CN102850726A - Composite material, high frequency circuit substrate produced by using composite material, and production method of high frequency circuit substrate - Google Patents
Composite material, high frequency circuit substrate produced by using composite material, and production method of high frequency circuit substrate Download PDFInfo
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- CN102850726A CN102850726A CN2012103300333A CN201210330033A CN102850726A CN 102850726 A CN102850726 A CN 102850726A CN 2012103300333 A CN2012103300333 A CN 2012103300333A CN 201210330033 A CN201210330033 A CN 201210330033A CN 102850726 A CN102850726 A CN 102850726A
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Abstract
The present invention relates to a composite material, a high frequency circuit substrate produced by using the composite material, and a production method of the high frequency circuit substrate. The composite material comprises the following components, by volume, 10-90% of a polyetherimide reinforcing material and 10-90% of a thermosetting resin composition. The high frequency circuit substrate produced by using the composite material comprises: multiple layers of mutually superposed prepregs and copper foils pressed and covered on one side or on both sides of the superposed prepregs, wherein at least one of the multiple layers of the mutually superposed prepregs is made from the composite material. According to the composite material of the present invention, the polyetherimide reinforcing material is adopted so as to provide characteristics of low dielectric constant, low dielectric loss angle tangent, high heat resistance and good process workability; and the composite material is suitable for high frequency high speed printed wiring board fields. The high frequency circuit substrate produced by using the composite material in the present invention has characteristics of low dielectric constant, good heat resistance and good fire retardation.
Description
Technical field
The present invention relates to a kind of matrix material, with high-frequency circuit board of its making and preparation method thereof, relate in particular to a kind of thermoset ting resin composite, with high-frequency circuit board of its making and preparation method thereof.
Background technology
In recent years, along with the development of information technology, communication equipment is more and more obvious towards the development of high performance, multifunction and networking, and the frequency of electronic signal transmission is more and more higher.In order to realize high-speed transfer and to process large capacity information, high frequencyization has been an irresistible trend, the frequency of utilization of electronic product constantly raises, and requires more and more highlyer for the dielectric characteristics as the baseplate material of wiring board, and main manifestations is low specific inductivity and Dielectric loss tangent value.
At present, do a large amount of technical works for the low-k and the Dielectric loss tangent value that realize high-frequency circuit board, mainly comprised two aspects of resin and strongthener.At first, the most common with epoxy as the resin of circuit substrate, because it has good thermotolerance, manufacturability and cohesiveness, but its specific inductivity is higher, has limited its use on high-frequency circuit board.The resins such as cyanate, polyphenylene oxide, bismaleimides, polyimide, tetrafluoroethylene are superior more a lot of than Resins, epoxy aspect dielectric properties, but because the thermotolerance of cyanate is relatively poor, often needing to carry out modification could use, and this has also just sacrificed the dielectric properties of itself excellence greatly.Polyphenylene oxide resin itself has good thermotolerance and joint behavior, but because its molecular weight is too large, causes its technique poor and can't obtain good application always; Tetrafluoroethylene itself has dielectric properties best in the current material, but because it belongs to thermoplastic material, second-order transition temperature itself is too low, cause course of processing difficulty, because the chemical resistant properties of itself is strong, causes follow-up wiring board processing difficulties in addition.The strongthener aspect, what be most widely used in circuit substrate at present is electronic-grade glass fiber cloth, it has good reinforced effects, thermotolerance and chemical resistant properties, but owing to itself composition, its specific inductivity is very high, reaches 6.6; In order further to improve its dielectric properties, low-k NE cloth appears, by adjusting its component, can reduce to a certain extent its specific inductivity, be generally about 4.6.But its dielectric constant values still height than resin system is a lot, brings very large restriction for the reduced dielectric constant of copper-clad plate material.
Summary of the invention
The object of the present invention is to provide a kind of matrix material, by adopting the polyetherimide strongthener, have lower specific inductivity and dielectric loss angle tangent, and have high heat resistance and good processes, be fit to high-frequency high-speed printed circuit board field.
Another object of the present invention also is to provide a kind of high-frequency circuit board that uses above-mentioned matrix material to make, and has lower specific inductivity, good thermotolerance and flame retardant resistance.
A further object of the present invention is to provide a kind of making method of above-mentioned high frequency substrate, and is simple to operate, and technique is convenient.
For achieving the above object, the invention provides a kind of matrix material, it comprises that component and volume percent thereof are as follows: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%;
The structural formula of the polyetherimide of described polyetherimide strongthener is shown below:
Wherein R1, R2 are
Or-(CH
2)
m-, m is 2 ~ 10 integer.
Described polyimide strongthener volume percent is preferably 25 ~ 80%, and more preferably 30 ~ 60%.
Described polyetherimide strongthener is polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.
Described compositions of thermosetting resin includes thermosetting resin, this thermosetting resin be Resins, epoxy, resol, benzoxazine resin, polyphenylene oxide resin, cyanate ester resin, polyimide resin, bimaleimide resin, hydrocarbon resin, polyorganosiloxane resin, teflon resin, polyethersulfone resin, polyether ketone resin, and the modified resin of aforementioned each thermosetting resin in one or more compositions.
Described compositions of thermosetting resin also includes solidifying agent and curing catalyst, solidifying agent is one or more mixtures in Dyhard RU 100, aromatic amine, resol, the anhydride compound, and curing catalyst is one or more mixtures in glyoxaline compound and derivative compound, piperidines, Lewis acid, triphenylphosphine and the organometallic complex.
Described compositions of thermosetting resin also includes fire retardant, and fire retardant adopts brominated or halogen-free flame retardants, and described brominated flame-retardant is the two tetrabromo phthalimides of decabromodiphynly oxide, TDE, brominated styrene or ethylene; Described halogen-free flame retardants is three (2, the 6-3,5-dimethylphenyl) phosphine, 10-(2, the 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2,6-two (2, the 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is assorted-10-phosphine phenanthrene-10-oxide compound, phenoxy group phosphine cyanogen compound, phosphoric acid ester, phosphate ester salt compound or hydrated metal compound.
Described compositions of thermosetting resin also includes mineral filler or organic filler, and mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride, boron nitride, silicon carbide, aluminium hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, boehmite, zinc borate and the mica; Organic filler is selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide and the polyethersulfone powder.
The present invention also provides a kind of usefulness high-frequency circuit board that above-mentioned matrix material is made, it comprises: several layers of mutual superimposed prepreg and be overlaid on Copper Foil on these superimposed prepreg one or both sides, at least one prepreg made by described matrix material in these several layers of prepregs.
Further, the present invention also provides a kind of making method of above-mentioned high-frequency circuit board, comprises the steps:
Step 1, by volume per-cent provides matrix material each component: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%;
Step 2, compositions of thermosetting resin is mixed with glue;
Step 3, the glue dipping polyetherimide strongthener made from above-mentioned, baking obtains prepreg;
Step 4, getting above-mentioned prepreg, to count Zhang Jinhang superimposed, is covered with Copper Foil in the one or both sides of superimposed prepreg, is cured in press and makes described high-frequency circuit board, and solidification value is 150 ~ 300 ℃, solidifying pressure 5 ~ 50Kg/cm
2
Described polyetherimide strongthener is polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.
Beneficial effect of the present invention: at first, adopt the polyetherimide strongthener, its specific inductivity is 3.0, and traditional glass fibre reinforcement of comparing can reduce the specific inductivity of circuit substrate effectively;
Secondly, the present invention adopts the polyetherimide strongthener, has high heat resistance, second-order transition temperature has the intrinsic flame retardant resistance simultaneously greater than 200 ℃, the existing organic fibre of comparing, have higher thermotolerance and flame retardant resistance such as polyethylene fibre, be more suitable in circuit substrate, using;
In a word, matrix material of the present invention is made easily, has low specific inductivity with the high-frequency circuit board of its making, good heat resistance, and the circuit card handling ease, and have good flame retardant resistance.
Embodiment
The invention provides a kind of matrix material, it comprises that component and volume percent thereof (by total composite volume per-cent than calculating) are as follows: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%.
The structural formula of the polyetherimide of described polyetherimide strongthener is shown below:
Wherein R1, R2 represent to have aromatic residue or and the group of alkylidene group, can be identical between R1 and the R2 can be not identical yet, for
Or-(CH
2)
m-, m is 2 ~ 10 integer.
Described polyimide strongthener volume percent is preferably 25 ~ 80%, further is preferably 30 ~ 60%.
Described polyetherimide strongthener can be polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.The present invention adopts the polyetherimide strongthener, is 3.0 such as its specific inductivity of polyether-imide fiber cloth, and traditional glass fibre reinforcement of comparing has lower specific inductivity, can effectively reduce the specific inductivity of material.
Described compositions of thermosetting resin includes thermosetting resin, the present invention is to this thermosetting resin and be not particularly limited, can for Resins, epoxy, resol, benzoxazine resin, polyphenylene oxide resin, cyanate ester resin, polyimide resin, bimaleimide resin, hydrocarbon resin, polyorganosiloxane resin, teflon resin, polyethersulfone resin, polyether ketone resin, and the modified resin of aforementioned each thermosetting resin in one or more compositions.Consider one or more in the preferred cyanate ester resin of thermosetting resin, bimaleimide resin, polyolefin resin, modified polyolefin resin, teflon resin and the polyphenylene oxide resin from considering more excellent dielectric properties angle.Described Resins, epoxy can be for the bisphenol A-type brominated epoxy resin, without bromine bisphenol A type epoxy resin, phenol resol, face cresol novolac resin, bisphenol A-type novolac epoxy, DCPC type Resins, epoxy, biphenyl type epoxy resin, naphthol type epoxy resin, alkylbenzene phenol-type epoxy resin, aliphatic epoxy resin, trifunctional Resins, epoxy or nitrogen-containing epoxy thermoset; Described cyanate ester resin can be bisphenol A cyanate ester resin, DCPD type cyanate ester resin, bis-phenol M type cyanate ester resin, Bisphenol F type cyanate ester resin, Novolac Cyanate Ester Resins, alkylphenol type cyanate ester resin or naphthol type cyanate; Described maleimide resin is chosen as DDM type bimaleimide resin, diamines modified bismaleimide resin or allyl group modified bismaleimide resin; Described benzoxazine resin is chosen as aniline type benzoxazine resin, bisphenol A-type benzoxazine resin, Bisphenol F type benzoxazine resin, naphthol type benzoxazine resin or phenolphthalein type benzoxazine resin; Described polyphenylene oxide resin is chosen as terminal hydroxy group polyphenylene oxide resin, epoxy group(ing) modified polyphenylene ether resin, vinylated modified polyphenylene ether resin or acylations modified polyphenylene ether resin; Described unsaturated polyester is chosen as polybutadiene, butadiene-styrene copolymer resin, maleimide modified polybutadiene resin, epoxy group(ing) modified polybutadiene resin, hydroxy-terminated polybutadienes resin, styrene resin, vinyl toluene resin, ethyl styrene resin, divinylbenzene resin, isopentene resin, acrylate, acrylonitrile resin or benzocyclobutane olefine resin.Calculate with 100 weight part compositions of thermosetting resin, above-mentioned thermosetting resin accounts for described compositions of thermosetting resin 50 ~ 99% weight parts.
Can also comprise as required solidifying agent and curing catalyst in the described compositions of thermosetting resin, there is no particular limitation in the selection of solidifying agent, mainly plays and improve the cross-linking density effect.Can be one or more mixtures in Dyhard RU 100, aromatic amine, resol, the anhydride compound etc.Described aromatic amine is chosen as diaminodiphenylsulfone(DDS), diaminodiphenyl oxide sulfobenzide, diamino phenylate phenyl ether, diaminodiphenyl oxide dihydroxyphenyl propane, diaminodiphenyl oxide-6F-dihydroxyphenyl propane or fluorenamine compound; Described resol is chosen as bisphenol A-type resol, phenol resol, faces cresol novolac resin, dicyclopentadiene type resol, xenol urea formaldehyde, naphthol novolac resin, alkylphenol urea formaldehyde or triphenol resol; Described anhydride compound is chosen as methyl tetrahydrochysene acid anhydrides, methyl six hydracid acid anhydrides or vinylbenzene span and comes acid anhydrides; Calculate with 100 parts of weight compositions of thermosetting resin, described solidifying agent accounts for compositions of thermosetting resin 1 ~ 50% weight part.
Described curing catalyst is not particularly limited, as long as the reaction of energy catalysis compositions of thermosetting resin, the temperature of reaction of reduction curing system are preferably one or more mixtures in glyoxaline compound and derivative compound thereof, piperidines, Lewis acid, triphenylphosphine, the organometallic complex.Described glyoxaline compound can have been enumerated glyoxal ethyline, 2-phenylimidazole and 2-ethyl-4-methylimidazole, described piperidine compounds can enumerate 2,3-diamino piperidines, 2,5-diamino piperidines 2,6-diamino piperidines, 2,5-diamino, 2-amino-3-methyl piperidine, 2-amino-4-4 methyl piperidine, 2-amino-3-nitro piperidines, 2-amino-5-nitro piperidines and 4-dimethylamino phenylpiperidines; Described lewis acid catalyst is chosen as Boron Trifluoride Ethylamine; Described organometallic complex is chosen as acetylacetone copper, acetylacetone cobalt, zinc octoate or naphthenic acid vanadium.With described compositions of thermosetting resin 100 listed as parts by weight, the addition of curing catalyst is 0.05 ~ 3 weight part, is preferably the 0.1-2.5 weight part, and more preferably the 0.15-2.0 weight part particularly preferably is the 0.15-1.0 weight part.
Compositions of thermosetting resin of the present invention can optionally add fire retardant, and the fire retardant that optionally adds is not particularly limited, and the selected fire retardant that uses non-response type is not to affect dielectric properties as good.Can adopt brominated or halogen-free flame retardants, described brominated flame-retardant can be the two tetrabromo phthalimides of decabromodiphynly oxide, TDE, brominated styrene or ethylene; Described halogen-free flame retardants is three (2, the 6-3,5-dimethylphenyl) phosphine, 10-(2, the 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2,6-two (2, the 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is assorted-10-phosphine phenanthrene-10-oxide compound, phenoxy group phosphine cyanogen compound, phosphoric acid ester, phosphate ester salt compound or hydrated metal compound.With respect to described compositions of thermosetting resin 100 listed as parts by weight, the addition of fire retardant is preferably the 5-100 weight part, and more preferably the 5-90 weight part particularly preferably is the 5-80 weight part.
If needed, filler be can also further contain in the compositions of thermosetting resin of the present invention, organic filler or mineral filler are.The filler that optionally adds is not particularly limited, and mineral filler can be selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride, boron nitride, silicon carbide, aluminium hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, boehmite, zinc borate and the mica etc.; Organic filler can be selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide and the polyethersulfone powder etc.In addition, the shape of mineral filler, particle diameter etc. also are not particularly limited, and particle diameter is 0.01-50 μ m usually, is preferably 0.01-20 μ m, particularly preferably is 0.1-10 μ m, and the mineral filler of this particle size range more easily disperses in resin liquid.Moreover the addition of filler also is not particularly limited, and with respect to described compositions of thermosetting resin 100 listed as parts by weight, the addition of filler is the 5-1000 weight part, is preferably the 5-300 weight part, and more preferably the 5-200 weight part particularly preferably is the 15-100 weight part.
The high-frequency circuit board that uses above-mentioned matrix material to make comprises several layers of mutual superimposed prepreg and is overlying on respectively the Copper Foil of one or both sides, in these several layers of prepregs at least one or all made by described matrix material.
The making method of above-mentioned high-frequency circuit board comprises the steps:
Step 1, by volume per-cent provides matrix material each component: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%.
Step 2, compositions of thermosetting resin is mixed with glue: adopt suitable solvent compositions of thermosetting resin to be mixed with according to a certain percentage the glue of certain solids content.
Step 3, the glue dipping polyetherimide strongthener made from above-mentioned, and control suitable thickness, namely control the thickness of the glue on the polyetherimide strongthener dipping to suitable thickness range, then toast the removal solvent, obtain prepreg;
Step 4, getting above-mentioned prepreg, to count Zhang Jinhang superimposed, is covered with Copper Foil in the one or both sides of superimposed prepreg, is cured in press and makes described high-frequency circuit board, and solidification value is 150 ~ 300 ℃, solidifying pressure 5 ~ 50Kg/cm
2
For the dielectric properties of the above-mentioned high-frequency circuit board of making, namely specific inductivity and Dielectric loss tangent value reach resistance toheat, and following embodiment further describes in detail and describes.
Embodiment 1
The allotment of resin adhesive liquid:
Get a container, the brominated bisphenol a type epoxy resin DER530A80(DOW company that adds 100 weight parts, EEW is 435g/eq), then with dicy-curing agent (the Ningxia Daiei of 2.0 weight parts, amino equivalent 21g/eq) in solvent and the DMF solvent, adds in the above-mentioned resin and stir, add again the curing catalyst 2-ethyl-4-methylimidazole of 0.075 weight part, add at last an amount of solvent DMF, continue to stir glue.
Prepreg and board making:
With polyether-imide fiber cloth (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 50%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 180 ℃, and solidifying pressure is 25Kg/cm
2, be 45min set time.
Embodiment 2
The allotment of resin adhesive liquid:
Get a container, the brominated bisphenol a type epoxy resin DER530A80(DOW company that adds 100 weight parts, EEW is 435g/eq), then with the phenolic curing agent TD-2090(Ningxia Daiei of 24.1 weight parts, hydroxyl equivalent 105g/eq) is dissolved in the butanone solvent, adds in the above-mentioned resin and stir, add again the curing catalyst 2-ethyl-4-methylimidazole of 0.075 weight part, add at last an amount of solvent PM, continue to stir glue.
Prepreg and board making:
With polyether-imide fiber cloth (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 50%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 190 ℃, and solidifying pressure is 30Kg/cm
2, be 90min set time.
Embodiment 3
The allotment of resin adhesive liquid:
Get a container; the dicyclopentadiene type novolac epoxy HP-7200-H(Japan DIC company that adds 70 weight parts; EEW is 288g/eq); then the cyanate (Shanghai Hui Feng company system) with 30 weight parts is dissolved in the butanone solvent; add in the above-mentioned resin and stir; add again the curing catalyst zinc octoate of 0.075 weight part, add at last an amount of butanone solvent, continue to stir glue.
Prepreg and board making:
With polyether-imide fiber cloth (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 50%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 200 ℃, and solidifying pressure is 35Kg/cm
2, be 100mi set time.
Embodiment 4
The allotment of resin adhesive liquid:
Get a container, add 100 weight part polyhutadiene B3000(Japan Cao Da company, 1,2-ethylene content 90%), then in dicumyl peroxide solidifying agent (the Shanghai Gaoqiao company system) solvent and toluene solvant with 3.0 weight parts, add in the above-mentioned resin and stir, continue to stir glue.
Prepreg and board making:
With polyether-imide fiber cloth (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 50%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 220 ℃, and solidifying pressure is 25Kg/cm
2, be 120min set time.
Embodiment 5
The allotment of resin adhesive liquid:
Get a container; the dicyclopentadiene type novolac epoxy HP-7200-H(Japan DIC company that adds 70 weight parts; EEW is 288g/eq); then the cyanate (Shanghai Hui Feng company system) with 30 weight parts is dissolved in the butanone solvent; add in the above-mentioned resin and stir; add again the curing catalyst zinc octoate of 0.075 weight part, add at last an amount of butanone solvent, continue to stir glue.
Prepreg and board making:
With polyether-imide fiber cloth (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 30%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 220 ℃, and solidifying pressure is 25Kg/cm
2, be 120min set time.
Embodiment 6
The allotment of resin adhesive liquid:
Get a container; the dicyclopentadiene type novolac epoxy HP-7200-H(Japan DIC company that adds 70 weight parts; EEW is 288g/eq); then the cyanate (Shanghai Hui Feng company system) with 30 weight parts is dissolved in the butanone solvent; add in the above-mentioned resin and stir; add again the curing catalyst zinc octoate of 0.075 weight part, add at last an amount of butanone solvent, continue to stir glue.
Prepreg and board making:
With polyether-imide fiber cloth (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 75%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 220 ℃, and solidifying pressure is 25Kg/cm
2, be 120min set time.
Embodiment 7
The allotment of resin adhesive liquid:
Get a container, add 100 weight part polyhutadiene B3000(Japan Cao Da company, 1,2-ethylene content 90%), then in dicumyl peroxide solidifying agent (the Shanghai Gaoqiao company system) solvent and toluene solvant with 3.0 weight parts, add in the above-mentioned resin and stir, continue to stir glue.
Prepreg and board making:
With polyetherimide non-woven fabrics (Japanese KURARAY company system), under 80 ~ 150 ℃ of conditions, processed 30 ~ 90 minutes, then with above-mentioned deployed glue dipping polyether-imide fiber cloth, and the volume content of control cloth is 50%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes high-frequency circuit board in thermocompressor, and its solidification value is 220 ℃, and solidifying pressure is 25Kg/cm
2, be 120min set time.
Comparative example 1
The allotment of resin adhesive liquid:
Get a container, the brominated bisphenol a type epoxy resin DER530A80(DOW company that adds 100 weight parts, EEW is 435g/eq), then with dicy-curing agent (the Ningxia Daiei of 2.0 weight parts, amino equivalent 21g/eq) in solvent and the DMF solvent, adds in the above-mentioned resin and stir, add again the curing catalyst 2-ethyl-4-methylimidazole of 0.075 weight part, add at last an amount of solvent DMF, continue to stir glue.
Prepreg and board making:
Then be 50% with above-mentioned deployed glue dipping electronic-grade E glass-fiber-fabric 2116 (company is spun, thickness 0.09mm in day east) and the volume content of controlling cloth, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes circuit substrate in thermocompressor, and its solidification value is 180 ℃, and solidifying pressure is 25Kg/cm
2, be 45min set time.
Comparative example 2
The allotment of resin adhesive liquid:
Get a container, the brominated bisphenol a type epoxy resin DER530A80(DOW company that adds 100 weight parts, EEW is 435g/eq), then with dicy-curing agent (the Ningxia Daiei of 2.0 weight parts, amino equivalent 21g/eq) in solvent and the DMF solvent, adds in the above-mentioned resin and stir, add again the curing catalyst 2-ethyl-4-methylimidazole of 0.075 weight part, add at last an amount of solvent DMF, continue to stir glue.
Prepreg and board making:
Then (company is spun in day east with above-mentioned deployed glue stain low-k electronic-grade NE glass-fiber-fabric 2116, thickness 0.09mm) and the volume content of controlling cloth be 50%, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes circuit substrate in thermocompressor, and its solidification value is 180 ℃, and solidifying pressure is 25Kg/cm
2, be 45min set time.
Comparative example 3
The allotment of resin adhesive liquid:
Get a container, the brominated bisphenol a type epoxy resin DER530A80(DOW company that adds 100 weight parts, EEW is 435g/eq), then with dicy-curing agent (the Ningxia Daiei of 2.0 weight parts, amino equivalent 21g/eq) in solvent and the DMF solvent, adds in the above-mentioned resin and stir, add again the curing catalyst 2-ethyl-4-methylimidazole of 0.075 weight part, add at last an amount of solvent DMF, continue to stir glue.
Prepreg and board making:
Then be 50% with above-mentioned deployed glue stain polyvinyl fibre cloth UHMWPE (Shanghai Rui Si company) and the volume content of controlling cloth, then toasted 5 ~ 10 minutes under 155 ℃ of conditions, desolventizing makes prepreg.Use several prepared prepregs to be superimposed with each other, respectively cover a Copper Foil on its both sides, curing makes circuit substrate in thermocompressor, and its solidification value is 180 ℃, and solidifying pressure is 25Kg/cm
2, be 45min set time.
Each embodiment physical data of table 1.
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Dk(10G) | 3.7 | 3.6 | 3.4 | 2.7 | 3.6 | 3.2 | 2.68 |
| Df(10G) | 0.012 | 0.0012 | 0.008 | 0.0038 | 0.0085 | 0.007 | 0.035 |
| Flame retardant resistance | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
Each comparative example physical data of table 2.
| Performance | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Dk(10G) | 4.4 | 4.2 | 2.6 |
| Df(10G) | 0.018 | 0.016 | 0.003 |
| Flame retardant resistance | V-0 | V-0 | V-2 |
Physical Property Analysis
Physical data result from table 1 and table 2 can find out, the high-frequency circuit board material that embodiment 1 ~ 4 makes has lower specific inductivity and Dielectric loss tangent value, high frequency characteristics is good, and use electronic-grade E glass-fiber-fabric and NE glass-fiber-fabric all higher as strongthener specific inductivity and Dielectric loss tangent value in the comparative example 1 ~ 2, comparative example 3 uses polyvinyl fibre cloth as strongthener, although have low specific inductivity and dielectric loss, but because polyethylene itself does not possess flame retardant resistance, can't satisfy the requirement of the UL 94V-0 of electronic product.
Above embodiment, be not that content to composition of the present invention imposes any restrictions, every foundation technical spirit of the present invention or composition composition or content all still belong in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment does.
Claims (10)
1. a matrix material is characterized in that, it comprises that component and volume percent thereof are as follows: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%;
The structural formula of the polyetherimide of described polyetherimide strongthener is shown below:
Wherein R1, R2 are
Or-(CH
2)
m-, m is 2 ~ 10 integer.
2. matrix material as claimed in claim 1 is characterized in that, the volume percent of described polyimide strongthener is 25 ~ 80%.
3. matrix material as claimed in claim 2 is characterized in that, the volume percent of described polyimide strongthener is 30 ~ 60%.
4. matrix material as claimed in claim 1 is characterized in that, described polyetherimide strongthener is polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.
5. matrix material as claimed in claim 1, it is characterized in that, described compositions of thermosetting resin includes thermosetting resin, this thermosetting resin be Resins, epoxy, resol, benzoxazine resin, polyphenylene oxide resin, cyanate ester resin, polyimide resin, bimaleimide resin, hydrocarbon resin, polyorganosiloxane resin, teflon resin, polyethersulfone resin, polyether ketone resin, and the modified resin of aforementioned each thermosetting resin in one or more compositions.
6. matrix material as claimed in claim 5, it is characterized in that, described compositions of thermosetting resin also includes solidifying agent and curing catalyst, solidifying agent is one or more mixtures in Dyhard RU 100, aromatic amine, resol and the anhydride compound, and curing catalyst is one or more mixtures in glyoxaline compound and derivative compound, piperidines, Lewis acid, triphenylphosphine and the organometallic complex.
7. matrix material as claimed in claim 5, it is characterized in that, described compositions of thermosetting resin also includes fire retardant and filler, fire retardant adopts brominated or halogen-free flame retardants, and described brominated flame-retardant is the two tetrabromo phthalimides of decabromodiphynly oxide, TDE, brominated styrene or ethylene; Described halogen-free flame retardants is three (2, the 6-3,5-dimethylphenyl) phosphine, 10-(2, the 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2,6-two (2, the 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, phenoxy group phosphine cyanogen compound, phosphoric acid ester, phosphate ester salt compound or hydrated metal compound, described filler is for having mineral filler or organic filler, and mineral filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride, boron nitride, silicon carbide, aluminium hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, boehmite, in zinc borate and the mica one or more; Organic filler is selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide and the polyethersulfone powder.
8. high-frequency circuit board that uses matrix material as claimed in claim 1 to make, it is characterized in that, it comprises: several layers of mutual superimposed prepreg and be overlaid on Copper Foil on these superimposed prepreg one or both sides, at least one prepreg made by described matrix material in these several layers of prepregs.
9. the making method of a high-frequency circuit board as claimed in claim 8 is characterized in that, comprises the steps:
Step 1, by volume per-cent provides matrix material each component: polyetherimide strongthener 10 ~ 90% and compositions of thermosetting resin 10 ~ 90%;
Step 2, compositions of thermosetting resin is mixed with glue;
Step 3, the glue dipping polyetherimide strongthener made from above-mentioned, baking obtains prepreg;
Step 4, getting above-mentioned prepreg, to count Zhang Jinhang superimposed, is covered with Copper Foil in the one or both sides of superimposed prepreg, is cured in press and makes described high-frequency circuit board, and solidification value is 150 ~ 300 ℃, solidifying pressure 5 ~ 50Kg/cm
2
10. the making method of high-frequency circuit board as claimed in claim 9 is characterized in that, described polyetherimide strongthener is polyether-imide fiber woven cloth, polyetherimide non-woven fabrics or polyetherimide glass fiber paper.
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