CN102295742B - Epoxy resin composition and prepreg material as well as printed circuit board prepared by same - Google Patents
Epoxy resin composition and prepreg material as well as printed circuit board prepared by same Download PDFInfo
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Abstract
The invention relates to an epoxy resin composition and a prepreg material as well as a printed circuit board prepared by the same. The epoxy resin composition comprises (A) epoxy resin and (B) a composite curing agent, wherein the composite curing agent comprises amino triazine novolac, dicyandiamide and diamino diphenyl sulfone which are mixed according to a specific proportion. In the invention, the amino triazine novolac, the dicyandiamide and the diamino diphenyl sulfone are used as a composite curing agent; and the composite curing agent and the epoxy resin are subjected to crosslinking reaction to obtain an epoxy composite material with high glass conversion temperature; and a laminated board or the printed circuit board made of the epoxy composite material has high glass conversion temperature and good heat resistance, chemical resistance, toughness, processability and electrical characteristic.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, especially a kind of composition epoxy resin that contains composite curing agent with and preimpregnation material (Prepreg) and the printed circuit board (PCB) (Printed Circuit Board) made.
Background technology
In electronic assemblies, printed circuit board (PCB) 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 veneer sheet (the Copper Clad Laminate of Copper Foil coating, be called for short CCL), it mainly is comprised of resin, supporting material and Copper Foil three.What resin wherein was commonly used has: Resins, epoxy, resol, polyamine formaldehyde, silicone and Teflon etc., supporting material are then commonly used to be had: glasscloth, glass fibre mats, insulation paper, even canvas, linen etc.
Usually, by impregnation resinous varnish in the supporting material of glass fabric etc., and be cured to semi-cured state (B-stage) and obtain preimpregnation material.Then give laminated with certain number of plies above-mentioned preimpregnation material, and the outermost layer of at least one side of the prepreg after laminated comes laminated tinsel and makes veneer sheet, then this veneer sheet is carried out heating and pressurizing and obtain the veneer sheet of metal coating, then on thus obtained metal coating layer pressing plate, open out the hole that through hole is used with drill bit etc., and in this hole, impose gold-plated to form through hole etc., the tinsel of etching metal coating layer clamp surface so can obtain printed circuit board (PCB) to form certain circuit pattern again.
Printed circuit board base board must meet certain requirement at aspects such as thermotolerance, endurance, workability, toughness and physical strengths, and the Resins, epoxy in the printed circuit board base board is then being played the part of considerable role in the lifting of substrate properties.Resins, epoxy is the organic high molecular compound that contains two or more epoxide groups in molecule of general reference, so Resins, epoxy is a kind of reactive monomeric, and it can obtain a highly cross-linked reticulated structure with the polyamine reaction.Although this highly cross-linked reticulated structure has quite high hardness and glass transfer temperature and endurance, this structure has easily the shortcomings such as crisp and shock-resistance is relatively poor usually.No. the 293831st, TaiWan, China patent and WO2006004118A1 disclose a kind of amido triazine resol (Amino Triazine Novolac, ATN), it can be used as the solidifying agent of Resins, epoxy, use comprises the composition epoxy resin of amido triazine resol and makes substrate, can improve the thermotolerance of substrate, can improve again the sticking power of Copper Foil simultaneously, but the processing of made substrate is difficult for, for example the boring surface planarization is not good, need be overcome.The basic structure of amido triazine resol wherein is as follows:
This amido triazine resol is by with oxybenzene compound, guanamines compound and aldehyde compound, in the presence of acidic catalyst (such as oxalic acid, tosic acid), react and make, wherein, this oxybenzene compound can be such as phenol, cresols, xylenol etc., and aldehyde compound can be such as formaldehyde.In addition, this guanamines compound is then as follows,
(in the formula R refer to amido, phenyl or such as alkyl such as methyl)
This guanamines compound is such as being melamine, benzyl guanamines, methyl guanamines etc., and it can use separately or mix, and the person uses jointly more than two kinds.
Although amido triazine resol (ATN) has good modularity to be easy to allotment, and for improving Copper Foil sticking power and thermotolerance good effect is arranged, can jointly modulate use with other solidifying agent again, but need further to be improved at toughness and the endurance of made substrate.Therefore, the combination of various solidifying agent constantly is developed, for example United States Patent (USP) the 6th, 716, No. 530, to utilize maleimide (Maleimide) and two kinds of solidifying agent of amido triazine resol (ATN) to mix to support by the arm modulation, and use these two kinds of solidifying agent will significantly improve the flame-retarding characteristic of made substrate, but on the characteristics such as the toughness of veneer sheet and thermotolerance, still can't satisfy the demand of currently available products, and still can't obtain to improve significantly to the surperficial endurance problem of made veneer sheet, remain unsolved.
The inventor also once utilized respectively Dicyanodiamide (Dicyandiamide, be called for short DICY) and amido triazine resol, and two amido sulfobenzide (Diamino Diphenyl Sulfone, be called for short DDS) form composite curing agent with amido triazine resol according to the specified proportion allotment, as No. the 099112368th, TaiWan, China number of patent application with No. 099112372, these two kinds of composite curing agents have good effect for the improvement of Resins, epoxy characteristic, as reducing the time of water-absorbent and better control curing reaction.
The problem that produces at toughness, thermotolerance and the endurance of substrate for the combination that further improves prior art use amido triazine phenolic resin curative or other solidifying agent, simultaneously can take into account again the low dielectric characteristics of substrate, then become research topic of the present invention.
Summary of the invention
Accordingly, the object of the invention is to, a kind of composition epoxy resin is provided, it is to form according to amido triazine resol, Dicyanodiamide and the two amido sulfobenzides that specified proportion mixes with the Resins, epoxy collocation, and amido triazine resol wherein, Dicyanodiamide and two amido sulfobenzides namely consist of composite curing agent of the present invention.By the made substrate of composition epoxy resin of the present invention on toughness, thermotolerance, endurance and workability improvement and the raising of glass transition temp significant effect is all arranged, especially reducing specific inductivity (Dielectric constant, Dk) and on the dissipation factor (Dissipation Factor, Df) have more effect.
Another object of the present invention is to be, a kind of preimpregnation material is provided, and it is in solvent, dissolves or disperses above-mentioned composition epoxy resin and make composition epoxy resin varnish, then the above-mentioned composition epoxy resin varnish of impregnation in the supporting material of glass fabric etc. bakes and makes.
Another purpose of the present invention is to be, a kind of printed circuit board (PCB) is provided, it is to utilize following method and make, the method comprises: give the above-mentioned prepreg of certain number of plies laminated, and form metal coating layer pressing plate in the laminated tinsel of outermost layer of at least one side of this prepreg, and this metal coating layer pressing plate is carried out pressurized, heated be shaped, then remove the tinsel of the part of above-mentioned metal coating layer clamp surface, to form certain circuit pattern, so can obtain printed circuit board (PCB).
In order to achieve the above object, the invention provides a kind of composition epoxy resin, it comprises: (A) Resins, epoxy; And (B) composite curing agent, comprise the amido triazine resol, Dicyanodiamide and the two amido sulfobenzides that mix according to specified proportion.
Composition epoxy resin of the present invention can further comprise one or more in curing catalyst, inorganic filler and the additive.
The present invention carries out crosslinking reaction with amido triazine resol, Dicyanodiamide and two amido sulfobenzides as composite curing agent and with Resins, epoxy and obtains to have the epoxy composite material of high glass transition temp, and veneer sheet or the printed circuit board (PCB) made by this epoxy composite material have high glass transition temp and good thermotolerance, endurance, toughness, workability and electrical specification.
Embodiment
For making above-mentioned purpose of the present invention and the other objects, features and advantages can be more clear, hereinafter will enumerate preferred embodiment, be described in detail below.
Composition epoxy resin of the present invention comprises: (A) Resins, epoxy of 100 weight parts, and this Resins, epoxy a part contains two or more cycloalkyl groups; (B) composite curing agent comprises the amido triazine resol of 10 to 15 weight parts, the Dicyanodiamide of 0.1 to 5 weight part and two amido sulfobenzides of 4 to 8 weight parts; (C) curing catalyst of 0.01 to 1.0 weight part; And (D) inorganic filler of 0 to 80 weight part, and above each composition is that Resins, epoxy take 100 weight parts is as benchmark.
Resins, epoxy in the composition epoxy resin of the present invention is the resin that a part contains two or more cycloalkyl groups, and it comprises the bisphenol A-type novolac epoxy; Bisphenol F type novolac epoxy; And phosphorous epoxy resin, for example be with 9, the 10-dihydro-9-oxy is assorted-and 10-phosphine phenanthrene-10-oxide compound (DOPO) introduces in o-cresol formaldehyde epoxy resin (o-Cresol Novolac Epoxy Resin the is called for short CNE) resin structure and phosphorous (DOPO) o-cresol formaldehyde epoxy resin that forms.Above-mentioned resin can use separately or can make up simultaneously that the person uses jointly more than two kinds.
Composite curing agent in the composition epoxy resin of the present invention comprises amido triazine resol, Dicyanodiamide and two amido sulfobenzides, and this amido triazine resol, this Dicyanodiamide and this two amidos sulfobenzide can with the Resins, epoxy molecule in functional group reaction and form crosslinking net type epoxy composite material.Amido triazine resol in the composite curing agent of the present invention and the ratio of two amido sulfobenzides, can be by weight 1.25: 1 to 3.75: 1, wherein again with 2.0: 1 for better, and the weight of the Dicyanodiamide in this composite curing agent can be 0.033: 1 to 0.083: 1 with respect to the ratio of the gross weight of amido triazine resol and two amido sulfobenzides, wherein again with 0.056: 1 for better.In addition, the Resins, epoxy of composite curing agent and collocation calculates at blend proportion, removes and should calculate in conjunction with the epoxy equivalent theory, and need decide on the characteristic of made preimpregnation material and supporting material.The quality of crosslinking net type epoxy composite material character depends on the crosslinking degree between the polymer, accordingly, the weight ratio of the amido triazine resol in Resins, epoxy and the composite curing agent of the present invention need be maintained 1: 0.10 to 1: 0.15 at least, wherein again with 1: 0.12 for better.
Curing catalyst in the composition epoxy resin of the present invention comprises glyoxal ethyline (2-Methyl-Imidazole, 2MI), 2-ethyl-4-methylimidazole (2-Ethyl-4-Methyl-Imidazole, 2E4MI) and the imidazole compound such as 2-phenylimidazole (2-Phenyl-Imidazole, 2PI).And above-mentioned curing catalyst can use separately or can make up simultaneously jointly use more than two kinds.These curing catalysts can accelerate the set time of prepreg.
The inorganic filler that can add as required in the composition epoxy resin of the present invention comprises the powders such as silicon-dioxide, glass powder, talcum, kaolin, white mountain range soil, mica.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 the characteristics such as Resins, epoxy workability, flame retardant resistance, thermotolerance or wet fastness.Take the Resins, epoxy of 100 weight parts as benchmark, the consumption of inorganic filler is 0 to 80 weight part.
Also can comprise additive in the composition epoxy resin of the present invention, it comprises dispersion agent (for example silane coupling agent), toughner and fire retardant.And above-mentioned additive can use separately or can make up simultaneously jointly use more than two kinds.
The solvent that composition epoxy resin varnish of the present invention is used for example is acetone, methylethylketone (MEK), propylene glycol monomethyl ether (PM), pimelinketone, 1-Methoxy-2-propyl acetate (Propylene Glycol Methyl Ether Acetate, PMA) and dimethyl formamide (Dimethyl Formamide, DMF).And above-mentioned solvent can use separately or can make up simultaneously jointly use more than two kinds.Take the Resins, epoxy of 100 weight parts as benchmark, the consumption of solvent is 60 to 90 weight parts.
Composition epoxy resin of the present invention is to modulate by above-mentioned (A) Resins, epoxy, (B) composite curing agent, (C) curing catalyst and the inorganic filler that (D) adds are as required evenly mixed with agitator (mixer).Then, be dissolved or dispersed in the solvent by the composition epoxy resin that will modulate, and the viscosity of adjustment ring epoxy resins slurry, and make composition epoxy resin varnish.
Then, the made composition epoxy resin varnish of impregnation in being used to form the reinforcing material of prepreg 2 to 10 minute carries out drying and reaction with 150 ℃ to 180 ℃ heating with it in drying machine, produce by this prepreg of semi-cured state.Wherein, in addition employed supporting material also can use kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc. such as the glasscloth that is glass fabric, glassine paper, glassmat etc.
Carry out laminated and the form layers pressing plate to resulting prepreg with certain number of plies, then at the laminated Copper Foil of the outermost layer of at least one side of this veneer sheet, and carry out the pressurized, heated shaping, obtain by this veneer sheet of Copper Foil coating.Then, by subtractive process such as etchings, the Copper Foil that makes Copper Foil coating layer clamp surface is the part of residual formation circuit pattern only, and the part of removing other so just can obtain to have the printed circuit board (PCB) of circuit to form circuit pattern.
The embodiment that hereinafter provides in the technique means of setting forth the present invention, is not to limit technology category of the present invention only.
Embodiment one to seven and comparative example one to four are take weight epoxy as 100 parts, and other each composition all represents with relative parts by weight.In addition, identical composition all uses the product of identical label in following examples and the comparative example.
Embodiment one
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin (label Kolon 5138) of 100 weight parts, the amido triazine resol of 12 weight parts (large Japan chemistry, label LA 7054), the glyoxal ethyline of the Dicyanodiamide of two amido sulfobenzides of 6 weight parts, 1 weight part, 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment two
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, the amido triazine resol of 10 weight parts, two amido sulfobenzides of 8 weight parts, the Dicyanodiamide of 1 weight part, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment three
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, the amido triazine resol of 15 weight parts, two amido sulfobenzides of 4 weight parts, the Dicyanodiamide of 1 weight part, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment four
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, the amido triazine resol of 12 weight parts, two amido sulfobenzides of 6 weight parts, the Dicyanodiamide of 0.6 weight part, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment five
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, the amido triazine resol of 12 weight parts, two amido sulfobenzides of 6 weight parts, Dicyanodiamide and the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts of 1.5 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment six
With the bisphenol A-type novolac epoxy (label Kolon 1138) of 100 weight parts, the amido triazine resol of 12 weight parts, two amido sulfobenzides of 6 weight parts, the Dicyanodiamide of 0.8 weight part and the glyoxal ethyline of 0.5 weight part, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Embodiment seven
Two amido sulfobenzides of phosphorous (DOPO) o-cresol formaldehyde epoxy resin of the bisphenol A-type novolac epoxy of 50 weight parts, 50 weight parts, the amido triazine resol of 12 weight parts, 6 weight parts, the Dicyanodiamide of 1 weight part, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Comparative example one
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, two amido sulfobenzides of 12 weight parts, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Comparative example two
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, the Dicyanodiamide of 2 weight parts, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Comparative example three
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, two amido sulfobenzides of 12 weight parts, the Dicyanodiamide of 2 weight parts, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.Above-mentioned material after stirring 120 minutes under the room temperature, is formed composition epoxy resin varnish.
Comparative example four
With phosphorous (DOPO) o-cresol formaldehyde epoxy resin of 100 weight parts, the amido triazine resol of 24 weight parts, the glyoxal ethyline of 0.5 weight part and the talcum of 50 weight parts, under room temperature, use agitator to mix 60 minutes, add again the methylethylketone of 80 weight parts.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 to four prepared composition epoxy resin varnish are coated on 7628 (R/C:43%) glasscloth, then, be placed in the drying machine, and 180 ℃ of lower heat dryings 2 to 10 minutes, produce by this prepreg of semi-cured state.Then four prepregs are given laminated, and at the Copper Foil of each laminated 1oz of outermost layer of its both sides.Then, its pressurized, heated is carried out pressing, obtain by this Copper Foil coating layer pressing plate, 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 Copper Foil coating layer pressing plate.Then, by subtractive process such as etchings, the Copper Foil that makes Copper Foil coating layer clamp surface is the part of residual formation circuit pattern only, and removes other part, forms by this circuit pattern.According to this, just can obtain to be formed with on the top layer printed circuit board (PCB) of circuit.
To above-described embodiment and the water-absorbent of the prepared Copper Foil coating layer of comparative example pressing plate, anti-immersed solder (Solder Floating), tearing strength (Peeling Strength), glass transfer temperature (Glass TransitionTemperature, Tg), heat decomposition temperature, flame retardancy, toughness, specific inductivity, the dissipation factor and substrate surface elching resistant measure, the composition epoxy resin of embodiment one to seven and comparative example one to four and evaluation result thereof are then as shown in Table 1.
Property detection:
[water-absorbent test]
Carry out pressure cooker cooking test (PCT) test, veneer sheet 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 layer pressing plate.
[property testing of anti-immersed solder]
Whether the veneer sheet that drying is crossed behind the immersion certain hour, is observed defective and occurred in 288 ℃ soldering is bathed, for example determine with layering or the puff of veneer sheet.
[tearing strength test]
Tearing strength refers to Copper Foil to the sticking power of 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.
[glass transfer temperature test]
Utilize dynamic mechanical analysis instrument (DMA) to measure glass transfer temperature (Tg).The test specification of glass transfer temperature is interconnected IPC-TM-650.2.4.25C and the 24C detection method with encapsulating association (The Institute for Interconnecting and PackagingElectronic Circuits, IPC) 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, veneer sheet is fixed with the vertical position, with the Bunsen burner burning, relatively its spontaneous combustion is extinguished and combustion-supporting characteristic, and its report the test 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 with laminate surface with cross metal fixture, grant again vertical pressure, after remove this cross tool, observe cross shape vestige on the substrate, observe this laminate surface, occur then to be judged to be good without white scrimp, show slightly lineae ablicantes for general, it is bad that crackle or fracture person occur.
[specific inductivity and the dissipation factor measure]
According to ASTM D150 standard, under operating frequency 1GHz, calculate specific inductivity (Dk) and the dissipation factor (Df).
[test of substrate surface elching resistant]
Veneer sheet is immersed in the potassium permanganate solution, after soaking 10 minutes, again through neutralization, and weighing after the oven dry, detect the surface weight of unit surface and lose (mg/dm
2), to represent the etched degree of anti-solution.
Embodiment one to embodiment five adopts phosphorous (DOPO) o-cresol formaldehyde epoxy resin, and embodiment one expression the present invention is by the most preferred embodiment of the composite curing agent of amido triazine resol, two amido sulfobenzides and Dicyanodiamide combination.Amido triazine resol in embodiment two and three these composite curing agents of expression the present invention and the ratio of two amido sulfobenzides can be 1.25: 1 to 3.75: 1 by weight.The weight of the Dicyanodiamide in embodiment four and the five expressions composite curing agent of the present invention can be 0.033: 1 to 0.083: 1 with respect to the ratio of the gross weight of amido triazine resol and two amido sulfobenzides.Embodiment six adopts the bisphenol A-type novolac epoxy, and does not use the enforcement aspect of inorganic filler.The mixed enforcement aspect of supporting by the arm phosphorous (DOPO) o-cresol formaldehyde epoxy resin and bisphenol A-type novolac epoxy of embodiment seven expressions.Comparative example one expression solidifying agent only adopts two amido sulfobenzides, made veneer sheet poor toughness, and the Copper Foil tearing strength is poor.Comparative example two expression solidifying agent only adopt Dicyanodiamide, and made veneer sheet water-absorbent is high, poor heat resistance.Comparative example three expression solidifying agent adopt two amido sulfobenzide and Dicyanodiamides simultaneously, yet do not obtain significantly to promote on the Copper Foil tearing strength.When amido triazine resol was only used in comparative example four expressions as solidifying agent, the surface etching weight loss of veneer sheet reached 0.72mg/dm
2, therefore, the veneer sheet made with respect to the embodiment of the invention (using the composite curing agent that is combined into by amido triazine resol, two amido sulfobenzides and Dicyanodiamide), the surface of comparative example four made veneer sheets easily is etched.In addition, comparative example one to comparative example four shows that the glass tansition temperature (Tg) of its made veneer sheet is lower than the glass tansition temperature (can reach 180 ℃) of the made veneer sheet of the present invention.
As shown in Table 1, embodiment one to seven and comparative example one to four show, veneer sheet or the Copper Foil coating layer pressing plate made by the composition epoxy resin that contains composite curing agent of the present invention meet the specification that printed circuit board (PCB) requires, and represent in the characteristic of veneer sheet, the glass tansition temperature of the veneer sheet made from composition epoxy resin of the present invention can rise to that (for example embodiment one more than 180 ℃, three, four, five, seven), and on electric property, its specific inductivity (Dk) can be lower than 4.40 (for example embodiment two), and the dissipation factor (Df) can be lower than 0.020.In addition, veneer sheet of the present invention all presents good in tough sex expression.In addition, the weight loss after laminate surface of the present invention corrodes with etching solution ties up to 0.6mg/dm
2Below, therefore, veneer sheet of the present invention has good substrate and processes etched endurance.
Accordingly, made veneer sheet or the printed circuit board (PCB) of composition epoxy resin of the present invention has high glass tansition temperature and good thermotolerance, endurance, toughness, workability and electrical specification.
For all those skilled in the art, the present invention can make various modifications and changes 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 all in claims and the equivalency range thereof.
Claims (8)
1. composition epoxy resin comprises: (A) Resins, epoxy of 100 weight parts, and this Resins, epoxy a part contains two above cycloalkyl groups; And (B) composite curing agent, take the Resins, epoxy of 100 weight parts as benchmark, this composite curing agent is comprised of the amido triazine resol of 10 to 15 weight parts, the Dicyanodiamide of 0.1 to 5 weight part and the diamino diphenyl sulfone of 4 to 8 weight parts.
2. composition epoxy resin according to claim 1, wherein, the weight of the Dicyanodiamide in this composite curing agent is 0.033: 1 to 0.083: 1 with respect to the ratio of the gross weight of amido triazine resol and diamino diphenyl sulfone.
3. composition epoxy resin according to claim 1, wherein, this amido triazine resol is by the formed cocondensation resin of oxybenzene compound, aldehyde compound and guanamines compound.
4. composition epoxy resin according to claim 1 wherein, also comprises curing catalyst, and take the Resins, epoxy of 100 weight parts as benchmark, the content of this curing catalyst is 0.01 to 1.0 weight part.
5. composition epoxy resin according to claim 4, wherein, this curing catalyst is imidazole compound.
6. composition epoxy resin according to claim 1 wherein, also comprises inorganic filler, and take the Resins, epoxy of 100 weight parts as benchmark, the content of this inorganic filler is greater than 0 to 80 weight part.
7. preimpregnation material, be in supporting material impregnation according to claim 1,4,5 or 6 described composition epoxy resins, and carry out drying and make.
8. printed circuit board (PCB), be by with preimpregnation material according to claim 7 with certain number of plies laminated and form layers pressing plate, and obtain metal coating layer pressing plate in the laminated tinsel of the outermost layer of this one of them side of veneer sheet, and form certain circuit pattern and make in this tinsel of this metal coating layer clamp surface.
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| TWI288157B (en) * | 2001-07-11 | 2007-10-11 | Ind Tech Res Inst | Resin composition with low dielectric constant and its use |
| TWI342322B (en) * | 2007-03-28 | 2011-05-21 | Grand Tek Advance Material Science Co Ltd | Halogen-free flame retardant epoxy resin composition, prepreg, and copper clad laminate |
| CN101457012B (en) * | 2008-12-31 | 2011-06-15 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
-
2010
- 2010-06-22 CN CN 201010211684 patent/CN102295742B/en active Active
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| Publication number | Publication date |
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| CN102295742A (en) | 2011-12-28 |
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