CN102295742A - 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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- CN102295742A CN102295742A CN 201010211684 CN201010211684A CN102295742A CN 102295742 A CN102295742 A CN 102295742A CN 201010211684 CN201010211684 CN 201010211684 CN 201010211684 A CN201010211684 A CN 201010211684A CN 102295742 A CN102295742 A CN 102295742A
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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 the veneer sheet (Copper Clad Laminate is called for short CCL) of Copper Foil coating, and it mainly is made up of resin, supporting material and Copper Foil three.What resin wherein was commonly used has: what Resins, epoxy, resol, polyamine formaldehyde, silicone and Teflon etc., supporting material were then commonly used has: 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.Give laminated with certain number of plies above-mentioned preimpregnation material then, and the outermost layer of at least one side of the preimpregnation material 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.Though this highly cross-linked reticulated structure has quite high hardness and glass transfer temperature and endurance, this structure has easily 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 curing agent for epoxy resin, use comprises the composition epoxy resin of amido triazine resol and makes substrate, can improve the thermotolerance of substrate, can improve the sticking power of Copper Foil simultaneously again, 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 (as oxalic acid, tosic acid), react and make, wherein, this oxybenzene compound can be as phenol, cresols, xylenol etc., and aldehyde compound can be as formaldehyde.In addition, this guanamines compound is then as follows,
(in the formula R be meant amido, phenyl or as alkyl such as methyl)
This guanamines compound for example is melamine, benzyl guanamines, methyl guanamines etc., and it can use separately or mix, and the person uses jointly more than two kinds.
Though amido triazine resol (ATN) has good modularity to be easy to allotment, and good effect is arranged for improving Copper Foil sticking power and thermotolerance, can use with other solidifying agent common modulation again, but on the toughness of made substrate and endurance, need further to be improved.Therefore, the combination of various solidifying agent constantly is developed, for example United States Patent (USP) the 6th, 716, No. 530, be 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 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 Dicyanodiamide (Dicyandiamide respectively, 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 preferable control curing reaction.
The problem that on toughness, thermotolerance and the endurance of substrate, produces in order further to improve prior art to use the combination of amido triazine phenolic resin curative or other solidifying agent, simultaneously can take into account the low dielectric characteristics of substrate again, then become research topic of the present invention.
Summary of the invention
In view of the above, the objective of the invention is to, a kind of composition epoxy resin is provided, it is to form according to specified proportion blended amido triazine resol, Dicyanodiamide and two amido sulfobenzides with the Resins, epoxy collocation, and amido triazine resol wherein, Dicyanodiamide and two amido sulfobenzides promptly constitute 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 the dissipation factor (Dissipation Factor has more effect on Df).
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, the above-mentioned composition epoxy resin varnish of impregnation in the supporting material of glass fabric etc. then 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, this method comprises: give the above-mentioned preimpregnation material 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 preimpregnation material, and this metal coating layer pressing plate is carried out pressurized, heated be shaped, remove the tinsel of the part of above-mentioned metal coating layer clamp surface then, 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 according to specified proportion blended amido triazine resol, Dicyanodiamide and two amido sulfobenzides.
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 make above-mentioned purpose of the present invention and other purpose, feature and advantage can be more clear, hereinafter will enumerate preferred embodiment, be described in detail below.
Composition epoxy resin of the present invention comprises: (A) 100 parts by weight of epoxy resin, 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 to be benchmark with 100 parts by weight of epoxy resin.
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 react and formation crosslinking net type epoxy composite material with the functional group in the Resins, epoxy molecule.The amido triazine resol in the composite curing agent of the present invention and the ratio of two amido sulfobenzides, can be 1.25: 1 to 3.75: 1 by weight, be preferable with 2.0: 1 again wherein, 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, is preferable with 0.056: 1 again wherein.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, in view of the above, 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, is preferable with 1: 0.12 again wherein.
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 2-phenylimidazole (2-Phenyl-Imidazole 2PI) waits imidazole compound.And above-mentioned curing catalyst can use separately or can make up use jointly more than two kinds simultaneously.These curing catalysts can quicken the set time of preimpregnation material.
The inorganic filler that can add as required in the composition epoxy resin of the present invention comprises 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 characteristics such as Resins, epoxy workability, flame retardant resistance, thermotolerance or wet fastness.With 100 parts by weight of epoxy resin is benchmark, and 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 use jointly more than two kinds simultaneously.
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 use jointly more than two kinds simultaneously.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 is can be by above-mentioned (A) Resins, epoxy, (B) composite curing agent, (C) curing catalyst and the inorganic filler that (D) adds are as required modulated with agitator (mixer) uniform mixing.Then, by the synthetic composition epoxy resin of institute is dissolved or dispersed in the solvent, and adjust the viscosity of Resins, epoxy slurry, and make composition epoxy resin varnish.
Then, the made composition epoxy resin varnish of impregnation in being used to form the reinforcement material of preimpregnation material 2 to 10 minute carries out drying and reaction with 150 ℃ to 180 ℃ heating with it in drying machine, produce the preimpregnation material of semi-cured state by this.Wherein, employed supporting material for example is the glasscloth of glass fabric, glassine paper, glassmat etc., in addition also can use kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc.
Carry out laminated and the form layers pressing plate to resulting preimpregnation material with certain number of plies,, and carry out the pressurized, heated shaping, obtain the veneer sheet of Copper Foil coating by this then at the laminated Copper Foil of the outermost layer of at least one side of this veneer sheet.Then,, make the part of the only residual formation circuit pattern of Copper Foil of Copper Foil coating layer clamp surface, and the part of removing other so just can obtain to have the printed circuit board (PCB) of circuit to form circuit pattern by subtractive process such as etchings.
Hereinafter the embodiment that is provided in the technique means of setting forth the present invention, is not in order to limit technology category of the present invention only.
Embodiment one to seven and comparative example one to four are to be 100 parts with weight epoxy, and other each composition is all represented 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 (big 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 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
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 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
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 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
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 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
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 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
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 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
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 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
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 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 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 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 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 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 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 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 to four 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-cured state by this 180 ℃ of following heat dryings 2 to 10 minutes.Then four preimpregnation materials 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 Copper Foil coating layer pressing plate by this, 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, make the part of the only residual formation circuit pattern of Copper Foil of Copper Foil coating layer clamp surface, and remove other part, form circuit pattern by this.According to this, just can obtain to be formed with the printed circuit board (PCB) of circuit on the top layer.
To the foregoing description 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 the layering or the puff of veneer sheet.
[tearing strength test]
Tearing strength is meant the sticking power of Copper Foil for 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 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, 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 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 with cross metal fixture with laminate surface, grant vertical pressure again, after remove this cross tool, observe cross shape vestige on the substrate, observe 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 measure]
According to ASTM D150 standard, under operating frequency 1GHz, calculate the 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 oven dry back weighing, 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.The 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.Embodiment seven expressions mix the enforcement aspect of supporting by the arm phosphorous (DOPO) o-cresol formaldehyde epoxy resin and bisphenol A-type novolac epoxy.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, made veneer sheet water-absorbent height, 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 (using the composite curing agent that is combined into by amido triazine resol, two amido sulfobenzides and Dicyanodiamide) with respect to the embodiment of the invention, 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 (for example embodiment one, three, four, five, seven) more than 180 ℃, 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.
In view of the above, 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 (10)
1. composition epoxy resin comprises: (A) 100 parts by weight of epoxy resin, and this Resins, epoxy a part contains two or more cycloalkyl groups; And (B) composite curing agent, be benchmark with 100 parts by weight of epoxy resin, this 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.
2. composition epoxy resin according to claim 1, wherein, the amido triazine resol in this composite curing agent and the ratio of two amido sulfobenzides are 1.25: 1 to 3.75: 1 by weight.
3. 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 two amido sulfobenzides.
4. composition epoxy resin according to claim 1, wherein, the ratio of the amido triazine resol in this Resins, epoxy and this composite curing agent is 1: 0.10 to 1: 0.15 by weight.
5. 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.
6. composition epoxy resin according to claim 1 wherein, also comprises curing catalyst, is benchmark with 100 parts by weight of epoxy resin, and the content of this curing catalyst is 0.01 to 1.0 weight part.
7. composition epoxy resin according to claim 6, wherein, this curing catalyst is an imidazole compound.
8. composition epoxy resin according to claim 1 wherein, also comprises inorganic filler, is benchmark with 100 parts by weight of epoxy resin, and the content of this inorganic filler is 0 to 80 weight part.
9. preimpregnation material is that impregnation and is carried out drying and made according to claim 1,6,7 or 8 described composition epoxy resins in supporting material.
10. printed circuit board (PCB), be by with preimpregnation material according to claim 9 with certain number of plies laminated and form layers pressing plate, and obtain metal coating layer pressing plate, and on this tinsel of this metal coating layer clamp surface, form certain circuit pattern and make in the laminated tinsel of the outermost layer of this one of them side of veneer sheet.
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| CN104228309A (en) * | 2014-08-26 | 2014-12-24 | 铜陵浩荣华科复合基板有限公司 | Preparation method of halogen-free Tg150 copper clad laminate |
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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 |
| TW200838926A (en) * | 2007-03-28 | 2008-10-01 | Grand Tek Advance Material Science Co Ltd | Halogen-free flame retardant epoxy resin composition, prepreg, and copper clad laminate |
| CN101457012A (en) * | 2008-12-31 | 2009-06-17 | 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 |
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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 |
| TW200838926A (en) * | 2007-03-28 | 2008-10-01 | Grand Tek Advance Material Science Co Ltd | Halogen-free flame retardant epoxy resin composition, prepreg, and copper clad laminate |
| US20080241578A1 (en) * | 2007-03-28 | 2008-10-02 | Grand Tek Advance Material Science Co., Ltd. | Halogen-free flame retardant epoxy resin composition, prepreg, and copper clad lamination |
| CN101457012A (en) * | 2008-12-31 | 2009-06-17 | 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104228309A (en) * | 2014-08-26 | 2014-12-24 | 铜陵浩荣华科复合基板有限公司 | Preparation method of halogen-free Tg150 copper clad laminate |
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| CN102295742B (en) | 2013-01-02 |
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