CN102372900A - Epoxy resin composition, and prepreg material and printed circuit board prepared from the same - Google Patents
Epoxy resin composition, and prepreg material and printed circuit board prepared from the same Download PDFInfo
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- CN102372900A CN102372900A CN2010102510458A CN201010251045A CN102372900A CN 102372900 A CN102372900 A CN 102372900A CN 2010102510458 A CN2010102510458 A CN 2010102510458A CN 201010251045 A CN201010251045 A CN 201010251045A CN 102372900 A CN102372900 A CN 102372900A
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Abstract
An epoxy resin composition comprises (A) epoxy resin containing dicyclopentadiene (DCPD) type epoxy resin and (B) styrene-maleic anhydride copolymer as a hardener.
Description
Technical field
The present invention is relevant a kind of composition epoxy resin, and by its preimpregnation material (prepreg) processed and printed substrate (printed circuit board).
Background technology
In electronic assemblies, printed substrate is a vital part.It carries other electronic component and connection circuit; So that a stable circuit working environment to be provided; And modal printed circuit board base board is that (copper clad laminate, CCL), it mainly is made up of resin, reinforcement material and Copper Foil three for the laminated board of Copper Foil coating.What resin wherein was commonly used has: what epoxy resin, resol, polyamine formaldehyde, silicone and Teflon etc., reinforcement material were then commonly used has: glasscloth, glass fibre mats, insulation paper, even canvas, linen etc.
Generally be through impregnation resinous varnish in the reinforcement material of glass fabric etc., and be cured to semi-harden state (B-stage) and obtain the preimpregnation material.Then the preimpregnation material that is obtained being carried out layer with certain number of plies closes; And on the outermost layer of at least one side of the preimpregnation material after layer closes, layer metal paper tinsel and make laminated board, and then this laminated board heated, pressurizes and obtain the laminated board of metal coating; Then on thus obtained metal coating laminated board; Leave through hole with drill bit etc., and in this through hole, impose gold-plated etc., the then lip-deep tinsel of etching laminated board again; To form certain circuit pattern, so can obtain printed substrate.
Applied scope of printed substrate and field are quite extensive at present; Electronic package in the general electronic products all is plugged on the printed substrate; And printed substrate now is in order to meet the range of application of superpower, high-transmission and heat-stable assembly, so through dielectric characteristics (specific inductivity (dielectric constant; D
k) and the dissipation factor (dissipation factor; D
f)) improvement improve the speed that signal transmits, and further expectation can promote the glass tansition temperatures (Tg) of printed substrate, and the thermotolerance of taking into account the electronic package heating is simultaneously used.In addition, because the lifting of environmental consciousness recently, many consumption electronic products do not use the copper clad laminate that contains halogen gradually, and use halogen-free copper foil base plate instead, and therefore, the Application Areas of halogen-free copper foil base plate will heal and become extensive.
For reaching the requirement of high-transmission efficient electronic package, prior art imports for example ppe (PPO) resin etc. of thermoplastic material usually in the laminated board material, to reduce the specific inductivity and the dissipation factor of laminated board.Yet though import the demand that thermoplastic material can satisfy electrical specification, this kind practice is prone to cause the reduction of the glass tansition temperatures (Tg) of made laminated board, and the glass tansition temperatures is low more representes that the thermotolerance of material is poor more.The Taiwan patent then proposes another kind of solution No. 216439; It is to utilize NSC 7352 (DCPD) type epoxy resin that the good thermotolerance of substrate, wet fastness and electrical specification are provided; But this patent is that collocation dicyan diamide (DICY) is as stiffening agent; Though can promote the tear resistance of made substrate with the dicyan diamide as stiffening agent, but the dicyan diamide is little to choice of Solvent property, and is easy to the bad phenomenon that crystallisate is separated out occur in the making processes of preimpregnation material.
For improving the glass tansition temperatures of preimpregnation material; Prior art (for example No. the 455613rd, the Taiwan patent) is then with epoxy resin styrene-maleic anhydride copolymer (the styrene-maleic anhydride copolymer that arranges in pairs or groups; SMA) use; To improve the glass tansition temperatures of the made preimpregnation material of this based epoxy resin, it should be noted that still the consumption of styrene-maleic anhydride copolymer is difficult to control, so that made laminated board there was crisp problem; Add and be prone to produce break flour man-hour, therefore can cause the pollution of product and be badly in need of and improve.
In order to improve the shortcoming of above-mentioned prior art; Having needs to propose a kind of composition epoxy resin; Make by its made laminated board on glass tansition temperatures, thermotolerance, anti-immersed solder property and workability, all to promote to some extent, and can take into account the laminated board excellent electric characteristics again simultaneously.
Summary of the invention
In view of the above, the objective of the invention is is providing a kind of composition epoxy resin, and its improvement and raising of glass tansition temperatures on toughness, thermotolerance, anti-immersed solder property and workability all has significant effect, is especially reducing specific inductivity (D
k) and the dissipation factor (D
f) on have more effect.
Another object of the present invention is that a kind of preimpregnation material is being provided; It is through in solvent; Dissolving or disperse above-mentioned composition epoxy resin and make composition epoxy resin varnish, the above-mentioned composition epoxy resin varnish of impregnation in the reinforcement material of glass fabric etc. then, and bake and make.
Another purpose of the present invention is that a kind of printed substrate is being provided, and it is to utilize following method and make, and this method comprises: the above-mentioned preimpregnation material of certain number of plies is given layer close; And on the outermost layer of at least one side of this preimpregnation material; Layer metal paper tinsel and form metal coating laminated board, and this metal coating laminated board is carried out pressurized, heated be shaped, remove the tinsel of the part on above-mentioned metal coating laminated board surface then; To form certain circuit pattern, so can obtain printed substrate.
In order to achieve the above object, the present invention provides a kind of composition epoxy resin, and it comprises:
(A) 100 parts by weight of epoxy resin, this epoxy resin comprise NSC 7352 (DCPD) type epoxy resin, and the structural formula of this dicyclopentadiene type epoxy resin is as follows:
In the formula, n is 0 to 10 integer; And
(B) styrene-maleic anhydride copolymer is benchmark as stiffening agent with 100 parts by weight of epoxy resin, and the content of this styrene-maleic anhydride copolymer is 30 to 80 weight parts, and its structural formula is as follows:
In the formula, m is 1 to 6 integer, and n is 2 to 12 integer.
Epoxy resin in the composition epoxy resin of the present invention can further comprise the bisphenol type novolac epoxy.
Composition epoxy resin of the present invention can further comprise one or more in hardening accelerator, dispersion agent, incombustible agent, toughner and the inorganic filler.
The present invention carries out epoxy composite material that crosslinking reaction obtain have high glass tansition temperatures as stiffening agent with the epoxy resin that with dicyclopentadiene type epoxy resin is principal constituent with styrene-maleic anhydride copolymer, and laminated board or the printed substrate made by this epoxy composite material have high glass tansition temperatures and good thermotolerance, anti-immersed solder property, toughness, workability and electrical specification.
For make above and other objects of the present invention, feature and advantage can be more clear, hereinafter is lifted preferred embodiment with the spy, elaborates as follows.
Embodiment
The present invention provides a kind of composition epoxy resin; It mainly is to be arranged in pairs or groups by a certain percentage by dicyclopentadiene type epoxy resin and styrene-maleic anhydride copolymer to form; So that made preimpregnation material or laminated board be improved, and reach the raising and the specific inductivity (D of glass tansition temperatures simultaneously on workability
k) and the dissipation factor (D
f) effects such as reduction.Composition epoxy resin of the present invention can further comprise one or more in hardening accelerator, dispersion agent, incombustible agent, toughner and the inorganic filler.
Composition epoxy resin of the present invention comprises:
(A) epoxy resin, this epoxy resin comprise the bisphenol type novolac epoxy of 0 to 30 weight part and the dicyclopentadiene type epoxy resin of 70 to 100 weight parts, and the structural formula of this dicyclopentadiene type epoxy resin is as follows:
In the formula, n is 0 to 10 integer; And
(B) styrene-maleic anhydride copolymer is benchmark as stiffening agent with 100 parts by weight of epoxy resin, and the content of this styrene-maleic anhydride copolymer is 30 to 80 weight parts, and its structural formula is as follows:
In the formula, m is 1 to 6 integer, and n is 2 to 12 integer;
(C) hardening accelerator of 0.1 to 1.0 weight part; (D) dispersion agent of 0 to 1.0 weight part; (E) the phosphorous incombustible agent of 0 to 25.0 weight part; (F) toughner of 0 to 5.0 weight part; And (G) inorganic filler of 0 to 80 weight part, and above each composition is to be benchmark with 100 parts by weight of epoxy resin.
Epoxy resin in the composition epoxy resin of the present invention comprises dicyclopentadiene type epoxy resin, and the epoxy equivalent (weight) of this dicyclopentadiene type epoxy resin is 200 to 300 gram/equivalents, and its average functionality is 2 to 10.In this dicyclopentadiene type epoxy resin, can further mix again and support by the arm a spot of bisphenol type novolac epoxy, for example be the mixing of bisphenol A-type novolac epoxy, Bisphenol F type novolac epoxy or said two devices.Gross weight in epoxy resin is 100 weight parts, and this epoxy resin comprises the bisphenol type novolac epoxy of 0 to 30 weight part and the dicyclopentadiene type epoxy resin of 70 to 100 weight parts.
Stiffening agent in the composition epoxy resin of the present invention is a styrene-maleic anhydride copolymer, and the molecular weight of employed styrene-maleic anhydride copolymer can be between 1400 to 50,000.With 100 parts by weight of epoxy resin is benchmark, and the content of this styrene-maleic anhydride copolymer is 30 to 80 weight parts, is preferable with 40 weight parts again wherein.
Hardening accelerator in the composition epoxy resin of the present invention comprises acetate 4-butyl-phosphonium (tetrabutylphosphonium acetate), glyoxal ethyline (2-methyl-imidazole; 2MI), 2-ethyl-4-methylimidazole (2-ethyl-4-methyl-imidazole; 2E4MI) and the 2-phenylimidazole (2-phenyl-imidazole 2PI) waits compound.And above-mentioned hardening accelerator can use separately or can make up simultaneously that the person uses jointly more than two kinds.Those hardening accelerators can quicken the setting time of preimpregnation material.With 100 parts by weight of epoxy resin is benchmark, and the content of this hardening accelerator is 0.1 to 1.0 weight part, is preferable with 0.5 weight part again wherein.
The visual dispersion agent that needs to add in the composition epoxy resin of the present invention comprises silane (silane) coupler.With 100 parts by weight of epoxy resin is benchmark, and the content of this dispersion agent is between 0 to 1.0 weight part.
The visual phosphorous incombustible agent that need to add in the composition epoxy resin of the present invention comprises and gathers methyl-phosphorous acid 1 that 3-stretches phenylester (Poly (1,3-phenylene methylphosphonate)); The bisphenol A-type novolac epoxy of phosphorous (DOPO, that is 9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound); And phosphorus nitrence polymer, its structural formula is as follows:
R and R ' are alkyl in the formula.With 100 parts by weight of epoxy resin is benchmark, and the content of this phosphorous incombustible agent is between 0 to 25.0 weight part.
The visual toughner that need to add in the composition epoxy resin of the present invention comprises that molecular weight is greater than 4000 and the long-chain polymer rubber material of viscosity between 300,000 cps to 80, ten thousand cps; For example be nbr carboxyl terminal (carboxyl-terminated butadiene acrylonitrile rubber, CTBN).And a spot of toughner is made an addition in the composition epoxy resin, can significantly improve the not good problem of the toughness that combination produced of dicyclopentadiene type epoxy resin collocation styrene-maleic anhydride copolymer stiffening agent.With 100 parts by weight of epoxy resin is benchmark, and the content of this toughner ties up between 0 to 5.0 weight part, is preferable with 2.0 weight parts again wherein.
The visual inorganic filler that needs to add in the composition epoxy resin of the present invention comprises talcum (talc), lime carbonate, glass powder, silicon-dioxide, kaolin, mica, powders such as white lake, aluminium sesquioxide.And above-mentioned inorganic filler can use separately or can make up simultaneously that the person uses jointly more than two kinds.Those inorganic fillers can be given characteristics such as epoxy resin workability, flame retardancy, thermotolerance or wet fastness.With 100 parts by weight of epoxy resin is benchmark, and the content of this inorganic filler is between 0 to 80 weight part.
The solvent that composition epoxy resin varnish of the present invention uses for example is acetone, methylethylketone (MEK), propylene glycol monomethyl ether (PM), pimelinketone, 1-Methoxy-2-propyl acetate (propylene glycol methyl ether acetate; PMA) and N (dimethyl formamide, DMF).And above-mentioned solvent can use separately or can make up simultaneously that the person uses jointly more than two kinds.With 100 parts by weight of epoxy resin is benchmark, and the consumption of solvent is 60 to 90 weight parts.
Composition epoxy resin of the present invention system can through with above-mentioned (A) epoxy resin, (B) stiffening agent, (C) hardening accelerator and (D) dispersion agent that optionally adds, (E) phosphorous incombustible agent, (F) toughner and (G) inorganic filler modulate with whisking appliance (mixer) uniform mixing.Then, through the synthetic composition epoxy resin of institute is dissolved or dispersed in the solvent, and the viscosity of adjustment epoxy resin slurry, and process composition epoxy resin varnish.
Then, the made composition epoxy resin varnish of impregnation in being used to form the reinforcement material of preimpregnation material, and in drying machine, heated 2 to 10 minutes with 150 ℃ to 180 ℃, carry out drying and reaction, produce the preimpregnation material of semi-harden state thus.Wherein, employed reinforcement material for example is the glasscloth of glass fabric, zellglas, glassmat etc., in addition also can use kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc.
Resulting preimpregnation material is carried out layer with certain number of plies close and form laminated board, on the outermost layer of at least one side of this laminated board, Copper Foil is opened in layer unification then, and carries out the pressurized, heated shaping, obtains the laminated board of Copper Foil coating therefrom.Then,, make the part of the only residual formation circuit pattern of Copper Foil on Copper Foil coating laminated board surface, and the part of removing other so just can obtain to have the printed substrate of circuit to form circuit pattern through subtractive process such as etchings.
The embodiment that hereinafter provided setting forth technique means of the present invention, is not in order to limit technological category of the present invention only.
Embodiment one to seven and comparative example one are to be 100 parts with weight epoxy, and other each composition is all represented with relative parts by weight.
Embodiment one
NSC 7352 (DCPD) type epoxy resin (epoxy equivalent (weight) (EEW): 279 with 100 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of 40 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the phosphorus nitrence polymer of the silane coupling agent of the acetate 4-butyl-phosphonium of 0.5 weight part (Deep Water), 0.5 weight part, 22 weight parts (big tomb chemistry SPB-100), phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow ChemicalXZ-92741) of 15 weight parts, the nbr carboxyl terminal (Hexion 58005) of 2 weight parts and the talcum of 60 weight parts; Under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment two
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 100 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of 30 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the phosphorus nitrence polymer of the silane coupling agent of the acetate 4-butyl-phosphonium (DeepWater) of 0.5 weight part, 0.5 weight part, 22 weight parts (big tomb chemistry SPB-100), phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow ChemicalXZ-92741) of 15 weight parts, the nbr carboxyl terminal (Hexion 58005) of 2 weight parts and the talcum of 60 weight parts; Under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment three
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 100 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of 80 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the phosphorus nitrence polymer of the silane coupling agent of the acetate 4-butyl-phosphonium (DeepWater) of 0.5 weight part, 0.5 weight part, 22 weight parts (big tomb chemistry SPB-100), phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow ChemicalXZ-92741) of 15 weight parts, the nbr carboxyl terminal (Hexion 58005) of 2 weight parts and the talcum of 60 weight parts; Under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment four
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 80 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of the bisphenol A-type novolac epoxy of 20 weight parts (Kolon KEP-3165), 40 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the phosphorus nitrence polymer of the silane coupling agent of the acetate 4-butyl-phosphonium of 0.5 weight part (Deep Water), 0.5 weight part, 22 weight parts (big tomb chemistry SPB-100), phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow Chemical XZ-92741) of 15 weight parts, the nbr carboxyl terminal (Hexion 58005) of 2 weight parts and the talcum of 60 weight parts; Under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment five
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 100 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of 40 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the acetate 4-butyl-phosphonium (DeepWater) of 0.5 weight part, the silane coupling agent of 0.5 weight part, the nbr carboxyl terminal (Hexion 58005) of 2 weight parts and the talcum of 60 weight parts, under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment six
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 100 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of 40 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the acetate 4-butyl-phosphonium (DeepWater) of 0.5 weight part, the phosphorus nitrence polymer (big tomb chemistry SPB-100) of 22 weight parts, phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow Chemical XZ-92741) of 15 weight parts and the nbr carboxyl terminal (Hexion 58005) of 2 weight parts, under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment seven
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 70 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of the bisphenol A-type novolac epoxy of 30 weight parts (Kolon KEP-3165), 30 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the phosphorus nitrence polymer of the silane coupling agent of the acetate 4-butyl-phosphonium of 0.5 weight part (Deep Water), 0.5 weight part, 22 weight parts (big tomb chemistry SPB-100), phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow Chemical XZ-92741) of 15 weight parts and the talcum of 60 weight parts; Under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Comparative example one
NSC 7352 (DCPD) type epoxy resin (EEW:279 with 100 weight parts; The HP-7200H of Dai Nippon Printing), (molecular weight is 11 to the styrene-maleic anhydride copolymer of 40 weight parts; 000; Vinylbenzene is 4: 1 to the weight ratio of maleic anhydride; Sartomer EF40), the acetate 4-butyl-phosphonium (DeepWater) of 0.5 weight part, the silane coupling agent of 0.5 weight part, the phosphorus nitrence polymer (big tomb chemistry SPB-100) of 22 weight parts, phosphorous (DOPO) bisphenol A-type novolac epoxy (Dow ChemicalXZ-92741) of 15 weight parts and the talcum of 60 weight parts, under room temperature, use whisking appliance to mix 60 minutes, add the methylethylketone of 80 weight parts again.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Utilize the cylinder coating machine; Embodiment one to seven and comparative example one prepared composition epoxy resin varnish are coated on 7628 (R/C:43%) glasscloth; Then; Be placed in the drying machine, and, produce the preimpregnation material of semi-harden state thus 180 ℃ of following heat dryings 2 to 10 minutes.Then four preimpregnation materials are given layer and close, and open the Copper Foil of 1oz in each layer of outermost layer unification of its both sides.Then, its pressurized, heated is carried out pressing, obtain the laminated board of Copper Foil coating thus, wherein the condition of pressurized, heated is the heat-up rate with 2.0 ℃/minute, reaches 180 ℃, and at 180 ℃, total head 15kg/cm
2(first pressing 8kg/cm
2) descended pressurized, heated 60 minutes, and make the laminated board of Copper Foil coating.Then, through subtractive process such as etchings, make the part of the only residual formation circuit pattern of Copper Foil on the laminated board surface of Copper Foil coating, and remove other part, form circuit pattern thus.According to this, just can obtain to be formed with the printed substrate of circuit on the top layer.
To the foregoing description and the water-absorbent of the prepared Copper Foil coating of comparative example laminated board, anti-immersed solder property (solder floating), tearing strength (peeling strength), glass tansition temperatures (glass transitiontemperature; Tg), heat decomposition temperature, flame retardancy, toughness, specific inductivity and the dissipation factor measure, the composition epoxy resin of embodiment one to seven and comparative example one and evaluation result thereof are then shown in table one.
Table 1
Performance test:
[water-absorbent test]
Carry out pressure cooker cooking test (PCT) test, laminated board is placed pressurized vessel, under the environment of 121 ℃, saturated humidity (100%R.H.) and 2 air pressure 1 hour, the anti-high humidity ability of test laminated board.
[property testing of anti-immersed solder]
Whether the laminated board that drying is crossed behind the immersion certain hour, is observed defective and occurred in 288 ℃ soldering is bathed, for example confirm with the layering or the puff of laminated board.
[tearing strength test]
Tearing strength is meant the sticking power of Copper Foil as far as base material, and the Copper Foil with per inch (25.4mm) width vertically tears up on the plate face usually, expresses the power of sticking power with the size of its required strength.Its qualifying standard of substrate of MIL-P-55110E regulation 1oz Copper Foil is 4lb/in.
[test of glass tansition temperatures]
Utilize dynamic mechanical analysis appearance (DMA) to measure glass tansition temperatures (Tg).The test specification of glass tansition temperatures is interconnected and encapsulation association (The Institute for Interconnecting and PackagingElectronic Circuits, IPC-TM-650.2.4.25C IPC) and a 24C detection method of electronic circuit.
[heat decomposition temperature test]
Utilize thermogravimetric analyzer (TGA) to measure and compare with the initial stage quality, the temperature when quality reduces 5% is heat decomposition temperature.
[flame retardancy test]
Utilize UL 94V: the vertical combustion testing method, laminated board is fixed with the vertical position, with the Bunsen burner burning, relatively its spontaneous combustion is extinguished and combustion-supporting characteristic, and its result's report is divided into UL 94V-0 (the best) to the anti-combustion grade of UL94V-2.
[toughness test]
Basic unit's version is lain against on the tool of plane, vertically contact, grant vertical pressure again with the laminated board surface with cross metal fixture; After remove this cross tool; Observe cross shape vestige on the substrate, inspect this laminate surface, do not have white scrimp and take place then to be judged to be good; Show slightly lineae ablicantes for general, it is bad that crackle or fracture person are taken place.
[specific inductivity and the dissipation factor are measured]
According to ASTM D150 standard, under operating frequency 1GHz, calculate the specific inductivity (Dk) and the dissipation factor (Df).
The most preferred embodiment of embodiment one expression dicyclopentadiene type epoxy resin collocation of the present invention styrene-maleic anhydride copolymer.Embodiment one to three expression dicyclopentadiene type epoxy resin of the present invention and as the effect of the different proportionings of the styrene-maleic anhydride copolymer of stiffening agent, and show the adding proportion of showing dicyclopentadiene type epoxy resin and styrene-maleic anhydride copolymer and glass tansition temperatures and specific inductivity and the dissipation factor and present dependency each other.Embodiment two is presented under the situation of the styrene-maleic anhydride copolymer that adopts low amount, and the glass tansition temperatures can reduce and the specific inductivity and the dissipation factor can raise.Embodiment three is presented under the situation of the styrene-maleic anhydride copolymer that adopts higher amount, and the glass tansition temperatures can raise and the specific inductivity and the dissipation factor can reduce, but on toughness, can reduce to " generally " grade.Embodiment four, seven expression dicyclopentadiene type epoxy resin can mix with other epoxy resin (for example bisphenol A-type novolac epoxy) supports by the arm embodiment together; More reaching more than 185 ℃ in the performance of glass tansition temperatures, but be noted that specific inductivity and dissipation factor values can improve.The embodiment of incombustible agent such as phosphor-included additive is not used in embodiment five expressions, but difficult combustion characteristic still can reach the UL94V1 grade.The embodiment of weighting agent is not used in embodiment six expressions.The embodiment of toughner is not used in embodiment seven expressions, and it utilizes the mode of the ratio that increases the bisphenol A-type novolac epoxy to improve the toughness of laminated board, but flame retardancy only reaches the V-1 grade.Comparative example one is illustrated under the situation of not adding toughner, and the fragility of made laminated board can improve, and so also is prone to cause the break flour amount increase of laminated board and processing pollution is improved.
Can know that by table one embodiment one to seven and comparative example one show, can meet the specification that printed substrate requires by the made laminated board of composition epoxy resin of the present invention or the laminated board of Copper Foil coating.Embodiment one to seven shows that the anti-immersed solder property of laminated board of the present invention in 288 ℃ soldering is bathed can surpass more than 30 minutes, and specific inductivity can reach 4.2, and the dissipation factor values can reach 0.01.In addition, in the tough sex expression of laminated board, add a spot of long-chain polymer rubber after, its toughness shows as the grade of " good ", helps the processed and applied of laminated board.
In view of the above, laminated board that composition epoxy resin of the present invention is made or printed substrate have high glass tansition temperatures, and good thermotolerance, anti-immersed solder property, toughness, workability and electrical specification.
As far as all present technique field those of skill in the art, the present invention can make multiple modification and variation significantly and not break away from the spirit and scope of the present invention.Therefore, the present invention includes those modifications and variation, and it is included in down all in the claims and impartial person thereof that attach.
Claims (14)
1. composition epoxy resin comprises:
(A) 100 parts by weight of epoxy resin, this epoxy resin comprise NSC 7352 (DCPD) type epoxy resin, and the structural formula of this dicyclopentadiene type epoxy resin is as follows:
In the formula, n is 0 to 10 integer; And
(B) styrene-maleic anhydride copolymer is benchmark as stiffening agent with 100 parts by weight of epoxy resin, and the content of this styrene-maleic anhydride copolymer is 30 to 80 weight parts, and its structural formula is as follows:
In the formula, m is 1 to 6 integer, and n is 2 to 12 integer.
2. composition epoxy resin as claimed in claim 1, wherein, this epoxy resin further comprises the bisphenol type novolac epoxy.
3. composition epoxy resin as claimed in claim 2, wherein, this epoxy resin comprises the bisphenol type novolac epoxy of 0 to 30 weight part and the dicyclopentadiene type epoxy resin of 70 to 100 weight parts.
4. composition epoxy resin as claimed in claim 2, wherein, this bisphenol type novolac epoxy is to be selected from the group that bisphenol A-type novolac epoxy and Bisphenol F type novolac epoxy are formed.
5. composition epoxy resin as claimed in claim 1, wherein, the molecular weight of this styrene-maleic anhydride copolymer is between 1400 to 50,000.
6. composition epoxy resin as claimed in claim 1 further comprises hardening accelerator, is benchmark with 100 parts by weight of epoxy resin, and the content of this hardening accelerator is 0.1 to 1.0 weight part.
7. composition epoxy resin as claimed in claim 6, wherein, this hardening accelerator comprises the tetrabutylphosphoniuacetate acetate squama.
8. composition epoxy resin as claimed in claim 1 further comprises dispersion agent, is benchmark with 100 parts by weight of epoxy resin, and the content of this dispersion agent is between 0 to 1.0 weight part.
9. composition epoxy resin as claimed in claim 1 further comprises phosphorous incombustible agent, is benchmark with 100 parts by weight of epoxy resin, and the content of this phosphorous incombustible agent is between 0 to 25.0 weight part.
10. composition epoxy resin as claimed in claim 1 further comprises toughner, is benchmark with 100 parts by weight of epoxy resin, and the content of this toughner is between 0 to 5.0 weight part.
11. composition epoxy resin as claimed in claim 10, wherein, this toughner comprises nbr carboxyl terminal.
12. composition epoxy resin as claimed in claim 1 further comprises inorganic filler, is benchmark with 100 parts by weight of epoxy resin, the content of this inorganic filler is between 0 to 80 weight part.
13. a preimpregnation material is impregnation such as claim 1,2,3,6,8,9 or 10 described composition epoxy resins in the reinforcement material, and carries out drying and make.
14. printed substrate; Be to form laminated board through preimpregnation material as claimed in claim 13 is closed with certain number of plies layer; And on the outermost layer of this one of them side of laminated board; Layer metal paper tinsel and obtain the laminated board of metal coating, and on this tinsel on the laminated board surface of this metal coating, form certain circuit pattern and make.
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| CN201010251045.8A CN102372900B (en) | 2010-08-10 | 2010-08-10 | Epoxy resin composition, and prepreg material and printed circuit board prepared from the same |
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| CN201010251045.8A CN102372900B (en) | 2010-08-10 | 2010-08-10 | Epoxy resin composition, and prepreg material and printed circuit board prepared from the same |
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| CN102372900A true CN102372900A (en) | 2012-03-14 |
| CN102372900B CN102372900B (en) | 2014-04-02 |
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| CN115340737A (en) * | 2016-07-25 | 2022-11-15 | 伊索拉美国有限公司 | Improved SMA resin formulation |
| CN113061241A (en) * | 2021-04-20 | 2021-07-02 | 三河亮克威泽工业涂料有限公司 | High-iron putty polyester resin material, main agent and preparation method thereof, high-iron putty and application method thereof |
| CN113061241B (en) * | 2021-04-20 | 2022-07-12 | 三河亮克威泽工业涂料有限公司 | High-iron putty polyester resin material, main agent and preparation method thereof, high-iron putty and application method thereof |
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| CN102372900B (en) | 2014-04-02 |
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