyl terminal, this resin Composition can provide resin system good toughness, but its add-on needs certain regulation.Add the thermotolerance that too much can sharply reduce highly thermal-conductive resin composition, add the very few toughness reinforcing purpose that do not reach again.
In addition, can also comprise vibrin, vinyl resin, phenoxy resin, paracril; Contain the paracril of holding carboxyl, polyolefine, PS, polymeric amide, vinyl halides base resin; Polyacetal, saturated polyester, polycarbonate, polyene propyl group sulfone; Polyene propyl group ketone gathers (diphenyl sulfide) or PPSS, polyarylester, and liquid crystal polyester or fluoro-resin etc. can increase the flexible composition.Do not influencing the stable on heating while of compsn, said components can be used with phenoxy resin or nbr carboxyl terminal.
Among the present invention, biphenyl type resol is as solidifying agent.As everyone knows, it is with the amine curing agent of dicyandiamide as representative that thermally conductive material uses more, and when using Ammonia to make solidifying agent, though good snappiness can be provided, the thermotolerance of sheet material is poor, and anti-ion transport is poor, and water-intake rate is than higher simultaneously.And phenolic solidifying agent curing back material is general more crisp; Seldom as the solidifying agent of thermally conductive material; But through discovering of inventor, use biphenyl type resol or naphthalene type resol but can well provide the snappiness of material, and adhesiveproperties is fine.
Biphenyl type resol is the biphenyl type resol with following structure:
Wherein ,-CH
2Belong to flexible group, the snappiness of molecular chain and the rotation of main chain be provided in cured article,
Be a kind of rigid radical, higher thermotolerance is provided ,-OH is the response type group, is used for the curing of epoxy resin.Because of having stronger polarity, therefore, the compsn of this kind solidifying agent can be bonding with metal substrate or tinsel well, and higher stripping strength is arranged.And, what deserves to be mentioned is, adopt the resin combination of this solidifying agent to have higher thermal conductivity.
Highly thermal-conductive resin composition of the present invention; The polymkeric substance glue that utilizes epoxy resin and above-mentioned solidifying agent to form; Have concurrently high heat resistance, high thermal conductivity, good snappiness, and and metal substrate to have well be cohesiveness; Can be used as high heat conduction printed substrate the heat conductive insulating layer, thereby make high heat conduction printed substrate can the heat dissipation rapidly that electronic component produces be gone out, to promote the safety and the life-span of PC board and electronic devices and components.
Said high heat conductive filler is used for improving the needed thermal conductivity of thermally conductive material; This high heat conductive filler accounts for the 10-90% of composition component total weight percent; High heat conductive filler is mainly ceramic packing, is selected from metal nitride, MOX, carbide or the diamond one or more.Wherein, metal nitride is aluminium nitride AlN, SP 1 or silicon nitride, and MOX is aluminum oxide, Natural manganese dioxide or beryllium oxide, and carbide is silit or norbide, and they exist with the form that is dispersed in the resin combination under the effect of dispersion agent.In addition, combine in order to make the good infiltration of high heat conductive filler and matrix resin, can use coupling agent that filler is carried out surface treatment, coupling agent can use silane coupling agent, or titanic acid ester ester class coupling agent or the like.
Said highly thermal-conductive resin composition also comprises curing catalyst; This curing catalyst is selected from three second class amine and its esters, quaternary ammonium compound salt compound, 2; 4,6-three (dimethylin methylamine) phenol, benzyldimethylamine, imidazoles is (as 2; The 4-imidazoles; Glyoxal ethyline, 2-phenylimidazole, 1 benzyl 2 methyl imidazole), in three amylic phenol acid amides, list or polyphenolic substance, boron trifluoride and organic title complex, phosphoric acid or the triphenyl phosphite one or more, but be preferably tertiary amine, imidazoles or its mixture.
In order to improve the second-order transition temperature of highly thermal-conductive resin composition of the present invention, also can in said components, further add cyanate ester resin or bismaleimides quasi-polyimide resin, it accounts for the 0-40% of composition solid component total weight percent.
In addition, this highly thermal-conductive resin composition also can add flow agent, dispersion agent, and tinting material, thinner, inhibitor, heat and photostabilizer, fire retardant, auxiliary agents such as pigment or dyestuff improve performance.Wherein auxiliary agent accounts for the 0-10% of solid ingredient total weight percent in the component.
The high-heat-conductivity glue film that uses highly thermal-conductive resin composition of the present invention to make; Its making method is listed below; But its preparation method is not limited thereto: highly thermal-conductive resin composition is coated on the carrier film, and carrier film is polyester film or polyimide film, and thickness is 5-150 μ m; Heated 10 seconds-30 minutes down at 100-250 ℃ then, form sheet material, the thickness of formed high-heat-conductivity glue film is 5-500 μ m.The high-heat-conductivity glue film that this highly thermal-conductive resin composition is made has good tensile, snappiness and thermotolerance.
The resin laminated metal paper tinsel that uses highly thermal-conductive resin composition of the present invention to make; Its making method is listed below; Yet the method for preparing resin composition metal Copper Foil is not limited only to this: through manual or mechanical roll-on device described highly thermal-conductive resin composition glue is coated on the tinsel; Tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m; Then this tinsel that is coated with highly thermal-conductive resin composition is carried out heat drying; Make highly thermal-conductive resin composition be in semi-cured state (B-Stage); The Heating temperature here is 100-250 ℃; Be 10 seconds-30 minutes heat-up time, and the resin layer thickness of the resin laminated metal paper tinsel that forms at last is 5-500 μ m.
In addition; Highly thermal-conductive resin composition of the present invention also can be used for processing high heat conduction prepreg (prepreg) through the impregnation mode; The method of this high heat conduction prepreg (prepreg) is listed below; Yet the method for making prepreg is not limited only to this: highly thermal-conductive resin composition glue (having used solvent adjustment viscosity here) is immersed on the base-material, forms preliminary-dip piece, and the preliminary-dip piece that is impregnated with highly thermal-conductive resin composition is carried out heat drying; Make the highly thermal-conductive resin composition in the preliminary-dip piece be in the semicure stage (B-Stage), can obtain prepreg.The base-material that wherein uses can be inorganic or organic materials.Inorganic materials is woven fabric or the non-woven fabrics or the paper of spun glass, thomel, boron fibre, metal etc., and glasscloth wherein or non-woven fabrics can be E-glass, Q type cloth, NE cloth, D type cloth, S type cloth, high silica cloth etc.Organic materials is weaving cotton cloth or non-woven fabrics or paper of manufacturings such as polyester, polyamine, ROHM, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene.Yet base-material is not limited thereto.As a kind of selectivity embodiment, the Heating temperature of preliminary-dip piece can be 80-250 ℃, the time is 1-30 minute.The content of the highly thermal-conductive resin composition in the prepreg is 25-90%.
The high-heat-conductivity glue film, resin laminated metal paper tinsel or the prepreg that use highly thermal-conductive resin composition of the present invention to make; Be applicable as the heat conductive insulating layer of printed substrate; Make printed substrate have the characteristic of high heat conduction; Help the quick dissipation of heat that produced when the electronic component on the printed substrate operated, to promote the work-ing life and the stability of electronic component.
Further; The present invention also provides a kind of high heat conduction clad with metal foil plate that uses above-mentioned highly thermal-conductive resin composition to make; It comprises the high-heat-conductivity glue film and is laminated with in the tinsel of these high-heat-conductivity glue film both sides; Said high-heat-conductivity glue film comprises carrier film and is coated on the high thermal grease conduction compsn on this carrier film, and said carrier film is polyester film or polyimide film, and thickness is 5-150 μ m; Tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m.
The present invention provides the another kind of high heat conduction clad with metal foil plate that uses above-mentioned highly thermal-conductive resin composition to make; It comprises a resin laminated metal paper tinsel and is laminated with a tinsel or another resin laminated metal paper tinsel on this resin laminated metal paper tinsel; Said resin laminated metal paper tinsel comprises a tinsel, is coated on the highly thermal-conductive resin composition on this tinsel; Wherein tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m.When said this high heat conduction clad with metal foil plate comprised a resin laminated metal paper tinsel and is laminated with the tinsel on this resin laminated metal paper tinsel, this tinsel was laminated with in this resin laminated metal paper tinsel and is coated with on the one side of highly thermal-conductive resin composition; When this high heat conduction clad with metal foil plate comprised two resin laminated metal paper tinsels, this two resin laminated metals paper tinsel was laminated with along the one side that it is coated with highly thermal-conductive resin composition mutually.
Now the embodiment of the invention is specified as follows, but the present invention is confined to scope of embodiments.Making highly heat-conductive copper-clad plate with highly thermal-conductive resin composition and Copper Foil in embodiments of the present invention is that example describes.
Embodiment 1:
In a clean container, add following resin successively: brominated epoxy resin 100g, and then add nbr carboxyl terminal 253g, earlier with above-mentioned resin stir about 30min; After mixing; Add biphenyl type phenolic resin curative (admittedly containing 50%) 92.2g again, and curing catalyst 2-MI 0.05g, obtain virgin resin glue (is 40% admittedly contain) after continuing to mix 1h; Be coated with this glue then, the coating carrier adopts the thick Copper Foil of 35 μ m.In 110 ℃ of baking ovens, dry by the fire sheet 1.5min after coating is accomplished and carry out semicure, form resin composite copper foil, get two resin composite copper foils that make then and close folded with its glue surface plaster, at 190 ℃, 90min carries out the high temperature pressing, promptly gets highly heat-conductive copper-clad plate.
Embodiment 2:
In a clean container, add 40g solvent MC, add the 113g aluminum oxide then, continue stir about half a hour, add the glue that is disposed among the 50g embodiment 1, continue to stir half a hour, disperse through high-shear emulsion machine then, jitter time is 0.5 hour.Be coated with after being uniformly dispersed, the coating carrier adopts the thick Copper Foil of 35 μ m.In 110 ℃ of baking ovens, dry by the fire sheet 1.5min after coating is accomplished and carry out semicure, form resin composite copper foil, get two resin composite copper foils that make then and close folded with its glue surface plaster, at 190 ℃, 90min carries out the high temperature pressing, promptly gets highly heat-conductive copper-clad plate.
Embodiment 3:
In a clean container, add 48g solvent MC, add the 90g aluminum oxide then, continue stir about 10min; And then adding 23g SP 1; After continuing to stir 10min, add the glue that is disposed among the 50g embodiment 1, continue to stir half a hour; Disperse through high-shear emulsion machine then, jitter time is 0.5 hour.Be coated with after being uniformly dispersed.The coating carrier adopts the thick Copper Foil of 35 μ m.In 110 ℃ of baking ovens, dry by the fire sheet 1.5min after coating is accomplished and carry out semicure, form resin composite copper foil, get two resin composite copper foils that make then and close folded with its glue surface plaster, at 190 ℃, 90min carries out the high temperature pressing, promptly gets highly heat-conductive copper-clad plate.
Comparative example 1:
In a clean container, add following resin successively: brominated epoxy resin 100g, and then add nbr carboxyl terminal 253g, earlier with above-mentioned resin stir about 30min; After mixing, add good DICY (Dyhard RU 100) solidifying agent of DMF (N, dinethylformamide) dissolving; The Dyhard RU 100 consumption is 3.1g; Promotor 0.05g obtains the virgin resin glue after continuing to mix 1h, is coated with this glue then.The coating carrier adopts the thick Copper Foil of 35 μ m.In 110 ℃ of baking ovens, dry by the fire sheet 1.5min after coating is accomplished and carry out semicure, form resin composite copper foil, get two resin composite copper foils that make then and close folded with its glue surface plaster, at 190 ℃, 90min carries out the high temperature pressing, promptly gets highly heat-conductive copper-clad plate.
Comparative example 2:
In a clean container, add 40g solvent MEK, add the 113g aluminum oxide then, continue stir about half a hour, add the glue that is disposed in the 50g comparative example 1, continue to stir half a hour, disperse through high-shear emulsion machine then, jitter time is 0.5 hour.Be coated with after being uniformly dispersed.The coating carrier adopts the thick Copper Foil of 35 μ m.In 110 ℃ of baking ovens, dry by the fire sheet 1.5min after coating is accomplished and carry out semicure, form resin composite copper foil, get two resin composite copper foils that make then and close folded with its glue surface plaster, at 190 ℃, 90min carries out the high temperature pressing, promptly gets highly heat-conductive copper-clad plate.
Comparative example 3:
In a clean container, add 48g solvent MEK, add the 90g aluminum oxide then, stir about 10min; And then adding 23g SP 1; After continuing to stir 10min, add the glue that is disposed in the 50g comparative example 1, continue to stir half a hour; Disperse through high-shear emulsion machine then, jitter time is 0.5 hour.Be coated with after being uniformly dispersed.The coating carrier adopts the thick Copper Foil of 35 μ m.In 110 ℃ of baking ovens, dry by the fire sheet 1.5min after coating is accomplished and carry out semicure, form resin composite copper foil, get two resin composite copper foils that make then and close folded with its glue surface plaster, at 190 ℃, 90min carries out the high temperature pressing, promptly gets highly heat-conductive copper-clad plate.
The performance of the prescription of each embodiment of table 1. and comparative example and the highly heat-conductive copper-clad plate of preparation
| Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Brominated epoxy resin | g | 100 | 11 | 11 | 100 | 11 | 11 |
| Toughened resin | g | 253 | 28 | 28 | 253 | 28 | 28 |
| Aluminum oxide | g | 0 | 113 | 90 | 0 | 113 | 90 |
| SP 1 | g | 0 | 0 | 23 | 0 | 0 | 23 |
| The xenol urea formaldehyde | g | 92.2 | 10.2 | 10.2 | 0 | 0 | 0 |
| DICY | g | 0 | 0 | 0 | 3.1 | 0.35 | 0.35 |
| 2-MI | g | 0.05 | 0.005 | 0.005 | 0.05 | 0.05 | 0.05 |
| Tg(DMA) | ℃ | 156 | 162 | 165 | 142 | 151 | 153 |
| PS | N/mm | 2.67 | 1.4 | 1.2 | 1.69 | 1.02 | 0.8 |
| Thermal conductivity | W/M·K | 0.5 | 1.85 | 2.6 | 0.25 | 1.45 | 1.90 |
| Incendivity | UL-94 | V-O | V-O | V-O | V-O | V-O | V-O |
| Anti-immersed solder property | min | ＞5 | ＞5 | ＞5 | 3.5 | 2 | 1.5 |
| Screen resilience | N/15mm | 92 | 110 | 130 | 104.5 | 123 | Fracture |
| Tensile modulus/warp-wise | MPa | 1874.4 | 1532.6 | 1328.6 | 1808.2 | 1439.8 | 1109.5 |
| Unit elongation | ％ | 7.5 | 6.8 | 6.2 | 6.4 | 5.0 | 4.8 |
More than each embodiment and comparative example all copper-clad plate is detected according to the IPC4101 standard, detection method is following:
1, second-order transition temperature (Tg): according to dynamic thermomechanical analysis (DMA).
2, thermal conductivity test (λ): adopt ASTM D5470 standard method test.
3, stripping strength (PS): test condition is for receiving attitude.
4, incendivity: adopt the UL-94 testing standard.
5, anti-immersed solder property: in the fusion scolding tin that the entering of fingerboard material is 288 ℃, no layering and the time of bubbling and being continued.
6, screen resilience: being used for characterizing the snappiness of prepared cured article, is to bend to certain degree to sample, keeps surveying its screen resilience behind the 30s, and screen resilience is more little, and then flexibility is good more.
Can find out from the data of table 1; Having adopted biphenyl type resol or naphthalene type resol among the embodiments of the invention 1-3 is solidifying agent; Compare as solidifying agent with adopting Dyhard RU 100 (DICY) among the comparative example 1-3, the prepared highly heat-conductive copper-clad plate of embodiment 1-3 has very high stripping strength.Owing to the biphenyl type structure is arranged in the solidifying agent, so the thermal conductivity of the high-heat-conductivity glue film of gained also is about the twice of DICY solidified glue film, and well-known, it is more obvious to the thermal conductivity influence of compsn that the thermal conductivity of resin is compared filler.Therefore, this glued membrane for the preparation higher heat-conductivity provides prerequisite.The high-heat-conductivity glue film of gained also has good snappiness and tensile strength simultaneously; Because the cohesiveness of resin itself is good; Therefore, under high heat conductive filler is filled, even if stripping strength reduces; Also have good cohesiveness, and have good thermotolerance, processing characteristics and excellent flame-retardant performance simultaneously than DICY solidified glued membrane.As adopt composite filled mode, and can further improve its thermal conductivity, can satisfy the demand of high heat conduction.
In sum; Highly thermal-conductive resin composition highly thermal-conductive resin composition of the present invention, having adopted biphenyl type resol is solidifying agent, makes this highly thermal-conductive resin composition have excellent high thermal conductivity; Good thermotolerance, flame retardant resistance, snappiness and binding property; And processing characteristics can provide good snappiness and tensile strength by the high-heat-conductivity glue film of its making, satisfies high heat conduction demand.High heat conduction clad with metal foil plate with this highly thermal-conductive resin composition is made has high thermal conductivity, good performances such as anti-immersed solder property.
Above embodiment; Be not that the content of compsn of the present invention is done any restriction; Every foundation technical spirit of the present invention or compsn composition or content all still belong in the scope of technical scheme of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (6)
1. highly thermal-conductive resin composition; It is characterized in that; Comprise that component and weight percent thereof are following: epoxy resin 5-40%, at least a phenoxy resin or nbr carboxyl terminal 5-35%, biphenyl type resol 2-35%, and high heat conductive filler 10-90%, said biphenyl type resol is the biphenyl type resol with following structure:
Said epoxy resin is at least a epoxy resin shown in the following general structure that has:
R wherein
1Represent Wasserstoffatoms, halogen atom or phenyl, n represents the integer of 0-20, and X is-CH
2-,-O-,-CO-,-SO
2-,-S-,-CH (C
6H
5)-, C (C
6H
5)
2-, CH (CH
3), C (CH
3)
2Or chemical formula
R wherein
2Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents the integer of 0-20;
(Ⅲ)：
R wherein
3Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents the integer of 0-20;
R wherein
4Represent Wasserstoffatoms, halogen atom or phenyl, n represents the integer of 0-20;
R wherein
5Represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, the alkoxyl group or the phenyl of a 1-10 carbon atom, n represents the integer of 0-20;
Said epoxy resin is the epoxy resin, glycidyl amine type epoxy resin, glycolylurea epoxide resin of the epoxy resin, brominated epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, phenol-phenol aldehyde type epoxy resin, ortho-cresol-phenol aldehyde type epoxy resin, dihydroxyphenyl propane-phenol aldehyde type epoxy resin, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin and cyclopentadiene or two cyclic diolefines and phenols condensation resin, isocyanate-modified epoxy resin, nbr carboxyl terminal modification, through terpene modified epoxy resin, 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin, 10-(2; The 5-dihydroxy phenyl)-9; The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin or 10-(2; 9-dihydroxyl naphthyl)-9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin one or more;
Said high heat conductive filler is selected from one or more in metal nitride, MOX, carbide or the diamond; Wherein, Metal nitride is aluminium nitride AlN, SP 1 or silicon nitride, and MOX is aluminum oxide, Natural manganese dioxide or beryllium oxide, and carbide is silit or norbide.
2. highly thermal-conductive resin composition as claimed in claim 1 is characterized in that, said high heat conductive filler carries out surface treatment through coupling agent, and coupling agent is silane coupling agent or titanic acid ester ester class coupling agent.
3. highly thermal-conductive resin composition as claimed in claim 1; It is characterized in that; Also comprise curing catalyst; This curing catalyst is selected from tertiary amine and its esters, quaternary ammonium compound salt compound, 2,4, one or more in 6-three (dimethylin methylamine) phenol, benzyldimethylamine, imidazoles, three amylic phenol acid amides, list or polyphenolic substance, boron trifluoride and organic title complex, phosphoric acid or the triphenyl phosphite.
4. highly thermal-conductive resin composition as claimed in claim 1 is characterized in that, also comprises cyanate ester resin or bismaleimides quasi-polyimide resin, and its consumption accounts for the 0-40% of composition solid component total weight percent.
5. high heat conduction clad with metal foil plate that uses highly thermal-conductive resin composition as claimed in claim 1 to make; It is characterized in that; Comprise the high-heat-conductivity glue film and be laminated with in the tinsel of these high-heat-conductivity glue film both sides; Said high-heat-conductivity glue film comprises carrier film and is coated on the highly thermal-conductive resin composition on this carrier film, and carrier film is polyester film or polyimide film, and thickness is 5-150 μ m; Tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m.
6. high heat conduction clad with metal foil plate that uses highly thermal-conductive resin composition as claimed in claim 1 to make; It is characterized in that; Comprise a resin laminated metal paper tinsel and be laminated with a tinsel or another resin laminated metal paper tinsel on this resin laminated metal paper tinsel; Said resin laminated metal paper tinsel comprises a tinsel, is coated on the highly thermal-conductive resin composition on this tinsel; Wherein tinsel is the alloy or the composite metallic material of copper, brass, aluminium, nickel or those metals, and its thickness is 5-500 μ m.
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