CN103351581B - A kind of high-k resin combination and uses thereof - Google Patents
A kind of high-k resin combination and uses thereof Download PDFInfo
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- CN103351581B CN103351581B CN201310307404.0A CN201310307404A CN103351581B CN 103351581 B CN103351581 B CN 103351581B CN 201310307404 A CN201310307404 A CN 201310307404A CN 103351581 B CN103351581 B CN 103351581B
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- 0 C1CC2*(CCC3)=CC3*C2C1 Chemical compound C1CC2*(CCC3)=CC3*C2C1 0.000 description 4
- FOABIIOEBITTAH-HTAVTVPLSA-N CC1(C)CC(C2)[C@@H](CCC3)N3CC2C1 Chemical compound CC1(C)CC(C2)[C@@H](CCC3)N3CC2C1 FOABIIOEBITTAH-HTAVTVPLSA-N 0.000 description 1
Abstract
The present invention relates to a kind of high-k resin combination and the prepreg using it to make and copper-clad laminate.The prepreg using this high-k resin combination to make, comprises high-k glasscloth and by the high-k resin combination of the dry postadhesion of impregnation on high-k glasscloth.The copper-clad laminate using this high-k resin combination to make, the Copper Foil comprising at least one superimposed prepreg and cover on superimposed prepreg two sides.The copper-clad laminate that high-k resin combination of the present invention makes, has the performances such as high-k, low-dielectric loss, high glass-transition temperature, high-peeling strength, can meet the performance requriements of high-k antenna substrate.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of resin combination and uses thereof, be specifically related to a kind of high-k resin combination and uses thereof, relate more specifically to a kind of composite material with high dielectric constant and the prepreg using it to make and copper-clad laminate, the prepreg using this composite material with high dielectric constant to make and copper-clad laminate can be applicable to antenna substrate.
Background technology
Along with the development of the emerging micro-processing technology such as microelectronics, micromechanics, make to be not only numeral, baseband circuit blocks, even running fire frequency module also successfully achieves microminiaturization, the design of chip and production.Antenna is as important radio frequency front-end devices, and its index request is also day by day harsh, and miniaturization, built-inization, multiband, intellectuality are the development trends of mobile terminal miniature antenna.Because the size of printed antenna and the relative permittivity of substrate are inversely proportional to, so the medium substrate with high-k will be selected to reduce antenna size.
At the electric wave in high frequency field, require the power loss of electron device or conveyance loss little.Conveyance loss is consumed in electron device as thermal energy, becomes the reason of electron device heating.Conveyance loss is directly proportional to the tangent of the dielectric loss angle of substrate, so in order to reduce conveyance loss, needing tangent of the dielectric loss angle is diminished, namely will ensure that the dielectric loss of medium substrate is little.
Chinese patent CN100348661 discloses the composite dielectric layer of a kind of organic insulation and dielectric ceramic powder formation, organic insulation is the cured resin utilizing epoxy resin and active ester to be cured reaction formation, gained composite dielectric layer has higher specific inductivity and lower dielectric loss, but the second-order transition temperature of composite dielectric layer is very low, only have 131 ~ 135 DEG C.This patent uses active ester as solidifying agent, although cured article has lower dielectric loss, second-order transition temperature is lower.
Chinese patent CN101974205 discloses a kind of high-k resin combination, comprise epoxy resin, at least one phenoxy resin or end and complete base paracril, biphenyl type resol or bitter edible plant type resol, high-k filler, although cured article has higher specific inductivity, higher second-order transition temperature (T
greach 156 DEG C), but the dielectric loss of cured article is excessive, up to 0.038.
In high-k copper-clad laminate, in order to make specific inductivity higher, the content of high-k filler is very high, thus the stripping strength of copper-clad laminate is reduced.Meanwhile, in high-k copper-clad laminate, usually use E type glasscloth as strongthener, but the specific inductivity of E type glasscloth is lower, is difficult to make the dielectric constant values of high-k copper-clad laminate reach higher.
For above problem, the present invention proposes and a kind of there is more high-k, more low-dielectric loss, higher glass transition temperature and the antenna composite material with high dielectric constant compared with high-peeling strength.
Summary of the invention
An object of the present invention is to provide a kind of high-k resin combination, and it can provide the dielectric properties of the excellence needed for copper-clad laminate, high second-order transition temperature and high-peeling strength.
In order to achieve the above object, present invention employs following technical scheme:
A kind of high-k resin combination, comprising:
(a) flexible-epoxy, its chemical structural formula is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10;
(b) dicyclopentadiene type novolac epoxy, its chemical structural formula is as follows:
In formula, n
2represent that average repeat unit is 1 ~ 10;
C () difunctional epoxy resin except epoxy resin described in above-mentioned (a) and (b) is or/and multiple functionality epoxide resin;
(d) dicyclopentadiene type ethylene rhodanate resin, its chemical structural formula is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5;
(e) active ester resinoid, its chemical structural formula is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25.
According to the present invention, specific inductivity is greater than 10, is high-k resin combination of the present invention.
According to the present invention, described flexible-epoxy refers to the epoxy resin possessing structure described in following structural formula, the BPA skeleton of the epoxy resin of this structure maintains the thermotolerance of epoxy resin, hydrocarbon structure long-chain skeleton improves the snappiness of epoxy resin, especially still possess after solidification excellent snappiness, improve the stripping strength of copper-clad plate simultaneously.The exemplary commercial epoxy resin possessing this kind of structure has EXA-4816, EXA-4822, EXA-4850-150, EXA-4850-100 etc., be Dainippon Ink. & Chemicals Inc to manufacture, these flexible-epoxies can be used alone, or combinationally use with two or more different resins.The chemical structural formula of flexible-epoxy is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10.
According to the present invention, described dicyclopentadiene type novolac epoxy refers to the epoxy resin possessing structure described in following structural formula, the epoxy resin of this structure is compared with general bisphenol A type epoxy resin, except containing except phenyl ring in its molecular structure, also there is the alicyclic structure of dicyclopentadiene, thus improve the thermotolerance of product and reduce the water-intake rate of resin, the epoxy resin of this class formation has excellent thermotolerance, agent of low hygroscopicity, low-dielectric loss and high-peeling strength.In addition, carbon yield under the epoxy resin high temperature of this structure is higher, also good flame retardant effect can be reached, mainstream product is the HP-7200 series that Dainippon Ink. & Chemicals Inc produces, HP-7200L, HP-7200, HP-7200H and HP-7200HH is arranged as by epoxy equivalent (weight) order from small to large, in addition, the XD-1000 resene of Nippon Kayaku K. K is same as HP-7200H, wider in copper-clad plate sector application.These dicyclopentadiene type novolac epoxys can be used alone, or combinationally use with two or more different resins.
The chemical structural formula of dicyclopentadiene type novolac epoxy is as follows:
N
2represent that average repeat unit is 1 ~ 10.
According to the present invention, described difunctional epoxy resin is the mixture of any one or at least two kinds in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin or isocyanate modified epoxy resin.The mixture of described mixture such as bisphenol A type epoxy resin and bisphenol f type epoxy resin, the mixture of bisphenol-s epoxy resin and biphenyl type epoxy resin, the mixture of naphthalene nucleus type epoxy resin and isocyanate modified epoxy resin, the mixture of bisphenol A type epoxy resin, bisphenol f type epoxy resin and bisphenol-s epoxy resin, the mixture of biphenyl type epoxy resin, naphthalene nucleus type epoxy resin and isocyanate modified epoxy resin.
In order to make copper-clad plate have flame retardant resistance, the brominated bisphenol A type epoxy resin EPICLON153-60M that bisphenol A type epoxy resin can select Wuxi Di Aisheng epoxy company limited to produce, bromine content is 46% ~ 50%, and its chemical structural formula is as follows:
N in formula
5represent that average repeat unit is 0 ~ 10.
According to the present invention, namely described multiple functionality epoxide resin refers to the epoxy resin that functionality is greater than 2.
According to the present invention, described multiple functionality epoxide resin is the mixture of any one or at least two kinds in novolac epoxy, triphenol methylmethane type epoxy resin or four phenolic group ethane type epoxy resin.
According to the present invention, described novolac epoxy is the mixture of any one or at least two kinds in phenol type novolac epoxy, ortho-cresol type novolac epoxy, bisphenol A-type novolac epoxy, biphenyl type novolac epoxy or naphthalene nucleus type novolac epoxy.The mixture of described mixture such as phenol type novolac epoxy and ortho-cresol type novolac epoxy, the mixture of bisphenol A-type novolac epoxy and biphenyl type novolac epoxy, the mixture of naphthalene nucleus type novolac epoxy and phenol type novolac epoxy, the mixture of ortho-cresol type novolac epoxy and bisphenol A-type novolac epoxy, the mixture of biphenyl type novolac epoxy and naphthalene nucleus type novolac epoxy.The N-740 that phenol type novolac epoxy can select Dainippon Ink. & Chemicals Inc to produce, N-770, N-775, the PNE177 resin that the series plastics such as N-865 or Taiwan Changchun Artificial Resin Factory Co. Ltd. produce, the N-660 that ortho-cresol type novolac epoxy can select Dainippon Ink. & Chemicals Inc to produce, N-665, N-670, N-673, N-680, the EOCN-1020 series plastics that the series plastics such as N-695 or Nippon Kayaku K. K produce, the EPR627MEK80 resin that bisphenol A-type novolac epoxy can select HEXION company of the U.S. to produce, the NC-3000 that biphenyl type novolac epoxy can select Nippon Kayaku K. K to produce, the series plastics such as NC-3000-H, the NC-7300-L that naphthalene nucleus type novolac epoxy can select Nippon Kayaku K. K to produce, the series plastics such as NC-7300-2L.
Triphenol methylmethane type epoxy resin and four phenolic group ethane type epoxy resin can improve the cross-linking density of resin, increase resistance toheat and the second-order transition temperature of sheet material.The series plastics such as EPPN-501H, EPPN-501HY, EPPN-502H that triphenol methylmethane type epoxy resin can select Nippon Kayaku K. K to produce, its chemical structural formula is as follows:
N in formula
6represent that average repeat unit is 0 ~ 5.
The EPON1031 resin that four phenolic group ethane type epoxy resin can select MOMENTIVE company of the U.S. to produce, its chemical structural formula is as follows:
According to the present invention, described dicyclopentadiene type ethylene rhodanate resin refers to the cyanate ester resin possessing structure described in following structural formula, and the cyanate ester resin dicyclopentadiene of this structure can reduce the dielectric loss of cyanate ester resin further as the length that spacer groups increases main chain.The dielectric loss of cyanate ester resin is between 0.002 ~ 0.008, far below the dielectric loss 0.018 ~ 0.030 of epoxy resin, and, cyanate ester resin more can keep lower dielectric loss than other thermosetting resin under high temperature, wet condition and in wider range of frequency, and excellent dielectric properties make cyanate ester resin have very large advantage at design circuit and microwave transmission field.Typical cyanate ester resin at present as high-performance circuit board is the XU-71787 cyanate ester resin that DOW chemical company of the U.S. produces, and XU-71787 cyanate ester resin is a kind of dicyclopentadiene type ethylene rhodanate resin.The chemical structural formula of dicyclopentadiene type ethylene rhodanate resin is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5.
According to the present invention, described active ester resinoid refers to possess structure-activity esters resin described in following structural formula, the active ester of this structure is as the solidifying agent of epoxy resin, two or more ester group with greater activity is had in active ester solidifying agent molecule, reaction can be cured with epoxy resin, formed when same epoxy resin reaction not containing the rack of secondary hydroxyl group, so cured article has lower dielectric loss and water-intake rate, this is conventional solidified dose and cannot realizes as amine curing agent and phenols curing agent, the copper-clad plate prepared can be made to have low water-intake rate, low dielectric loss and excellent wet-hot aging performance.Possess the EXB-9460S-65T active ester or HPC-8000-65T active ester that Dainippon Ink. & Chemicals Inc can be selected to produce as shown in the formula structure-activity esters resin described in structural formula.The resinoid chemical structural formula of active ester is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25.
Preferably, described high-k resin combination also comprises high-k filler.
According to the present invention, described high-k filler, namely refers to the filler that specific inductivity is greater than 10.
Preferably, described high-k filler preferably has the high-dielectric constant inorganic particle of perovskite typed crystalline texture or composite perofskite type crystalline texture, preferred barium titanate further, strontium titanate, magnesium titanate, calcium titanate, strontium-barium titanate, calcium barium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, zirconium lanthanium titanate is plumbous, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnoniobate, barium magnesium niobate, Lithium niobium trioxide, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, the mixture of any one or at least two kinds in barium titanate rubidium or CaCu 3 Ti 4 O.The mixture of described mixture such as barium titanate and strontium titanate, the mixture of magnesium titanate and calcium titanate, the mixture of strontium-barium titanate and calcium barium titanate, the mixture of lead titanate and Pb-based lanthanumdoped zirconate titanates, the mixture of zirconium lanthanium titanate lead and lanthanium titanate barium, the mixture of zirconia titanate barium and titanium dioxide, the mixture of hafnium oxide and lead magnoniobate, the mixture of barium magnesium niobate and Lithium niobium trioxide, the mixture of potassium niobate and tantalic acid aluminium strontium, the mixture of potassium tantallum niobate (KTH) and strontium barium niobate, the mixture of lead bariun niobate and titanium niobate barium, bismuth tantalate strontium, bismuth titanates, the mixture of barium titanate rubidium and CaCu 3 Ti 4 O.
In resin combination, the non-volatility composition of component (a) and (b), (c), (d) and (e) is in mass parts, described component (a) is 5 ~ 15 mass parts, described component (b) is 15 ~ 40 mass parts, described component (c) is 10 ~ 25 mass parts, described component (d) is 10 ~ 25 mass parts, and described component (e) is 20 ~ 40 mass parts.
The mass fraction of described component (a) is such as 6 mass parts, 7 mass parts, 8 mass parts, 9 mass parts, 10 mass parts, 11 mass parts, 12 mass parts, 13 mass parts, 14 mass parts.
The mass fraction of described component (b) is such as 16 mass parts, 18 mass parts, 20 mass parts, 22 mass parts, 24 mass parts, 26 mass parts, 28 mass parts, 30 mass parts, 32 mass parts, 34 mass parts, 36 mass parts, 38 mass parts.
The mass fraction of described component (c) is such as 11 mass parts, 12 mass parts, 13 mass parts, 14 mass parts, 15 mass parts, 16 mass parts, 17 mass parts, 18 mass parts, 19 mass parts, 20 mass parts, 21 mass parts, 22 mass parts, 23 mass parts, 24 mass parts.
The mass fraction of described component (d) is such as 11 mass parts, 12 mass parts, 13 mass parts, 14 mass parts, 15 mass parts, 16 mass parts, 17 mass parts, 18 mass parts, 19 mass parts, 20 mass parts, 21 mass parts, 22 mass parts, 23 mass parts, 24 mass parts.
The mass fraction of described component (e) is such as 21 mass parts, 22 mass parts, 24 mass parts, 26 mass parts, 28 mass parts, 30 mass parts, 32 mass parts, 34 mass parts, 36 mass parts, 38 mass parts.
In high-k copper-clad laminate, specific inductivity is reached meet the service requirements of antenna substrate material, the content of high-k filler must reach certain amount, the quality of the non-volatility composition of high-k resin combination is 100wt%, the quality of high-k filler is 60 ~ 85wt%, such as 62wt%, 65wt%, 68wt%, 72wt%, 75wt%, 78wt%, 82wt%, 84wt%.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described resin combination different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
High-k resin combination of the present invention can also use together in conjunction with various superpolymer, as long as it does not damage the proper property of high-k resin combination.Concrete example is as being liquid crystalline polymers, thermosetting resin, thermoplastic resin, different flame-retardant compounds or additive etc.They can be used alone as required or multiple combination uses.
In addition, described high-k resin combination can also contain various additive, as concrete example, can enumerate oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material, lubricant etc.
As the preparation method of one of resin combination of the present invention, can by (a) flexible-epoxy described in known method cooperation, stirring, mixing, (b) dicyclopentadiene type novolac epoxy, (c) difunctional epoxy resin except epoxy resin described in above-mentioned (a) and (b) or/and prepared by multiple functionality epoxide resin, (d) dicyclopentadiene type ethylene rhodanate resin and (e) active ester resinoid.
A kind of high-k resin combination, comprising:
(a) flexible-epoxy, its chemical structural formula is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10;
(b) dicyclopentadiene type novolac epoxy, its chemical structural formula is as follows:
In formula, n
2represent that average repeat unit is 1 ~ 10;
C () difunctional epoxy resin except epoxy resin described in above-mentioned (a) and (b) is or/and multiple functionality epoxide resin;
(d) dicyclopentadiene type ethylene rhodanate resin, its chemical structural formula is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5;
(e) active ester resinoid, its chemical structural formula is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25;
In resin combination, the non-volatility composition of component (a) and (b), (c), (d) and (e) is in mass parts, described component (a) is 5 ~ 15 mass parts, described component (b) is 15 ~ 40 mass parts, described component (c) is 10 ~ 25 mass parts, described component (d) is 10 ~ 25 mass parts, and described component (e) is 20 ~ 40 mass parts;
F () high-k filler, the quality of the non-volatility composition of high-k resin combination is 100wt%, and the quality of high-k filler is 60 ~ 85wt%.That is, the quality of described high-k filler accounts for 60 ~ 85wt% of the quality of the non-volatility composition of high-k resin combination.
Two of object of the present invention is to provide a kind of composite material with high dielectric constant, and described matrix material comprises high-k resin combination as above and high-k glasscloth.The quality of composite material with high dielectric constant is 100wt%, and the quality of described high-k glasscloth is 10 ~ 40wt%, such as 11wt%, 15wt%, 18wt%, 20wt%, 25wt%, 30wt%, 37wt%, 39wt%.The mass percentage of high-k glasscloth can be controlled by following manner: the high-k glasscloth 1. selecting dissimilar (as 106 glass-fiber-fabrics, 1037 glass-fiber-fabrics, 1065 glass-fiber-fabrics, 1078 glass-fiber-fabrics, 2313 glass-fiber-fabrics, 3313 glass-fiber-fabrics, 1080 glass-fiber-fabrics, 2116 glass-fiber-fabrics, 7628 glass-fiber-fabrics etc.); 2. regulate the folder shaft clearance of adhesive applicator to control the thickness after high-k resin combination preimpregnation high-k glasscloth.
Namely high-k glasscloth of the present invention refers to the glasscloth that specific inductivity is greater than 10.
A kind of composite material with high dielectric constant, comprise (1) high-k resin combination and (2) high-k glasscloth, the quality of composite material with high dielectric constant is 100wt%, and the quality of described high-k glasscloth is 10 ~ 40wt%;
Wherein, (1) high-k resin combination comprises:
(a) flexible-epoxy, its chemical structural formula is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10;
(b) dicyclopentadiene type novolac epoxy, its chemical structural formula is as follows:
In formula, n
2represent that average repeat unit is 1 ~ 10;
C () difunctional epoxy resin except epoxy resin described in above-mentioned (a) and (b) is or/and multiple functionality epoxide resin;
(d) dicyclopentadiene type ethylene rhodanate resin, its chemical structural formula is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5;
(e) active ester resinoid, its chemical structural formula is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25;
In resin combination, the non-volatility composition of component (a) and (b), (c), (d) and (e) is in mass parts, described component (a) is 5 ~ 15 mass parts, described component (b) is 15 ~ 40 mass parts, described component (c) is 10 ~ 25 mass parts, described component (d) is 10 ~ 25 mass parts, and described component (e) is 20 ~ 40 mass parts;
F () high-k filler, the mass content of the non-volatility composition of high-k resin combination is 100wt%, and the quality of high-k filler is 60 ~ 85wt%.
The present invention additionally provide simultaneously a kind of use above-mentioned composite material with high dielectric constant to make prepreg and copper-clad laminate, it has high-k, low-dielectric loss, also has high second-order transition temperature and high-peeling strength simultaneously.
Three of object of the present invention is to provide a kind of prepreg using above-mentioned high-k resin combination to make, and described prepreg comprises high-k glasscloth and by the as above high-k resin combination of the dry postadhesion of impregnation on high-k glasscloth.
According to the present invention, described high-k glasscloth is lead containing glass fibre or non-lead class is fiberglass braided forms, and the main component of flint glass is PbO, SiO
2and Al
2o
3, the main component of non-lead class glass is titanosilicate.
High-k glasscloth containing lead composition can select Dong to spin the high-k glasscloth of exploitation, and the specific inductivity of this high-k glasscloth is 12 ~ 15, far above the specific inductivity of common E type glasscloth.The high-k glasscloth of titanosilicate composition can select the high-k glasscloth of PANASONIC electrician and Engineering Department of Kyoto University, the cooperative development of NEC glass company, it makes raw material with the titan silicate glass of non-lead class, and specific inductivity is 11.6.The specific inductivity of the alumnioborosilicate glass fibre that common copper-clad plate is used is 6.5, by comparison, the specific inductivity of titan silicate glass fiber has increased significantly, this titan silicate glass fiber not only specific inductivity significantly improves, and can not cause public hazards, dielectric loss angle tangent low (dielectric loss angle tangent is 0.003) when having unleaded, harmless, discarded and the advantage such as chemical resistance is good.
The preparation method of prepreg of the present invention does not have concrete restriction, as long as it is by high-k resin combination of the present invention is combined with high-k glasscloth the method preparing prepreg.The preparation method of exemplary prepreg is: high-k resin combination of the present invention is made certain density glue, by dipping high-k glasscloth, then dry at a certain temperature, carry out semicure except desolventizing, obtain prepreg.
Can as required with an organic solvent in the high-k resin combination of prepreg in above-mentioned preparation, to organic solvent, there is no particular limitation, as long as the solvent of each component compatibility with resin combination, described solvent, as concrete example, can enumerate: methyl alcohol, ethanol, the alcohols such as butanols, ethyl cellosolve, ethylene glycol butyl ether, ethylene glycol-methyl ether, diethylene glycol ether, the ethers such as butyl, acetone, butanone, ethyl methyl ketone, hexone, the ketones such as pimelinketone, toluene, dimethylbenzene, sym-trimethylbenzene etc. are aromatic hydrocarbon based, ethoxyethyl acetate, the ester classes such as vinyl acetic monomer, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, the nitrogenous kind solvent such as METHYLPYRROLIDONE.Above-mentioned solvent can be used alone one, also can two kinds or two or more used in combination.
Four of object of the present invention is to provide a kind of copper-clad laminate, described copper-clad laminate, comprise at least one prepreg as above and be overlying on superimposed after the Copper Foil of prepreg both sides.Often open prepreg and comprise high-k glasscloth and by the as above high-k resin combination of the dry postadhesion of impregnation on high-k glasscloth.
The preparation method of copper-clad laminate of the present invention can be prepared by known method, exemplary method as: high-k resin combination of the present invention is made certain density glue, by dipping high-k glasscloth, then dry at a certain temperature, carry out semicure except desolventizing, obtain prepreg.Then get above-mentioned prepreg one or more to be superimposed together according to a definite sequence, Copper Foil is covered respectively the prepreg both sides be superimposed with each other, the obtained copper-clad laminate of solidification in thermocompressor, its solidification value is 150 ~ 250 DEG C, and solidifying pressure is 25 ~ 60Kgf/cm
2.
Compared with prior art, the present invention has following beneficial effect:
1. dicyclopentadiene type epoxy resin, dicyclopentadiene type ethylene rhodanate resin and active ester resinoid is adopted to reduce dielectric loss, the dielectric loss of dicyclopentadiene type epoxy resin and dicyclopentadiene type ethylene rhodanate resin is lower, and active ester and epoxy reaction do not generate polar group, dielectric properties are also very excellent;
2. high-k filler and high-k glasscloth is adopted to improve specific inductivity, in high-k copper-clad laminate, in order to make specific inductivity higher, usual use high-k filler, but only use high-k filler, specific inductivity is difficult to reach a higher level, and the present invention adopts high-k filler and high-k glasscloth to improve specific inductivity further simultaneously;
3. flexible-epoxy is adopted to improve stripping strength, in high-k copper-clad laminate, in order to make specific inductivity higher, the content of high-k filler is very high, thus the stripping strength of copper-clad laminate is reduced, the present invention adopts flexible-epoxy to improve stripping strength;
4. the copper-clad laminate that composite material with high dielectric constant of the present invention makes can reach the performances such as high-k, low-dielectric loss, high glass-transition temperature, high-peeling strength simultaneously, over-all properties is very excellent, avoid the problem that prior art brings other degradation while a certain performance improves, the performance requriements of high-k antenna substrate material can be met.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
For the above-mentioned high-k copper-clad laminate made, survey the performances such as its specific inductivity, dielectric loss, second-order transition temperature, stripping strength, following embodiment gives to describe in detail and describe further, and wherein the mass parts of organic resin is by organic solid quality part.
Embodiment 1
Get a suitable vessel, add the flexible-epoxy EXA-4816 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, the phenol type novolac epoxy PNE177 of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 26.8 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 415 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 10%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 1.
Embodiment 2
Get a suitable vessel, add the flexible-epoxy EXA-4822 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, the triphenol methylmethane type epoxy resin PN-501H of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 27.3 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 416 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 40%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 1.
Embodiment 3
Get a suitable vessel, add the flexible-epoxy EXA-4816 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, four phenolic group ethane type epoxy resin ON1031 of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 25.8 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 411 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 20%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 1.
Embodiment 4
Get a suitable vessel, add the flexible-epoxy EXA-4822 of 15 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 40 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, the triphenol methylmethane type epoxy resin PN-501H of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 40 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 218 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 10%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 1.
Embodiment 5
Get a suitable vessel, add the flexible-epoxy EXA-4816 of 5 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 15 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, the phenol type novolac epoxy PNE177 of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 10 mass parts, the active ester resinoid of 20 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 425 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 10%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 1.
Embodiment 6
Get a suitable vessel, add the flexible-epoxy EXA-4816 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, four phenolic group ethane type epoxy resin ON1031 of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 21.6 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 343 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 10%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 1.
The formula composition of each embodiment of table 1. and physical data thereof
Comparative example 1
Get a suitable vessel, add the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, the phenol type novolac epoxy PNE177 of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 24 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 369 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 10%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 2.
Comparative example 2:
Get a suitable vessel, add the flexible-epoxy EXA-4822 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, the triphenol methylmethane type epoxy resin PN-501H of 10 mass parts, the active ester resinoid of 54.6 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor DMAP, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 425 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 40%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 2.
Comparative example 3
Get a suitable vessel, add the flexible-epoxy EXA-4816 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, four phenolic group ethane type epoxy resin ON1031 of 10 mass parts, the linear phenolic resin TD-2090-60M of 24.3 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor glyoxal ethyline, continue to stir, finally add the dielectric constant of barium titanate filler BT-300 of 317 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with high-k glasscloth, and control, to suitable thickness (mass content controlling high-k glasscloth is 20%), then to dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 2.
Comparative example 4
Get a suitable vessel, add the flexible-epoxy EXA-4816 of 10 mass parts, the dicyclopentadiene type novolac epoxy HP-7200L of 30 mass parts, the brominated epoxy resin ICLON153-60M of 15 mass parts, four phenolic group ethane type epoxy resin ON1031 of 10 mass parts, the dicyclopentadiene type ethylene rhodanate resin XU-71787 of 25 mass parts, the active ester resinoid of 25.8 mass parts, and appropriate solvent carries out stirring certain hour, and then add appropriate promotor zinc octoate and DMAP, continue to stir.Finally add the dielectric constant of barium titanate filler BT-300 of 411 mass parts, fully stir, and carry out emulsion dispersion glue.Flood above-mentioned glue with common E type glasscloth, and control to suitable thickness (mass content controlling common E type glasscloth is 20%), then dry except desolventizing obtains prepreg.Use the prepreg obtained by several to be superimposed with each other, respectively cover a Copper Foil on both sides, put solidification in thermocompressor into and make described high-k copper-clad laminate.Glue formula composition and copper-clad laminate physical data table as shown in table 2.
The formula composition of each comparative example of table 2. and physical data thereof
The material enumerated in table 1 and table 2 is specific as follows:
EXA-4816: containing the flexible-epoxy of hydrocarbon structure long-chain, epoxy equivalent (weight) 400g/eq, Japanese Dainippon Ink Chemicals produces;
EXA-4822: containing hydrocarbon structure long-chain and hydrocarbon structure long-chain two ends containing the flexible-epoxy of ester bond, epoxy equivalent (weight) 390g/eq, Japanese Dainippon Ink Chemicals produces;
HP-7200L: dicyclopentadiene type novolac epoxy, epoxy equivalent (weight) 247g/eq, Japanese Dainippon Ink Chemicals produces;
EPICLON153-60M: brominated epoxy resin, epoxy equivalent (weight) 400g/eq, bromine content 46% ~ 50%, Wuxi Di Aisheng company produces;
PNE177: phenol type novolac epoxy, epoxy equivalent (weight) 177g/eq, Changchun, Taiwan artificial resin factory produces;
EPPN-501H: triphenol methylmethane type epoxy resin, epoxy equivalent (weight) 166g/eq, Japanese chemical drug company produces;
EPON1031: four phenolic group ethane type epoxy resin, epoxy equivalent (weight) 210g/eq, MOMENTIVE company of the U.S. produces;
XU-71787: dicyclopentadiene type ethylene rhodanate resin, DOW chemical company of the U.S. produces;
HPC-8000-65T: active ester resinoid, active ester equivalent 223g/eq, Japanese Dainippon Ink Chemicals produces;
TD-2090-60M: linear phenolic resin, hydroxyl equivalent 105g/eq, Japanese Dainippon Ink Chemicals produces;
BT-300: barium titanate filler, Shandong Sinocera Functional Materials Co., Ltd. produces.
The testing method of above characteristic is as follows:
(1) dielectric properties Dk/Df: adopt capacity plate antenna method to measure specific inductivity Dk and the dielectric loss Df of sheet material under 1GHz.
(2) second-order transition temperature T
g: measure according to the DMA method of IPC-TM-6502.4.24 defined.
(3) stripping strength PS: according to " after thermal stresses " experiment condition in IPC-TM-6502.4.8 method, the stripping strength of test sheet material.
Physical Property Analysis:
From table 1 and table 2, do not use flexible-epoxy in the resin formula of comparative example 1, stripping strength is less; Be used alone active ester resinoid solidifying agent in the resin formula of comparative example 2, although dielectric loss is lower, second-order transition temperature is on the low side; Use linear phenolic resin as solidifying agent in the resin formula of comparative example 3, although specific inductivity is higher, dielectric loss is bigger than normal; The resin formula of comparative example 4 is identical with the resin formula of embodiment 3, but embodiment 3 uses high-k glasscloth, and comparative example 4 uses common E type glasscloth, from the specific inductivity of table 1 and the known comparative example of table 24, comparatively embodiment 3 is low.
Combine the above results known, the copper-clad laminate that composite material with high dielectric constant of the present invention makes can reach the performances such as high-k, low-dielectric loss, high glass-transition temperature, high-peeling strength simultaneously, over-all properties is very excellent, avoid prior art while a certain performance improves bring the problem of other degradation, the performance requriements of high-k antenna substrate material can be met.
The above, be only preferred embodiment of the present invention, not the content of composition of the present invention is imposed any restrictions, for the person of ordinary skill of the art, other various corresponding change and distortion can be made according to technical scheme of the present invention and technical conceive, every above embodiment is done according to technical spirit of the present invention or composition composition or content any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (16)
1. a high-k resin combination, is characterized in that, described resin combination comprises:
(a) flexible-epoxy, its chemical structural formula is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10;
(b) dicyclopentadiene type novolac epoxy, its chemical structural formula is as follows:
In formula, n
2represent that average repeat unit is 1 ~ 10;
C () difunctional epoxy resin except epoxy resin described in above-mentioned (a) and (b) is or/and multiple functionality epoxide resin;
(d) dicyclopentadiene type ethylene rhodanate resin, its chemical structural formula is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5; With,
(e) active ester resinoid, its chemical structural formula is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25.
2. high-k resin combination as claimed in claim 1, it is characterized in that, described high-k resin combination also comprises high-k filler.
3. high-k resin combination as claimed in claim 1 or 2, it is characterized in that, described difunctional epoxy resin is the mixture of any one or at least two kinds in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin or isocyanate modified epoxy resin.
4. the high-k resin combination as described in one of claim 1-2, it is characterized in that, described multiple functionality epoxide resin is the mixture of any one or at least two kinds in novolac epoxy, triphenol methylmethane type epoxy resin or four phenolic group ethane type epoxy resin.
5. high-k resin combination as claimed in claim 4, it is characterized in that, described novolac epoxy is the mixture of any one or at least two kinds in phenol type novolac epoxy, ortho-cresol type novolac epoxy, bisphenol A-type novolac epoxy, biphenyl type novolac epoxy or naphthalene nucleus type novolac epoxy.
6. high-k resin combination as claimed in claim 2, it is characterized in that, described high-k filler is the high-dielectric constant inorganic particle with perovskite typed crystalline texture or composite perofskite type crystalline texture.
7. high-k resin combination as claimed in claim 6, it is characterized in that, described high-k filler is barium titanate, strontium titanate, magnesium titanate, calcium titanate, strontium-barium titanate, calcium barium titanate, lead titanate, Pb-based lanthanumdoped zirconate titanates, zirconium lanthanium titanate is plumbous, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnoniobate, barium magnesium niobate, Lithium niobium trioxide, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, the mixture of any one or at least two kinds in barium titanate rubidium or CaCu 3 Ti 4 O.
8. the high-k resin combination as described in one of claim 1-2, it is characterized in that, in resin combination, the non-volatility composition of component (a), (b), (c), (d) and (e) is in mass parts, described component (a) is 5 ~ 15 mass parts, described component (b) is 15 ~ 40 mass parts, described component (c) is 10 ~ 25 mass parts, described component (d) is 10 ~ 25 mass parts, and described component (e) is 20 ~ 40 mass parts.
9. high-k resin combination as claimed in claim 2, it is characterized in that, the quality of the non-volatility composition of high-k resin combination is 100wt%, and the quality of described high-k filler is 60 ~ 85wt%.
10. the high-k resin combination as described in one of claim 1-2, is characterized in that, described high-k resin combination comprises:
(a) flexible-epoxy, its chemical structural formula is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10;
(b) dicyclopentadiene type novolac epoxy, its chemical structural formula is as follows:
In formula, n
2represent that average repeat unit is 1 ~ 10;
C () difunctional epoxy resin except epoxy resin described in above-mentioned (a), (b) is or/and multiple functionality epoxide resin;
(d) dicyclopentadiene type ethylene rhodanate resin, its chemical structural formula is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5; With,
(e) active ester resinoid, its chemical structural formula is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25;
In resin combination, the non-volatility composition of component (a), (b), (c), (d) and (e) is in mass parts, described component (a) is 5 ~ 15 mass parts, described component (b) is 15 ~ 40 mass parts, described component (c) is 10 ~ 25 mass parts, described component (d) is 10 ~ 25 mass parts, and described component (e) is 20 ~ 40 mass parts;
F () high-k filler, the quality of the non-volatility composition of high-k resin combination is 100wt%, and the quality of high-k filler is 60 ~ 85wt%.
11. 1 kinds of composite material with high dielectric constants, is characterized in that, described matrix material comprises high-k resin combination as described in one of claim 1-10 and high-k glasscloth.
12. composite material with high dielectric constants as claimed in claim 11, it is characterized in that, the quality of composite material with high dielectric constant is 100wt%, the quality of described high-k glasscloth is 10 ~ 40wt%.
13. composite material with high dielectric constants as claimed in claim 12, is characterized in that, described composite material with high dielectric constant comprises (1) high-k resin combination and (2) high-k glasscloth,
Wherein, (1) high-k resin combination comprises:
(a) flexible-epoxy, its chemical structural formula is as follows:
In formula, R represents hydrocarbon structure long chain alkyl group or simultaneously containing hydrocarbon structure long-chain and the hydrocarbon structure long-chain two ends group containing ester bond, hydrocarbon structure long-chain is selected from C2 ~ C20 straight chained alkyl, C2 ~ C20 branched-chain alkyl, n
1represent that average repeat unit is 1 ~ 10;
(b) dicyclopentadiene type novolac epoxy, its chemical structural formula is as follows:
In formula, n
2represent that average repeat unit is 1 ~ 10;
C () difunctional epoxy resin except epoxy resin described in above-mentioned (a) and (b) is or/and multiple functionality epoxide resin;
(d) dicyclopentadiene type ethylene rhodanate resin, its chemical structural formula is as follows:
In formula, n
3represent that average repeat unit is 0 ~ 5; With,
(e) active ester resinoid, its chemical structural formula is as follows:
R in formula
1for phenyl ring or naphthalene nucleus, k is 0 or 1, n
4represent that average repeat unit is 0.25 ~ 1.25;
In resin combination, the non-volatility composition of component (a), (b), (c), (d) and (e) is in mass parts, described component (a) is 5 ~ 15 mass parts, described component (b) is 15 ~ 40 mass parts, described component (c) is 10 ~ 25 mass parts, described component (d) is 10 ~ 25 mass parts, and described component (e) is 20 ~ 40 mass parts;
F () high-k filler, the quality of the non-volatility composition of high-k resin combination is 100wt%, and the quality of high-k filler is 60 ~ 85wt%.
14. composite material with high dielectric constants as claimed in claim 11, is characterized in that, described high-k glasscloth is lead containing glass fibre or non-lead class is fiberglass braided forms.
15. 1 kinds of prepregs, is characterized in that, described prepreg comprises high-k glasscloth and by the high-k resin combination as described in claim 1-10 one of of the dry postadhesion of impregnation on high-k glasscloth.
16. 1 kinds of copper-clad laminates, comprise at least one prepreg as claimed in claim 15 and be overlying on superimposed after the Copper Foil of prepreg both sides.
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| CN201310307404.0A CN103351581B (en) | 2013-07-19 | 2013-07-19 | A kind of high-k resin combination and uses thereof |
| TW103114854A TW201504325A (en) | 2013-07-19 | 2014-04-24 | High-dielectric-constant resin composition and application thereof |
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| JP6237155B2 (en) * | 2013-11-22 | 2017-11-29 | 味の素株式会社 | Resin composition |
| US10266986B2 (en) * | 2014-02-21 | 2019-04-23 | Cocona, Inc. | Incorporation of active particles into substrates |
| AU2014411037B2 (en) * | 2014-11-11 | 2018-10-25 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and prepreg and laminated board prepared therefrom |
| CN105778412B (en) * | 2014-12-26 | 2018-05-29 | 广东生益科技股份有限公司 | A kind of composition epoxy resin and use its prepreg and laminate |
| CN106317771A (en) * | 2015-07-08 | 2017-01-11 | 深圳光启创新技术有限公司 | Prepreg, preparation method of prepreg and composite material |
| US10252965B2 (en) * | 2015-11-11 | 2019-04-09 | Air Water Inc. | Vinylbenzylated phenol compound, method of manufacturing vinylbenzylated phenol compound, activated ester resin, method of manufacturing activated ester resin, thermoset resin composition, hardened material of thermoset resin composition, interlayer insulating material, prepreg, and method of manufacturing prepreg |
| CN105482339B (en) * | 2016-01-16 | 2017-10-13 | 苏州大学 | A kind of lithium salts/polyacrylonitrile/thermoset ting resin composite and preparation method thereof |
| CN106189082B (en) * | 2016-07-12 | 2018-05-08 | 东莞市强亚电子材料有限公司 | A kind of fire retarded epoxy resin composition and application thereof |
| CN106084667B (en) * | 2016-07-12 | 2018-08-03 | 佛山市顺德区雅蕾新材料有限公司 | A kind of high-k composition epoxy resin and application thereof |
| CN106189083B (en) * | 2016-07-12 | 2018-05-15 | 江门建滔积层板有限公司 | A kind of copper-clad plate of glass fabric enhancing |
| CN106317402A (en) * | 2016-08-19 | 2017-01-11 | 浙江皇马科技股份有限公司 | Polyether monomer and preparation method and application thereof |
| WO2018033995A1 (en) * | 2016-08-19 | 2018-02-22 | 大阪有機化学工業株式会社 | Curable resin composition for forming easily strippable film, and process for producing same |
| CN106633153A (en) * | 2016-12-29 | 2017-05-10 | 哈尔滨理工大学 | Polymer-based dielectric energy storage nanocomposite material in three-layer structure and preparation method thereof |
| CN107746206B (en) * | 2017-10-31 | 2019-09-10 | 福州大学 | A kind of High-energy-storage density dielectric material and preparation method thereof |
| CN109971139A (en) * | 2019-03-29 | 2019-07-05 | 苏州威普达新材料有限公司 | A kind of communication equipment PBT-PET modified plastics |
| CN111825947B (en) * | 2019-04-22 | 2021-08-27 | 广东生益科技股份有限公司 | Resin composition for metal substrate, resin glue solution containing resin composition and metal-based copper-clad laminate |
| CN111825955B (en) * | 2020-07-23 | 2023-07-21 | 海南大学 | Prepreg for high frequency, preparation method thereof and copper-clad plate and preparation method thereof |
| CN112375192B (en) * | 2020-11-16 | 2022-11-04 | 上海彤程电子材料有限公司 | Phenolic aldehyde-aralkyl resin and preparation method and application thereof |
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- 2013-07-19 CN CN201310307404.0A patent/CN103351581B/en not_active Expired - Fee Related
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| CN101974205A (en) * | 2010-08-20 | 2011-02-16 | 广东生益科技股份有限公司 | Resin composition for embedded capacitor, and dielectric layer and metal foil-clad plate manufactured by using same |
| CN101967265A (en) * | 2010-08-31 | 2011-02-09 | 广东生益科技股份有限公司 | High-frequency resin composition and high-frequency circuit substrate manufactured by using same |
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