CN102558858A - Resin compound for copper-coated laminated boards and prepreg - Google Patents
Resin compound for copper-coated laminated boards and prepreg Download PDFInfo
- Publication number
- CN102558858A CN102558858A CN2011104356651A CN201110435665A CN102558858A CN 102558858 A CN102558858 A CN 102558858A CN 2011104356651 A CN2011104356651 A CN 2011104356651A CN 201110435665 A CN201110435665 A CN 201110435665A CN 102558858 A CN102558858 A CN 102558858A
- Authority
- CN
- China
- Prior art keywords
- resin
- mass parts
- resin combination
- combination according
- mineral filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a resin compound for copper-coated laminated boards. The resin compound comprises 100 weight parts of epoxy resin, 50 to 200 weight parts of high-performance resin, 10 to 50 weight parts of polytetrafluoroethylene of which the surface is treated, 20 to 100 weight parts of inorganic filler of which the surface is treated, and 0 to 50 weight parts of curing agents. The resin compound has the advantages that the epoxy resin is modified by adopting the high-performance resin, so that the heat resistant performance and the dielectric performance of the resin compound are improved; the polytetrafluoroethylene of which the surface is treated is adopted by the resin compound, so that the dielectric performance and the flame retardant performance of the compound can be improved and the moisture absorption performance of the compound can be reduced on the premise that the high temperature resistant performance is guaranteed; the inorganic filler of which the surface is treated is adopted by the resin compound, so that the thermal expansibility of the compound can be reduced; and the resin compound is suitable for the high-frequency and high-heat-resistant copper-coated laminated boards and can satisfy the requirements for the processing and the assembly of printed circuit boards.
Description
Technical field
The invention belongs to the resin combination technical field, relate in particular to a kind of resin composition for copper clad laminate and prepreg.
Background technology
Copper clad laminate is with electronics glass cloth or other strongthener solvent impregnated resins, and one side or two-sided covering with Copper Foil and the board-like material processed through hot pressing are called copper-clad plate again.Copper-clad plate is a printed substrate ground foundation material; Effect to main its interconnected conducting of printed circuit board, insulation and support; Transmission speed, power loss and natural impedance etc. to signal in the circuit have considerable influence; Therefore, the performance of printed circuit board, quality, processibility, stability, safety etc. depend on copper-clad plate to a great extent.
Copper-clad plate mainly is made up of Copper Foil, base material and tackiness agent three parts.Make copper-clad plate tackiness agent commonly used resol, epoxy resin, polyimide resin, cyanate ester resin, polyphenylene oxide resin, BT resin etc. are arranged; Because epoxy resin has advantages such as raw material sources are extensive, processibility good, cost is lower, in the FR-4 veneer sheet, obtain using in a large number and widely.But; Along with the high capacity of the signal of the employed electronics in information communication field and the development of high speed; In order to keep the safety from the MHz frequency band to the high field of GHz frequency band, the FR-4 veneer sheet need satisfy high glass-transition temperature (Tg), low-k requirements such as (ε r).But ordinary epoxy resin has shortcomings such as thermotolerance is low, specific inductivity is big, is difficult to satisfy requirement heat-resisting, high frequency.
It is to improve one of effective ways of epoxy resin resistance toheat and dielectric properties that epoxy resin is carried out modification, and prior art discloses multiple method of epoxy resin being carried out modification.Like human cyanate ester resins such as Shimp epoxy resin is carried out modification, cyanate modified epoxy can improve wet-hot aging performance, dielectric properties and the resistance toheat of epoxy resin; People such as Ishihara kaivo add dielectric properties, resistance toheat and the water resistance that linear phenolic resin can improve veneer sheet in epoxy resin; The glass cloth laminated board that obtains behind usefulness benzoxazine such as Wang Jing and the epoxy blend has excellent mechanical property, thermotolerance, electrical insulating property and water tolerance; People such as Su Minshe are better through the dielectric properties of the PPO/ epoxy glass copper-clad plate that the molecular weight that reduces ppe, the methods such as polar group, adding compatilizer of in the ppe molecule, introducing obtain.Above-mentioned employing performance resins carries out thermotolerance and the dielectricity that modification all can improve resin combination to epoxy resin, still, compares with high frequency substrate, and its dielectric properties are still relatively poor, can reduce the dielectric properties of the copper-clad plate that obtains.
Summary of the invention
In view of this; The technical problem that the present invention will solve is to provide a kind of resin composition for copper clad laminate and prepreg; Resin combination provided by the invention has higher thermotolerance, excellent dielectric properties, lower hot expansibility and better machining property, can be used for the high frequency copper clad laminate.
The invention provides a kind of resin composition for copper clad laminate, comprising:
The epoxy resin of 100 mass parts;
The performance resins of 50～200 mass parts;
The tetrafluoroethylene of 10～50 mass parts, said tetrafluoroethylene is through surface treatment;
The mineral filler of 20～100 mass parts, said mineral filler is through surface treatment;
The solidifying agent of 0～50 mass parts.
Preferably, said epoxy resin is one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phenol aldehyde type epoxy resin and the biphenyl type resol.
Preferably, said performance resins is one or more in cyanate ester resin, modified polyphenylene ether resin, benzoxazine colophony and the bimaleimide resin.
Preferably, said tetrafluoroethylene is through one or more surface treatments in cationic styrene base amido, ten trifluoro octyltri-ethoxysilane, 3-aminopropyl triethoxysilane and the water-soluble modified fluorosilicone.
Preferably, the particle diameter of said tetrafluoroethylene is 0.1 μ m-10 μ m.
Preferably; Said mineral filler is through γ-An Bingjisanyiyangjiguiwan, γ-(2; 3-glycidoxy propyl group) one or more surface treatments in Trimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane and the β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan.
Preferably, said mineral filler is one or more in silicon powder, aluminum oxide, Natural manganese dioxide, wollastonite, boehmite, clay, talcum, mica, kaolin, permanent white, lime carbonate and the zinc borate.
Preferably, the particle diameter of said mineral filler is 0.05 μ m～5 μ m.
Preferably, said solidifying agent be in 4,4, MDA, diaminodiphenyl oxide, the nitrogenous resol of triazine modification and the acid anhydrides one or more.
The present invention also provides a kind of prepreg that utilizes the described resin combination preparation of technique scheme.
Compared with prior art, resin composition for copper clad laminate provided by the invention comprises: the epoxy resin of 100 mass parts; The performance resins of 50～200 mass parts; The tetrafluoroethylene of 10～50 mass parts, said tetrafluoroethylene is through surface treatment; The mineral filler of 20～100 mass parts, said mineral filler is through surface treatment; The solidifying agent of 0～50 mass parts.The present invention adopts performance resins that epoxy resin is carried out modification, improves the resistance toheat and the dielectric properties of resin combination; The present invention adopts surface treated tetrafluoroethylene, can under the prerequisite that guarantees resistance to elevated temperatures, improve the dielectric properties and the flame retardant properties of compsn, and reduce the hygroscopic property of compsn; The present invention adopts surface treated mineral filler, can reduce the thermal expansivity of compsn.Therefore; Resin composition for copper clad laminate provided by the invention has good heat-resistant, dielectric properties, flame retardant properties, processing characteristics, lower hot expansibility and lower hygroscopic property; Be applicable to high frequency, high heat-resisting copper clad laminate, can satisfy the requirement of printed circuit board processing and assembling.Experiment shows, adopts the second-order transition temperature of the copper clad laminate that resin combination provided by the invention and glasscloth substrate preparation obtain higher, and specific inductivity is lower, water-intake rate is lower, flame retardant properties is better.
Embodiment
The invention provides a kind of resin composition for copper clad laminate, comprising:
The epoxy resin of 100 mass parts;
The performance resins of 50～200 mass parts;
The tetrafluoroethylene of 10～50 mass parts, said tetrafluoroethylene is through surface treatment;
The mineral filler of 20～100 mass parts, said mineral filler is through surface treatment;
The solidifying agent of 0～50 mass parts.
Resin combination provided by the invention comprises the epoxy resin of 100 mass parts; Said epoxy resin is elected no bromine epoxy resin as; More preferably one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phenol aldehyde type epoxy resin and the biphenyl type resol most preferably are bisphenol A epoxide resin.
Resin combination provided by the invention also comprises performance resins, and said performance resins can improve the resistance toheat and the dielectric properties of epoxy resin as properties-correcting agent.Said performance resins is meant fire resistant resin, is the resin more than 200 ℃ like fusing point.Said performance resins is preferably cyanate ester resin well known to those skilled in the art, Noryl, resol, benzoxazine, Noryl, span and comes amide resins etc.; Be preferably cyanate ester resin, Noryl, benzoxazine and span and come in the amide resins one or more, more preferably cyanate ester resin, Noryl or benzoxazine.The content of said performance resins is 50～200 mass parts, is preferably 70～180 mass parts, more preferably 90～150 mass parts.
Resin combination provided by the invention also comprises tetrafluoroethylene, and said tetrafluoroethylene is surface treated tetrafluoroethylene.Said tetrafluoroethylene has good temperature resistance ability, dielectric properties and flame retardant properties, it is carried out can under the prerequisite that guarantees resistance to elevated temperatures, improving the dielectric properties and the flame retardant properties of compsn after the surface treatment, and reduce the hygroscopic property of compsn.In the present invention; One or more surface treatment agents that said tetrafluoroethylene preferably passes through in cationic styrene base amido (Z-6032), ten trifluoro octyltri-ethoxysilane (F8261), 3-aminopropyl triethoxysilane (AMEO) and the water-soluble modified fluorosilicone (F8800) carry out surface treatment; Be the present invention preferably with in cationic styrene base amido, ten trifluoro octyltri-ethoxysilane, 3-aminopropyl triethoxysilane and the water-soluble modified fluorosilicone one or more, more preferably as surface treatment agent tetrafluoroethylene is carried out surface treatment with ten trifluoro octyltri-ethoxysilane.The present invention does not have particular restriction to said surface-treated method, and method well known to those skilled in the art gets final product, and can be following method: with tetrafluoroethylene and surface-modifying agent thorough mixing in organic solvent, obtain surface treated tetrafluoroethylene.Said organic solvent is preferably one or more in acetone, N and the EGME, more preferably the mixed solution of acetone and N or N.
In said surface treated tetrafluoroethylene, said surface treatment agent preferably accounts for the 3wt%～10wt% of said tetrafluoroethylene, more preferably 4wt%～8wt%; The particle diameter of said tetrafluoroethylene is preferably 0.1 μ m～10 μ m, more preferably 0.5 μ m～9 μ m.
In the present invention, the content of said tetrafluoroethylene is 10～50 mass parts, is preferably 15～45 mass parts.
Also comprise mineral filler in the resin combination provided by the invention, said mineral filler is surface treated mineral filler.Said mineral filler has good wear resistance, through reducing the thermal expansivity of resin combination after the surface treatment.In the present invention; Said mineral filler is through surface treatment; Preferably pass through γ-An Bingjisanyiyangjiguiwan, γ-(2; 3-glycidoxy propyl group) one or more surface treatments in Trimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane and the β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan.That is to say; The present invention is preferably with γ-An Bingjisanyiyangjiguiwan, γ-(2; 3-glycidoxy propyl group) Trimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane and β-(3; The 4-epoxycyclohexyl) one or more in the ethyl trimethoxy silane more preferably carry out surface treatment as surface treatment agent to said mineral filler with γ-(2,3-glycidoxy propyl group) Trimethoxy silane.The present invention does not have particular restriction to said surface-treated method, and method well known to those skilled in the art gets final product, and can be following method: with mineral filler and surface-modifying agent thorough mixing in organic solvent, obtain surface treated mineral filler.Said organic solvent is preferably one or more in acetone, N and the EGME, more preferably the mixed solution of acetone and N or N.
In said surface treated mineral filler, said surface treatment agent preferably accounts for the 3wt%～10wt% of said mineral filler, more preferably 4wt%～8wt%; Said mineral filler is preferably one or more in silicon powder, aluminum oxide, Natural manganese dioxide, wollastonite, boehmite, clay, talcum, mica, kaolin, permanent white, lime carbonate and the zinc borate, more preferably silicon powder; The particle diameter of said mineral filler is preferably 0.1 μ m～10 μ m, more preferably 0.5 μ m～9 μ m.
In the present invention, the content of said mineral filler is 20～100 mass parts, is preferably 25～95 mass parts.
Resin combination provided by the invention also comprises solidifying agent, and the present invention does not have particular restriction to the kind of said solidifying agent, is preferably 4,4 (DDS), MDA
(DDM), in diaminodiphenyl oxide, the nitrogenous resol of triazine modification and the acid anhydrides one or more, DDM more preferably.Said solidifying agent is preferably 0～50 mass parts at the content of said resin combination, more preferably 10～40 mass parts.
Said resin combination is mixed with organic solvent, be mixed with and promptly can be used as sticker behind the colloidal solution of desired concn and use.Said organic solvent is preferably one or more in acetone, N and the EGME, more preferably the mixed solution of acetone and N or N.The present invention does not have particular restriction to the concentration of said colloidal solution, and those skilled in the art can confirm according to title product voluntarily.
Resin combination provided by the invention can be used for preparing prepreg, may further comprise the steps:
A) the described resin combination of technique scheme is dissolved in the solvent, obtains resin solution;
B) base material is immersed in the resin solution that step a) obtains;
C) obtain prepreg after the curing.
The present invention at first is dissolved in the described resin combination of technique scheme in the solvent, obtains resin solution.Said solvent is preferably one or more in acetone, N and the EGME, more preferably the mixed solution of acetone and N or N.The present invention does not have particular restriction to the concentration of said resin solution, and those skilled in the art can confirm according to title product voluntarily.
After obtaining resin solution, base material impregnated in the said resin solution, obtain prepreg after the curing.In the present invention, said base material is preferably glasscloth; Said solidification value is preferably 100 ℃～200 ℃, more preferably 120 ℃～180 ℃; Be preferably 3min～7min said set time.
Resin combination provided by the invention can also be used to prepare copper clad laminate, may further comprise the steps:
A) the described resin combination of technique scheme is dissolved in the solvent, obtains resin solution;
B) base material is immersed in the resin solution that step a) obtains;
C) obtain prepreg after the curing;
D) join many prepregs that make are folded, the surface is covered with Copper Foil, obtains copper clad laminate after the pressing.
After obtaining some prepregs according to the described method of technique scheme, with many prepregs are folded join after, place Copper Foils on folded two surfaces of joining the product that obtains, obtaining copper clad laminate after the pressing under the condition of heating and pressurizing.The present invention does not have particular restriction to said Copper Foil, and those skilled in the art can carry out the selection of Copper Foil according to title product.In the present invention, the temperature of said pressing is preferably 150 ℃～250 ℃, and more preferably 180 ℃～200 ℃, the pressure of said pressing is preferably 1.5MPa～3.5MPa, more preferably 2MPa～3MPa; The time of said pressing is preferably 1.5h～3h, more preferably 2h～2.5h.
After obtaining copper clad laminate, it is carried out performance test, the result shows, the copper clad laminate that resin combination provided by the invention obtains has high glass transition, lower specific inductivity, lower water-intake rate and good water-intake rate.
Resin composition for copper clad laminate provided by the invention comprises: the epoxy resin of 100 mass parts; The performance resins of 50～200 mass parts; The tetrafluoroethylene of 10～50 mass parts, said tetrafluoroethylene is through surface treatment; The mineral filler of 20～100 mass parts, said mineral filler is through surface treatment; The solidifying agent of 0～50 mass parts.The present invention adopts performance resins that epoxy resin is carried out modification, improves the resistance toheat and the dielectric properties of resin combination; The present invention adopts surface treated tetrafluoroethylene, can under the prerequisite that guarantees resistance to elevated temperatures, improve the dielectric properties and the flame retardant properties of compsn, and reduce the hygroscopic property of compsn; The present invention adopts surface treated mineral filler, can reduce the thermal expansivity of compsn.Therefore; Resin composition for copper clad laminate provided by the invention has good heat-resistant, dielectric properties, flame retardant properties, processing characteristics, lower hot expansibility and lower hygroscopic property; Be applicable to high frequency, high heat-resisting copper clad laminate, can satisfy the requirement of printed circuit board processing and assembling.
In order to further specify the present invention, resin composition for copper clad laminate provided by the invention and prepreg are described in detail below in conjunction with embodiment.
Embodiment 1
With 2.5g γ-(2; 3-glycidoxy propyl group) Trimethoxy silane is that the silicon-dioxide of 0.1 μ m～1 μ m carries out surface treatment to 50g available from the rich auspicious silicon materials in Guangzhou ltd, particle diameter; Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% fill composition;
Is that XY-300, particle diameter be the polytetrafluorethylepowder powder of 0.5 μ m～10 μ ms carry out surface treatment to 20g available from the prosperous win industry development in Zhuhai ltd, model with 1g ten trifluoro octyltri-ethoxysilane (F8261); Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% polyetetrafluoroethycompsn compsn;
100g is dissolved in the N available from dihydroxyphenyl propane two cyanates, said fill composition, said polyetetrafluoroethycompsn compsn and the 0.2g stannous octoate of Zibo Qi Fengchuan profit chemical industry ltd available from bisphenol A type epoxy resin E20, the 120g of South Asia epoxy resin (Kunshan) ltd, obtains the glue that concentration is 65wt%; Use is that the glasscloth of 2116 cloth, 1080 cloth floods said glue available from the diligent Materials Co., Ltd in sky, Chongqing, model, and the adhesive plaster behind the dipping glue is solidified 5min at 150 ℃, processes prepreg; 4 said prepregs are superimposed, and after Copper Foil was placed on the two sides, pressing 2h under 190 ℃, 2MPa～3Mpa obtained copper clad laminate.
Said copper clad laminate is carried out performance test, and the result is referring to table 1, the The performance test results of the copper clad laminate that table 1 provides for the embodiment of the invention and comparative example.
Embodiment 2
With 2.5g γ-(2; 3-glycidoxy propyl group) Trimethoxy silane is that the silicon-dioxide of 0.1 μ m～1 μ m carries out surface treatment to 50g available from the rich auspicious silicon materials in Guangzhou ltd, particle diameter; Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% fill composition;
Is that XY-300, particle diameter be the polytetrafluorethylepowder powder of 0.5 μ m～10 μ ms carry out surface treatment to 20g available from the prosperous win industry development in Zhuhai ltd, model with 1g ten trifluoro octyltri-ethoxysilane (F8261); Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% polyetetrafluoroethycompsn compsn;
Is that Noryl, 25gDDM, said fill composition and the said polyetetrafluoroethycompsn compsn of MPPO be dissolved in N available from the bisphenol A type epoxy resin E20 of South Asia epoxy resin (Kunshan) ltd, 120g available from Research Inst. of Chemical Industry, Beijing, code name with 100g, obtains the glue that concentration is 65wt%; Use is that the glasscloth of 2116 cloth, 1080 cloth floods said glue available from the diligent Materials Co., Ltd in sky, Chongqing, model, and the adhesive plaster behind the dipping glue is solidified 5min at 150 ℃, processes prepreg; 4 said prepregs are superimposed, and after Copper Foil was placed on the two sides, pressing 2h under 190 ℃, 2MPa～3Mpa obtained copper clad laminate.
Said copper clad laminate is carried out performance test, and the result is referring to table 1, the The performance test results of the copper clad laminate that table 1 provides for the embodiment of the invention and comparative example.
Embodiment 3
With 2.5g γ-(2; 3-glycidoxy propyl group) Trimethoxy silane is that the silicon-dioxide of 0.1 μ m～1 μ m carries out surface treatment to 50g available from the rich auspicious silicon materials in Guangzhou ltd, particle diameter; Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% fill composition;
Is that XY-300, particle diameter be the polytetrafluorethylepowder powder of 0.5 μ m～10 μ ms carry out surface treatment to 20g available from the prosperous win industry development in Zhuhai ltd, model with 1g ten trifluoro octyltri-ethoxysilane (F8261); Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% polyetetrafluoroethycompsn compsn;
With 100g available from the bisphenol A type epoxy resin E20 of South Asia epoxy resin (Kunshan) ltd, 120g available from Shandong should macromolecular material ltd, code name is that the benzoxazine colophony of PX-PN001, said fill composition and said polyetetrafluoroethycompsn compsn are dissolved in the N, obtains the glue that concentration is 65wt%; Use is that the glasscloth of 2116 cloth, 1080 cloth floods said glue available from the diligent Materials Co., Ltd in sky, Chongqing, model, and the adhesive plaster behind the dipping glue is solidified 5min at 150 ℃, processes prepreg; 4 said prepregs are superimposed, and after Copper Foil was placed on the two sides, pressing 2h under 190 ℃, 2MPa～3Mpa obtained copper clad laminate.
Said copper clad laminate is carried out performance test, and the result is referring to table 1, the The performance test results of the copper clad laminate that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 1
Being dissolved in by mass ratio available from the bisphenol A type epoxy resin E20 of South Asia epoxy resin (Kunshan) ltd, 120g available from dihydroxyphenyl propane two cyanates of Zibo Qi Fengchuan profit chemical industry ltd and 0.2g stannous octoate 100g is in the mixing solutions formed of 1: 1 N and acetone, obtains the glue that concentration is 65wt%; Use is that the glasscloth of 2116 cloth, 1080 cloth floods said glue available from the diligent Materials Co., Ltd in sky, Chongqing, model, and the adhesive plaster behind the dipping glue is solidified 5min at 150 ℃, processes prepreg; 4 said prepregs are superimposed, and after Copper Foil was placed on the two sides, pressing 2h under 190 ℃, 2MPa～3Mpa obtained copper clad laminate.
Said copper clad laminate is carried out performance test, and the result is referring to table 1, the The performance test results of the copper clad laminate that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 2
With 100g available from Research Inst. of Chemical Industry, Beijing, code name be available from the bisphenol A type epoxy resin E20 of South Asia epoxy resin (Kunshan) ltd, 120g MPPO Noryl, 25gDDM, 20g available from the prosperous win industry development in Zhuhai ltd, model be XY-300, particle diameter be 0.5 μ m～10 μ m polytetrafluorethylepowder powder and 50g available from the rich auspicious silicon materials in Guangzhou ltd, particle diameter be the silicon-dioxide of 0.1 μ m～1 μ m to be dissolved in mass ratio be in 1: 1 the mixed solvent of N and acetone, obtain the glue that concentration is 65wt%; Use is that the glasscloth of 2116 cloth, 1080 cloth floods said glue available from the diligent Materials Co., Ltd in sky, Chongqing, model, and the adhesive plaster behind the dipping glue is solidified 5min at 150 ℃, processes prepreg; 4 said prepregs are superimposed, and after Copper Foil was placed on the two sides, pressing 2h under 190 ℃, 2MPa～3Mpa obtained copper clad laminate.
Said copper clad laminate is carried out performance test, and the result is referring to table 1, the The performance test results of the copper clad laminate that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 3
With 2.5g γ-(2; 3-glycidoxy propyl group) Trimethoxy silane is that the silicon-dioxide of 0.1 μ m～1 μ m carries out surface treatment to 50g available from the rich auspicious silicon materials in Guangzhou ltd, particle diameter; Adding is the mixing solutions that 1: 1 acetone and N forms by mass ratio, obtains solid content behind the thorough mixing and be 70% fill composition;
With 100g available from the bisphenol A type epoxy resin E20 of South Asia epoxy resin (Kunshan) ltd, 120g available from Shandong should macromolecular material ltd, code name is that benzoxazine colophony, 25gDDM, said fill composition and the 20g of PX-PN001 is that XY-300, particle diameter are that the polytetrafluorethylepowder powder of 0.5 μ m～10 μ m is dissolved in by mass ratio being in 1: 1 the mixed solvent of N and acetone, obtaining the glue that concentration is 65wt% available from the prosperous win industry development in Zhuhai ltd, model; Use is that the glasscloth of 2116 cloth, 1080 cloth floods said glue available from the diligent Materials Co., Ltd in sky, Chongqing, model, and the adhesive plaster behind the dipping glue is solidified 5min at 150 ℃, processes prepreg; 4 said prepregs are superimposed, and after Copper Foil was placed on the two sides, pressing 2h under 190 ℃, 2MPa～3Mpa obtained copper clad laminate.
Said copper clad laminate is carried out performance test, and the result is referring to table 1, the The performance test results of the copper clad laminate that table 1 provides for the embodiment of the invention and comparative example.
The The performance test results of the copper clad laminate that table 1 embodiment of the invention and comparative example provide
Can know that by table 1 copper clad laminate that adopts resin combination provided by the invention to prepare has high glass transition, lower specific inductivity, lower water-intake rate and flame retardant properties preferably.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. resin composition for copper clad laminate comprises:
The epoxy resin of 100 mass parts;
The performance resins of 50～200 mass parts;
The tetrafluoroethylene of 10～50 mass parts, said tetrafluoroethylene is through surface treatment;
The mineral filler of 20～100 mass parts, said mineral filler is through surface treatment;
The solidifying agent of 0～50 mass parts.
2. resin combination according to claim 1 is characterized in that, said epoxy resin is one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phenol aldehyde type epoxy resin and the biphenyl type resol.
3. resin combination according to claim 1 is characterized in that, said performance resins is one or more in cyanate ester resin, modified polyphenylene ether resin, benzoxazine colophony and the bimaleimide resin.
4. resin combination according to claim 1; It is characterized in that said tetrafluoroethylene is through one or more surface treatments in cationic styrene base amido, ten trifluoro octyltri-ethoxysilane, 3-aminopropyl triethoxysilane and the water-soluble modified fluorosilicone.
5. resin combination according to claim 4 is characterized in that, the particle diameter of said tetrafluoroethylene is 0.1 μ m-10 μ m.
6. resin combination according to claim 1; It is characterized in that; Said mineral filler is through γ-An Bingjisanyiyangjiguiwan, γ-(2; 3-glycidoxy propyl group) one or more surface treatments in Trimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane and the β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan.
7. resin combination according to claim 6; It is characterized in that said mineral filler is one or more in silicon powder, aluminum oxide, Natural manganese dioxide, wollastonite, boehmite, clay, talcum, mica, kaolin, permanent white, lime carbonate and the zinc borate.
8. resin combination according to claim 7 is characterized in that, the particle diameter of said mineral filler is 0.05 μ m～5 μ m.
9. resin combination according to claim 1 is characterized in that, said solidifying agent be in 4,4, MDA, diaminodiphenyl oxide, the nitrogenous resol of triazine modification and the acid anhydrides one or more.
10. utilize the prepreg of any described resin combination preparation of claim 1～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110435665.1A CN102558858B (en) | 2011-12-22 | 2011-12-22 | Resin compound for copper-coated laminated boards and prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110435665.1A CN102558858B (en) | 2011-12-22 | 2011-12-22 | Resin compound for copper-coated laminated boards and prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102558858A true CN102558858A (en) | 2012-07-11 |
| CN102558858B CN102558858B (en) | 2014-03-26 |
Family
ID=46405540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110435665.1A Active CN102558858B (en) | 2011-12-22 | 2011-12-22 | Resin compound for copper-coated laminated boards and prepreg |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102558858B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263306A (en) * | 2014-09-26 | 2015-01-07 | 四川东材科技集团股份有限公司 | Preparation method of polyphenyl ether adhesive and copper-clad plate thereof |
| CN104559177A (en) * | 2013-10-25 | 2015-04-29 | 深圳光启创新技术有限公司 | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate |
| WO2015127860A1 (en) * | 2014-02-25 | 2015-09-03 | 广东生益科技股份有限公司 | Halogen-free flame retardant type resin composition |
| CN105131527A (en) * | 2015-09-17 | 2015-12-09 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Copper clad laminate with low dielectric constant and manufacturing method of copper clad laminate |
| CN106366566A (en) * | 2016-08-27 | 2017-02-01 | 安徽天瞳智能科技有限公司 | Epoxy resin composition for flexible wiring board |
| CN106433122A (en) * | 2016-09-07 | 2017-02-22 | 深圳先进技术研究院 | Modified cyanate ester composite material, and preparation method and application thereof |
| US9873789B2 (en) | 2014-12-26 | 2018-01-23 | Shengyi Technology Co., Ltd. | Halogen-free epoxy resin composition, prepreg and laminate using same |
| CN107663367A (en) * | 2016-07-28 | 2018-02-06 | 广科工业股份有限公司 | Low dielectric constant materials and precursors thereof |
| CN108129835A (en) * | 2015-09-02 | 2018-06-08 | 苏州益可泰电子材料有限公司 | High-frequency electronic dielectric material glue and preparation method thereof |
| CN108659461A (en) * | 2018-04-17 | 2018-10-16 | 南京大学 | A kind of preparation method of PTFE bases PCB copper-clad plate prepregs |
| US10208156B2 (en) | 2014-12-26 | 2019-02-19 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate using same |
| CN109988299A (en) * | 2017-12-29 | 2019-07-09 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified polyphenylene oxide resin and its preparation method and application containing epoxy group |
| US10544255B2 (en) | 2015-12-28 | 2020-01-28 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate prepared therefrom |
| CN111138856A (en) * | 2018-11-05 | 2020-05-12 | 味之素株式会社 | Resin composition |
| US20200317913A1 (en) * | 2017-12-22 | 2020-10-08 | Teijin Limited | Thermosetting resin composition |
| CN112549689A (en) * | 2020-12-11 | 2021-03-26 | 广东生益科技股份有限公司 | High-frequency flexible copper clad laminate and preparation method and application thereof |
| CN113574118A (en) * | 2019-03-12 | 2021-10-29 | Ａｇｃ株式会社 | Liquid composition, powder, and method for producing powder |
| CN114181496A (en) * | 2021-12-25 | 2022-03-15 | 广东盈骅新材料科技有限公司 | Epoxy resin composite material, prepreg and laminated board |
| CN114932727A (en) * | 2022-05-27 | 2022-08-23 | 江苏耀鸿电子有限公司 | Heat-resistant hydrocarbon resin-based copper-clad plate and preparation method thereof |
| CN114953646A (en) * | 2022-06-09 | 2022-08-30 | 山东金宝电子股份有限公司 | Preparation method of copper-clad plate for mini LED backboard and copper-clad plate |
| CN115595105A (en) * | 2022-12-15 | 2023-01-13 | 建滔（广州）电子材料制造有限公司（Cn） | Composite adhesive for copper-clad plate and preparation method thereof |
| CN116425977A (en) * | 2023-04-20 | 2023-07-14 | 电子科技大学 | Preparation method of low-temperature curing phthalonitrile type bismaleimide-triazine resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220160A (en) * | 2007-12-07 | 2008-07-16 | 广东生益科技股份有限公司 | Prepreg applied for multi-layer board of printed electronic circuit |
| CN102212250A (en) * | 2011-04-15 | 2011-10-12 | 广东生益科技股份有限公司 | Filler compound and copper clad laminate made of same |
-
2011
- 2011-12-22 CN CN201110435665.1A patent/CN102558858B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220160A (en) * | 2007-12-07 | 2008-07-16 | 广东生益科技股份有限公司 | Prepreg applied for multi-layer board of printed electronic circuit |
| CN102212250A (en) * | 2011-04-15 | 2011-10-12 | 广东生益科技股份有限公司 | Filler compound and copper clad laminate made of same |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559177B (en) * | 2013-10-25 | 2018-10-23 | 深圳光启创新技术有限公司 | The preparation method of resin combination and prepreg, composite base material and PCB substrate |
| CN104559177A (en) * | 2013-10-25 | 2015-04-29 | 深圳光启创新技术有限公司 | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate |
| WO2015127860A1 (en) * | 2014-02-25 | 2015-09-03 | 广东生益科技股份有限公司 | Halogen-free flame retardant type resin composition |
| US10696844B2 (en) | 2014-02-25 | 2020-06-30 | Shengyi Technology Co., Ltd. | Halogen-free flame retardant type resin composition |
| CN104263306B (en) * | 2014-09-26 | 2016-02-10 | 四川东材科技集团股份有限公司 | The preparation method of a kind of polyphenylene oxide sizing agent and copper-clad plate thereof |
| CN104263306A (en) * | 2014-09-26 | 2015-01-07 | 四川东材科技集团股份有限公司 | Preparation method of polyphenyl ether adhesive and copper-clad plate thereof |
| US9873789B2 (en) | 2014-12-26 | 2018-01-23 | Shengyi Technology Co., Ltd. | Halogen-free epoxy resin composition, prepreg and laminate using same |
| US10208156B2 (en) | 2014-12-26 | 2019-02-19 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate using same |
| CN108129835A (en) * | 2015-09-02 | 2018-06-08 | 苏州益可泰电子材料有限公司 | High-frequency electronic dielectric material glue and preparation method thereof |
| CN105131527B (en) * | 2015-09-17 | 2017-04-12 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Copper clad laminate with low dielectric constant and manufacturing method of copper clad laminate |
| CN105131527A (en) * | 2015-09-17 | 2015-12-09 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Copper clad laminate with low dielectric constant and manufacturing method of copper clad laminate |
| US10544255B2 (en) | 2015-12-28 | 2020-01-28 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate prepared therefrom |
| CN107663367A (en) * | 2016-07-28 | 2018-02-06 | 广科工业股份有限公司 | Low dielectric constant materials and precursors thereof |
| CN107663367B (en) * | 2016-07-28 | 2020-06-16 | 广科工业股份有限公司 | Low dielectric constant materials and precursors thereof |
| CN106366566A (en) * | 2016-08-27 | 2017-02-01 | 安徽天瞳智能科技有限公司 | Epoxy resin composition for flexible wiring board |
| CN106433122A (en) * | 2016-09-07 | 2017-02-22 | 深圳先进技术研究院 | Modified cyanate ester composite material, and preparation method and application thereof |
| US20200317913A1 (en) * | 2017-12-22 | 2020-10-08 | Teijin Limited | Thermosetting resin composition |
| CN109988299A (en) * | 2017-12-29 | 2019-07-09 | 广东生益科技股份有限公司 | A kind of organic-silicon-modified polyphenylene oxide resin and its preparation method and application containing epoxy group |
| CN109988299B (en) * | 2017-12-29 | 2021-10-19 | 广东生益科技股份有限公司 | Epoxy-containing organic silicon modified polyphenyl ether resin and preparation method and application thereof |
| CN108659461A (en) * | 2018-04-17 | 2018-10-16 | 南京大学 | A kind of preparation method of PTFE bases PCB copper-clad plate prepregs |
| CN111138856A (en) * | 2018-11-05 | 2020-05-12 | 味之素株式会社 | Resin composition |
| CN111138856B (en) * | 2018-11-05 | 2024-01-23 | 味之素株式会社 | Resin composition |
| CN113574118A (en) * | 2019-03-12 | 2021-10-29 | Ａｇｃ株式会社 | Liquid composition, powder, and method for producing powder |
| CN112549689A (en) * | 2020-12-11 | 2021-03-26 | 广东生益科技股份有限公司 | High-frequency flexible copper clad laminate and preparation method and application thereof |
| CN114181496B (en) * | 2021-12-25 | 2023-10-20 | 广东盈骅新材料科技有限公司 | Epoxy resin composite material, prepreg and laminated board |
| CN114181496A (en) * | 2021-12-25 | 2022-03-15 | 广东盈骅新材料科技有限公司 | Epoxy resin composite material, prepreg and laminated board |
| CN114932727A (en) * | 2022-05-27 | 2022-08-23 | 江苏耀鸿电子有限公司 | Heat-resistant hydrocarbon resin-based copper-clad plate and preparation method thereof |
| CN114953646A (en) * | 2022-06-09 | 2022-08-30 | 山东金宝电子股份有限公司 | Preparation method of copper-clad plate for mini LED backboard and copper-clad plate |
| CN115595105A (en) * | 2022-12-15 | 2023-01-13 | 建滔（广州）电子材料制造有限公司（Cn） | Composite adhesive for copper-clad plate and preparation method thereof |
| CN116425977A (en) * | 2023-04-20 | 2023-07-14 | 电子科技大学 | Preparation method of low-temperature curing phthalonitrile type bismaleimide-triazine resin |
| CN116425977B (en) * | 2023-04-20 | 2024-04-26 | 电子科技大学 | Preparation method of low-temperature curing phthalonitrile type bismaleimide-triazine resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102558858B (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102558858B (en) | Resin compound for copper-coated laminated boards and prepreg | |
| CN103265791B (en) | Thermosetting resin composition for integrated circuit as well as prepreg and laminated board both fabricated by using composition | |
| CN103265810B (en) | A kind of resin combination for high-frequency high-speed substrate and use its prepreg made and veneer sheet | |
| CN101684191B (en) | Halogen-less high frequency resin composition, and prepreg and laminate manufacturing by using same | |
| CN102134375B (en) | Halogen-free Tg resin composite and presoaked material and laminated board made by adopting same | |
| CN103232705B (en) | High-frequency resin composition as well as semi-cured sheet and laminated board manufactured by high-frequency resin composition | |
| CN100539803C (en) | Lead-free compatible high frequency copper clad laminate and preparation method thereof | |
| CN103937156A (en) | Thermosetting resin composition and method for manufacturing prepreg and laminated board by using thermosetting resin composition | |
| CN103937157A (en) | Halogen-free resin composition and method for manufacturing prepreg and laminated board by using halogen-free resin composition | |
| CN103642446A (en) | Lead-free high heat-resisting copper-clad board and preparation method thereof | |
| CN103160229B (en) | Glue liquor for environment-friendly light laminated board, laminated board and preparation method of glue liquor | |
| CN104760368B (en) | A kind of Study of Epoxy-Imide Resin matrix copper-clad laminate and preparation method thereof | |
| CN104228216B (en) | A kind of low-loss high-performance copper coated foil plate and preparation method thereof | |
| CN102093672A (en) | Halogen-phosphorus-free flame retardant epoxy resin composition and application thereof in bonding sheet and copper-clad plate | |
| CN105601923A (en) | Fluorine-containing flexible-rigid polyimide film, and preparation method and application thereof | |
| CN102432836A (en) | Halogen-free thermosetting resin composition, and prepreg and laminated board manufactured by using same | |
| CN109535390A (en) | The prepreg and laminate of its preparation of phosphorous epoxy resin composition and application | |
| CN109747263A (en) | A kind of preparation process of novel copper-clad plate | |
| CN102304343A (en) | Glue solution for copper-clad substrate, and preparation method thereof | |
| CN105694451B (en) | A kind of halogen-free resin composition, prepreg, laminate and circuit board | |
| CN1935896A (en) | Epoxy vesin complex and its use | |
| CN112175354A (en) | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof | |
| CN113292824B (en) | Long-chain alkyl polyphenyl ether resin composition and application thereof | |
| CN102529222B (en) | High-insulation metal-based copper-clad plate with low thermal resistance and preparation method thereof | |
| TWI388622B (en) | And a thermosetting resin composition having an acid anhydride hardening |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161021 Address after: 401220 Changshou District of Chongqing economic and Technological Development Zone United Road No. 22 Patentee after: Chongqing Yuntianhua hanen New Material Development Co Ltd Patentee after: Yutianhua Co., Ltd., Yunnan Address before: 657800 Zhaotong City, Yunnan province Shuifu county to jingjiaba Patentee before: Yutianhua Co., Ltd., Yunnan |