CN103937157A - Halogen-free resin composition and method for manufacturing prepreg and laminated board by using halogen-free resin composition - Google Patents
Halogen-free resin composition and method for manufacturing prepreg and laminated board by using halogen-free resin composition Download PDFInfo
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Abstract
The present invention discloses a halogen-free resin composition and a method for manufacturing a prepreg and a laminated board by using the halogen-free resin composition. The halogen-free resin composition is prepared by dispersing the following components in an organic solvent, wherein the components comprise, by weight, 10-100 parts of a halogen-free epoxy resin, 10-80 parts of cyanate, 10-70 parts of an anhydride curing agent, 10-100 parts of a benzoxazine resin, 0.01-1.0 part of a curing accelerator, 1-15 parts of a toughening agent, 0-50 parts of a fire retardation agent, and 0-100 parts of an inorganic filler, and the solid content of the halogen-free resin composition is 30-70 wt%. The prepared prepreg and the copper foil-clad laminated board have characteristics of good heat resistance, high glass-transition temperature, low water absorption rate, excellent fire retardation, low dielectric constant and low dielectric loss factor.
Description
Technical field
The invention belongs to polymer composite and manufacture field, be specifically related to a kind of halogen-free resin composition, and adopt this halogen-free resin composition to manufacture the method for prepreg and used for printed circuit veneer sheet.
Background technology
In recent years, along with the fast development of cloud computing and mobile Internet, the transmission capacity of signal is increasing, and transmission speed is more and more faster, and signal processing frequency is to high frequency future development.The specific inductivity of circuit substrate (Dk) and dielectric loss factor (Df) have larger impact to the signal transmission of end product, high Dk can make signal transmission rate slack-off, high Df can make signal section electromagnetic energy be converted into heat energy loss in baseplate material, larger on the transmission impact of high-frequency signal.Therefore, reduce the Dk of circuit substrate and the focus that Df becomes research in copper-clad plate industry.
In order to reduce copper-clad laminate specific inductivity and dielectric loss, the researchist of the art adopts the resin system of other low-ks and the low dielectric loss factor to replace common epoxy-resin systems, as: cyanate, polyphenylene oxide, polyimide resin, tetrafluoroethylene, TPO, vinylbenzene-bis-copolymer-maleic anhydrides etc.Wherein, cyanate has obtained more application due to its lower specific inductivity with compared with the low dielectric loss factor and good processing characteristics in high-frequency copper-clad plate field, but it also has the defect of self, as high in water-intake rate, humidity resistance is poor, fragility is large, when application, need to carry out modification to it.
For making the resin combination of circuit substrate, conventionally need to have flame retardant resistance, traditional product custom is used brominated resin combination or is added containing bromine addition in resin combination, realizes the fire-retardant object of circuit substrate.In recent years along with the promulgation of Rosh and WEEE instruction, and the enhancing of common people's environmental consciousness, the non-halogen trend of circuit substrate is more and more obvious.For realizing circuit substrate halogen-free flameproof, its method be generally in resin matrix, add the flame retardant resistance element resins such as phosphorous, nitrogen, silicon or addition type is phosphorous, containing nitrogen combustion inhibitor.
No. 46-41112, Japanese Patent examined patent publication, JP 50-132099 communique and JP 57-143320 communique are used the ordinary epoxy resins such as bisphenol A type epoxy resin, brominated bisphenol a type epoxy resin, phenol aldehyde type epoxy resin to mix with cyanate, form resin combination.This resin combination is improving aspect toughness and humidity resistance compared with cyanate, but large lossy the dielectric properties of cyanate ester resin, resin system is for there being halogen system simultaneously.
Summary of the invention
The invention provides a kind of halogen-free resin composition, this resin combination has good dielectric properties, thermal characteristics and higher second-order transition temperature, can meet the application requiring of high-frequency high-speed circuit substrate.
The present invention also provides a kind of method that adopts above-mentioned halogen-free resin composition to manufacture prepreg, and its prepared prepreg has the feature of the flame retardant resistance of low-k, the low dielectric loss factor, thermotolerance, low water absorption, high glass-transition temperature and excellence.
The present invention also provides a kind of method that adopts above-mentioned prepreg to manufacture laminate for printed circuits, and its prepared veneer sheet has the feature of the flame retardant resistance of low-k, the low dielectric loss factor, low water absorption, high heat resistance, high glass-transition temperature and excellence.
The present invention takes following technical scheme: a kind of halogen-free resin composition, this resin combination comprises each component of following parts by weight: 10～100 parts of halogen-free epoxy resins, cyanate 10～80,10～70 parts of anhydride curing agents, 10～100 parts of benzoxazine colophonies, 0.01～1.0 part of curing catalyst, 1～15 part of toughner, 0～50 part of fire retardant, 0～100 part of mineral filler, by said ratio, each component is scattered in organic solvent, obtains the resin combination that solid content is 30wt%～70wt%.
As preferably, halogen-free epoxy resin is phosphorous epoxy resin, nitrogen-containing epoxy thermoset, containing one or more combinations in epoxy silicone, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene nucleus type epoxy resin, double bond containing modified epoxy.
Preferably, increase phosphorous epoxy resin and benzoxazine.Benzoxazine is a kind of more special solidifying agent, itself can self cure, and also its carbon yield is higher, and Nitrogen element, has good flame retardant resistance.Phosphorous epoxy resin plays fire retardation.
As preferably, cyanate is one or more combinations in bisphenol A cyanate ester, dicyclopentadiene bisphenol type cyanate, Novolac Cyanate Eater Resin, polyfunctional group type cyanate, tetramethyl-Bisphenol F type cyanate, bis-phenol M type cyanate, Bisphenol F type cyanate, bisphenol E-type cyanate, bisphenol A cyanate ester prepolymer.
As preferably, anhydride curing agent is the alternating copolymer of vinylbenzene and maleic anhydride, and the mol ratio of vinylbenzene and maleic anhydride is 1～12:1, and the weight-average molecular weight of its multipolymer (Mw) is 1000～60000.
As preferably, benzoxazine colophony is bisphenol A-type benzoxazine colophony, Bisphenol F type benzoxazine colophony, allyl group bisphenol A-type benzoxazine colophony, 4, one or more combinations in 4 '-diaminodiphenylmethane type benzoxazine colophony.
As preferably, curing catalyst is one or more combinations in glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecyl imidazole.
As preferably, toughner is one or more combinations in nbr carboxyl terminal, epoxy terminated butyronitrile paracril, hydroxy'terminated butadiene nitrile rubber, phenoxy resin, core shell rubbers, acrylate elastomer, isocyanate modified epoxy resin, rubber modified epoxy resin.
As preferably, fire retardant is that halogen-free flame retardants is one or more combinations in hypophosphite, phosphonitrile, phosphoric acid ester, trimeric cyanamide urate.
As preferably, mineral filler is one or more combinations in aluminum oxide, aluminium hydroxide, aluminium nitride, boron nitride, boehmite, talcum, mica, kaolin, light calcium carbonate, magnesium hydroxide, fused silica, silicon powder, preparing spherical SiO 2, clay, zinc borate.
As preferably, organic solvent is one or more combinations in acetone, butanone, pimelinketone, ethyl acetate, toluene, ether, DMF, N,N-dimethylacetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.The solid content of the compositions of thermosetting resin that the preparation of interpolation organic solvent obtains is 30-70wt%, has good processibility.
The present invention adopts above-mentioned halogen-free resin composition to manufacture the method for prepreg, and it takes following technical scheme: by above-mentioned halogen-free resin composition mixing and stirring, make finely dispersed prepreg; By glass-fiber-fabric, flood aforesaid prepreg, then at 80～180 ℃, toast 2～15 minutes, can make described prepreg.
The present invention adopts above-mentioned prepreg to manufacture the method for high-frequency high-speed substrate (veneer sheet) for circuit, its technical scheme is as follows: by above-mentioned prepreg, one or more layers is superimposed with each other and forms layer of prepreg, one or both sides in layer of prepreg are covered with tinsel, at 0.5MPa～5MPa pressure and 150 ℃～250 ℃ temperatures 1-5 processed hour, form.
The present invention has following technique effect:
(1) halogen-free resin composition of the present invention, has good thermotolerance, high glass-transition temperature, low water absorption, excellent advantages such as flame retardant resistance, low-k and the low dielectric loss factor.
(2) use prepreg and the copper-clad laminate that above-mentioned halogen-free resin composition makes to there is good thermotolerance, high glass-transition temperature, flame retardant resistance, low-k and the low dielectric loss factor of low water absorption, excellence.
Embodiment
Below the preferred embodiment of the present invention is elaborated.
Embodiment 1
Get dicyclopentadiene (DCPD) type epoxy resin (XD-1000, Japan's chemical drug) 25 parts, phosphorous epoxy resin (XZ92530, DOW) 20 parts, bisphenol A cyanate ester resin (BA-3000S, Lonza) 45 parts, anhydride curing agent (SMA EF40, Sartomer) 10 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 15 parts, 0.08 part of glyoxal ethyline (four countries change into), nbr carboxyl terminal (1072CG, Zeon Corporation) 5 parts, preparing spherical SiO 2 (SFP-30M, DENKA) 40 parts, with butanone solvent, regulating the solid content of resin combination is 40wt%.
This compositions of thermosetting resin is flooded and be coated on E type woven fiber glass (2116, substance 104g/m
2) upper, and toast the prepreg that 4min makes resin content 50% in 170 ℃ of baking ovens.
By the prepreg of the resin content making 50%, respectively put up and down a Copper Foil, be placed in vacuum hotpressing machine compacting and obtain copper-clad laminate.Concrete process for pressing is under 2MPa pressure, and 200 ℃ of temperatures are closed 2 hours.
The specific inductivity (Dk), dielectric loss factor (Df), second-order transition temperature (Tg), stripping strength, thermotolerance, water-intake rate, flame retardant resistance, the impelling strength that detect copper-clad laminate, concrete outcome is in Table 1.
Embodiment 2
Get biphenyl type epoxy resin (NC-3000, Japan's chemical drug) 50 parts, bisphenol A cyanate ester resin (CY-1, Wuqiao, Jiangdu resin processing plant) 30 parts, anhydride curing agent (SMA EF40, Sartomer) 12 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 40 parts, 0.12 part of 2-ethyl-4-methylimidazole (four countries change into), core shell rubbers (Fortegra351, DOW Chemical) 3 parts, hypo-aluminum orthophosphate (OP935, Germany Clariant company) 5 parts, 50 parts of molten silicon micro mists (East Sea, Lianyun Harbour silicon powder), boehmite (BS100, lime is closed in river) 20 parts, with butanone solvent, regulating the solid content of resin combination is 60wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
Embodiment 3
Get dicyclopentadiene (DCPD) type epoxy resin (XD-1000, Japan's chemical drug) 30 parts, phosphorous epoxy resin (XZ92530, DOW) 10 parts, dicyclopentadiene type ethylene rhodanate resin (CY-3, Wuqiao, Jiangdu resin processing plant) 50 parts, anhydride curing agent (SMA EF60, Sartomer) 15 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 20 parts, 0.06 part of 2-ethyl-4-methylimidazole (four countries change into), rubber modified epoxy resin (EponResin58005, Hexion Specialty Chemicals, Inc.) 10 parts, large eight chemistry of PX-200(Japan) 6 parts, preparing spherical SiO 2 (SFP-30M, DENKA) 50 parts, with butanone solvent, regulating the solid content of resin combination is 50wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
Embodiment 4
Get dicyclopentadiene (DCPD) type epoxy resin (XD-1000, Japan's chemical drug) 40 parts, bisphenol A cyanate ester prepolymer (CY-10, Wuqiao, Jiangdu resin processing plant) 40 parts, anhydride curing agent (SMA EF40, Sartomer) 8 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 30 parts, 0.06 part of 2-ethyl-4-methylimidazole (four countries change into), core shell rubbers (Fortegra351, DOW Chemical) 6 parts, SPB-100(Japan large tomb chemistry) 8 parts, preparing spherical SiO 2 (SFP-30M, DENKA) 50 parts, with butanone solvent, regulating the solid content of resin combination is 30wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
Embodiment 5
Get biphenyl type epoxy resin (NC-3000, Japan's chemical drug) 60 parts, phosphorous epoxy resin (XZ92530, DOW) 25 parts, bisphenol A cyanate ester resin (CY-1, Wuqiao, Jiangdu resin processing plant) 70 parts, anhydride curing agent (SMA EF60, Sartomer) 18 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 40 parts, 0.2 part of 2-ethyl-4-methylimidazole (four countries change into), core shell rubbers (Fortegra351, DOW Chemical) 8 parts, 50 parts of molten silicon micro mists (East Sea, Lianyun Harbour silicon powder), boehmite (BS100, lime is closed in river) 20 parts, with butanone solvent, regulating the solid content of resin combination is 70wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
Embodiment 6
Get dicyclopentadiene (DCPD) type epoxy resin (XD-1000, Japan's chemical drug) 70 parts, bisphenol A cyanate ester prepolymer (CY-10, Wuqiao, Jiangdu resin processing plant) 40 parts, anhydride curing agent (SMA EF40, Sartomer) 20 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 35 parts, 0.3 part of 2-ethyl-4-methylimidazole (four countries change into), core shell rubbers (Fortegra351, DOW Chemical) 5 parts, SPB-100(Japan large tomb chemistry) 10 parts, preparing spherical SiO 2 (SFP-30M, DENKA) 70 parts, with butanone solvent, regulating the solid content of resin combination is 50wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
Embodiment 7
Get dicyclopentadiene (DCPD) type epoxy resin (XD-1000, Japan's chemical drug) 70 parts, phosphorous epoxy resin (XZ92530, DOW) 15 parts, bisphenol A cyanate ester prepolymer (CY-10, Wuqiao, Jiangdu resin processing plant) 30 parts, anhydride curing agent (SMA EF40, Sartomer) 8 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 50 parts, 0.25 part of 2-ethyl-4-methylimidazole (four countries change into), core shell rubbers (Fortegra351, DOW Chemical) 3 parts, preparing spherical SiO 2 (SFP-30M, DENKA) 50 parts, boehmite (BS100, lime is closed in river) 10 parts, with butanone solvent, regulating the solid content of resin combination is 60wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
Embodiment 8
Get biphenyl type epoxy resin (NC-3000, Japan's chemical drug) 50 parts, bisphenol A cyanate ester resin (CY-1, Wuqiao, Jiangdu resin processing plant) 20 parts, anhydride curing agent (SMA EF40, Sartomer) 15 parts, benzoxazine (XTW8291, the graceful advanced material of Hensel) 50 parts, 0.25 part of 2-ethyl-4-methylimidazole (four countries change into), core shell rubbers (Fortegra351, DOW Chemical) 8 parts, hypo-aluminum orthophosphate (OP935, Germany Clariant company) 6 parts, 40 parts of molten silicon micro mists (East Sea, Lianyun Harbour silicon powder), boehmite (BS100, lime is closed in river) 40 parts, with butanone solvent, regulating the solid content of resin combination is 30wt%.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.
The performance of copper-clad laminate is as shown in table 1.
The performance of table 1 copper-clad laminate
As can be known from the above table, the present invention makes copper-clad laminate excellent performance, and its copper-clad laminate Dk, Df be low, have good PCT, lower water-absorbent, and its flame retardant properties reaches UL-94V-0 level, is suitable for use in high-frequency high-speed printed electronic circuit.
To sum up, halogen-free resin composition of the present invention has good dielectric properties, thermotolerance and higher second-order transition temperature, can meet the application requiring of high-frequency high-speed circuit substrate.
Starting material consumption and proportioning related in above-described embodiment are weight proportion, and each raw material if no special instructions, all can be obtained by commercially available.
Above the preferred embodiments of the present invention are had been described in detail, for those of ordinary skill in the art, according to thought provided by the invention, in embodiment, will change, and these changes also should be considered as protection scope of the present invention.
Claims (10)
1. a halogen-free resin composition, it is characterized in that, this halogen-free resin composition is scattered in organic solvent and is made by each components of following parts by weight: 10～100 parts of halogen-free epoxy resins, cyanate 10～80,10～70 parts of anhydride curing agents, 10～100 parts of benzoxazine colophonies, 0.01～1.0 part of curing catalyst, 1～15 part of toughner, 0～50 part of fire retardant, 0～100 part of mineral filler, the solid content of described halogen-free resin composition is 30wt%～70wt%.
2. halogen-free resin composition according to claim 1, it is characterized in that, described halogen-free epoxy resin is phosphorous epoxy resin, nitrogen-containing epoxy thermoset, containing one or more combinations in epoxy silicone, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene nucleus type epoxy resin, double bond containing modified epoxy.
3. halogen-free resin composition according to claim 1, it is characterized in that, described cyanate is one or more combinations in bisphenol A cyanate ester, dicyclopentadiene bisphenol type cyanate, Novolac Cyanate Eater Resin, polyfunctional group type cyanate, tetramethyl-Bisphenol F type cyanate, bis-phenol M type cyanate, Bisphenol F type cyanate, bisphenol E-type cyanate, bisphenol A cyanate ester prepolymer.
4. halogen-free resin composition according to claim 1, it is characterized in that, described anhydride curing agent is the alternating copolymer of vinylbenzene and maleic anhydride, and the mol ratio of vinylbenzene and maleic anhydride is 1～12:1, and the weight-average molecular weight of multipolymer is 1000～60000.
5. halogen-free resin composition according to claim 1, it is characterized in that, described benzoxazine colophony is bisphenol A-type benzoxazine colophony, Bisphenol F type benzoxazine colophony, allyl group bisphenol A-type benzoxazine colophony, 4, one or more combinations in 4 '-diaminodiphenylmethane type benzoxazine colophony.
6. according to the halogen-free resin composition described in claim 1-5 any one, it is characterized in that, described curing catalyst is one or more combinations in glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecyl imidazole.
7. according to the halogen-free resin composition described in claim 1-5 any one, it is characterized in that, described toughner is one or more combinations in nbr carboxyl terminal, epoxy terminated butyronitrile paracril, hydroxy'terminated butadiene nitrile rubber, phenoxy resin, core shell rubbers, acrylate elastomer, isocyanate modified epoxy resin, rubber modified epoxy resin.
8. according to the halogen-free resin composition described in claim 1-5 any one, it is characterized in that, described fire retardant is that halogen-free flame retardants is one or more combinations in hypophosphite, phosphonitrile, phosphoric acid ester, trimeric cyanamide urate;
Or described mineral filler is one or more combinations in aluminum oxide, aluminium hydroxide, aluminium nitride, boron nitride, boehmite, talcum, mica, kaolin, light calcium carbonate, magnesium hydroxide, fused silica, silicon powder, preparing spherical SiO 2, clay, zinc borate.
9. a manufacture method for prepreg, is characterized in that as follows: by the halogen-free resin composition mixing and stirring described in claim 1-8, make finely dispersed prepreg; By the described prepreg of glass-fiber-fabric dipping, then at 80～180 ℃, toast 2～15 minutes, make described prepreg.
10. the manufacture method of a veneer sheet, it is characterized in that as follows: one or more layers is stacked and form layer of prepreg for the prepreg that manufacture method described in claim 9 is obtained, one or both sides in layer of prepreg are covered with tinsel, then 0.5～5MPa pressure and 150～250 ℃ of temperatures systems 1～5 hour.
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Application publication date: 20140723 |