CN102093670A - Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same - Google Patents
Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same Download PDFInfo
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- CN102093670A CN102093670A CN 201010602875 CN201010602875A CN102093670A CN 102093670 A CN102093670 A CN 102093670A CN 201010602875 CN201010602875 CN 201010602875 CN 201010602875 A CN201010602875 A CN 201010602875A CN 102093670 A CN102093670 A CN 102093670A
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- BNTWBLLVHLIEHB-GVHYBUMESA-N CC(C)CC[C@H](C1)C1NN Chemical compound CC(C)CC[C@H](C1)C1NN BNTWBLLVHLIEHB-GVHYBUMESA-N 0.000 description 1
Abstract
The invention relates to a halogen-free flame retardant epoxy resin composition and a copper clad plate prepared from the same. The halogen-free flame retardant epoxy resin composition comprises bisphenol A epoxy resin, carboxyl-terminated butadiene acrylonitrile, phosphorous resin, nitrogen fire retardant, amine curing agent, curing accelerator, filler and organic solvent. The copper clad plate prepared from the halogen-free flame retardant epoxy resin composition comprises a halogen-free flame retardant epoxy resin composition layer arranged on one or both surfaces of the laminated plate, and a copper foil pressed on the halogen-free flame retardant epoxy resin composition layer, wherein the laminated plate comprises a plurality of bonded sheets, and the halogen-free flame retardant epoxy resin composition layer is formed by coating the halogen-free flame retardant epoxy resin composition. The halogen-free flame retardant epoxy resin composition provided by the invention has high tracking property. The copper clad plate prepared from the halogen-free flame retardant epoxy resin composition has high CTI (comparative tracking index), good fire resistance and other good overall properties, has good processing characteristics, avoids dried flower dry flowers, cloth mark exposure and defects, and is suitable for fabricating single-sided or double-sided printed circuit boards with manufacturing requirement on CTI larger than or equal to 400 V.
Description
Technical field
The present invention relates to a kind of resin combination, particularly a kind of halogen-free flame retardant epoxy resin composition and use the copper-clad plate of its making.
Background technology
Along with electronics develops towards light, thin, short and small and multifunctional direction,, also constantly move towards thin type, miniaturization and densification as the tellite of electronics spare part main support; Along with the densification of circuit, requirements at the higher level, particularly environmental facies can be proposed to all the more so under the harsh conditions to the insulating reliability between circuit; At this moment, the insulating substrate surface of circuit card is subjected to that dust adheres to, moisture content dewfall or moisture corrodes and during the pollution of ionic contamination, under the impressed voltage effect, because its surperficial leakage current will increase greatly than clean surface, the moist pollutent of the heat of vaporization that leakage current produces plays pendulum the surface of insulating substrate, is easy to generate spark, insulativity is reduced, meeting puncture short when serious/open circuit; Common Resins, epoxy copper-clad plate, its relative anti creepage trace index is lower, generally is difficult to reach 240V, and therefore, it is necessary to improve insulating material relative discharge tracking index.
Existing high relative discharge tracking index (CTI) copper-clad laminate, be to adopt the woven fiber glass that high CTI characteristic is arranged to strengthen bonding sheet at its surface adhesion sheet, compacting forms again, but because bonding sheet occurs easily because matching, the bonding sheet control indexes of woven fiber glass and resin are bad, cause sheet material that the problem of dried flower or war proclamation line, thickness and precision control is arranged, influence the creepage trace index of sheet material.Attached resin Copper Foil and the copper-clad laminate of a kind of high CTI of halogen are disclosed and application number is 200810220680.2 patent application, though its attached resin Copper Foil can be realized applying continuously making, but Copper Foil is basic fixed after coating, the thickness specification can not change, in addition, attached resin Copper Foil is when cutting, and toner easily is scattered, and pollutes copper-clad surface.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flame retardant epoxy resin composition, not halogen-containing, environmental protection has excellent flame-retardant performance and high relative discharge tracking index.
Another object of the present invention is to provide a kind of copper-clad plate of using above-mentioned halogen-free flame retardant epoxy resin composition to make, have excellent comprehensive performances such as high relative discharge tracking index and flame retardancy, and have good processing properties, be applicable to the making printed circuit board.
For achieving the above object, the invention provides a kind of halogen-free flame retardant epoxy resin composition, press solid weight part and calculate, it comprises that component and weight part thereof are as follows: bisphenol A type epoxy resin 20-50 part, nbr carboxyl terminal 20-40 part, phosphorous resin 10-30 part, nitrogen flame retardant 5-30 part, amine curing agent 1-10 part, curing catalyst 0.01-1.0 part, filler 15-50 part and organic solvent are an amount of.
Wherein, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 40-60% of total weight percent.
Described bisphenol A type epoxy resin is meant that number-average molecular weight is the bisphenol A type epoxy resin of 600-4000.
Described nbr carboxyl terminal is an acrylonitrile butadiene copolymer, and wherein acrylonitrile content is 18-50 quality %, and the copolymer molecule chain end is by carboxylated, and vinyl cyanide, divinyl and carboxylic monomeric copolymer rubber.
Described phosphorous resin is phosphorous modified epoxy or phosphorus containing phenolic resin, wherein phosphorous modified epoxy is the phosphorous luxuriant and rich with fragrance type compound that has, comprise 9, the Resins, epoxy, 9 of 10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound correspondence, the Resins, epoxy of 10-dihydro-9-oxy-10-phospho hetero phenanthrene Resorcinol correspondence, and 9, the Resins, epoxy of 10-dihydro-9-oxy-10-phospho hetero phenanthrene naphthoquinones correspondence, it selects above-mentioned phosphorous one or more of luxuriant and rich with fragrance type compound of having for use; Phosphorus containing phenolic resin is the phosphorous luxuriant and rich with fragrance type compound that has, and comprises the resol of dihydro 9-oxo-10-phospho hetero phenanthrene correspondence, specifically select for use in the following structural formula-kind or multiple:
Described nitrogen flame retardant comprises compound in triazine class, is trimeric cyanamide and salt thereof.
Described amine curing agent is Dyhard RU 100, diaminodiphenylsulfone(DDS) or two amido ditanes.
Described filler is one or more in hydrated metal oxide or the metal sulfate.The preferred aluminium hydroxide of hydrated metal oxide; The metal sulfate preferably barium sulfate.
In addition, a kind of copper-clad plate of using above-mentioned halogen-free flame retardant epoxy resin composition to make also is provided, comprise: veneer sheet, be located at the halogen-free flame retardant epoxy resin composition layer of veneer sheet one or both sides and be overlaid on Copper Foil on the halogen-free flame retardant epoxy resin composition layer, this halogen-free flame retardant epoxy resin composition layer is formed by described halogen-free flame retardant epoxy resin composition coating.
Described veneer sheet comprises the bonding sheet that several pieces are bonding.
Beneficial effect of the present invention: halogen-free flame retardant epoxy resin composition of the present invention, has high creepage trace characteristic, copper-clad plate with its making, have excellent comprehensive performances such as high CTI and flame retardancy, and has good processing properties, avoided defectives such as dried flower or war proclamation line, be applicable to and make single, double the printed circuit board that requires CTI 〉=400V.
Embodiment
Halogen-free flame retardant epoxy resin composition of the present invention, press solid weight part and calculate, it comprises that component and weight part thereof are as follows: bisphenol A type epoxy resin 20-50 part, nbr carboxyl terminal 20-40 part, phosphorous resin 10-30 part, nitrogen flame retardant 5-30 part, amine curing agent 1-10 part, curing catalyst 0.01-1.0 part, filler 15-50 part and organic solvent are an amount of.Wherein, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 40-60% of total weight percent.
Described bisphenol A type epoxy resin is meant that number-average molecular weight is the bisphenol A type epoxy resin of 600-4000, the Epikote 1001,1002,1004,1007 of representational resin such as Hexion chemical company and 1009 etc.These specific epoxy resins can use separately, and perhaps two or more different rings epoxy resins are used in combination.
Described nbr carboxyl terminal, acrylonitrile butadiene copolymer normally, wherein acrylonitrile content can be 18-50 quality %, is preferably 20-30 quality %.Wherein the copolymer molecule chain end is by carboxylated, and the copolymer rubber of vinyl cyanide, divinyl and carboxylic monomer such as vinylformic acid or toxilic acid.The carboxylated of molecule chain end can realize as the monomer of methacrylic acid etc. with comprising carboxyl in the above-mentioned copolymer rubber.The object lesson of these commercially available carboxylic NBR comprises Nipol 1072CG (ZeonCorporation manufacturing) and high purity, hangs down the product XER-32 (JSR Corporation manufacturing) of ionic impurity.
Described phosphorous resin can be phosphorous modified epoxy or phosphorus containing phenolic resin, wherein phosphorous modified epoxy is the phosphorous luxuriant and rich with fragrance type compound that has, comprise 9, the Resins, epoxy, 9 of 10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound correspondence, the Resins, epoxy of 10-dihydro-9-oxy-10-phospho hetero phenanthrene Resorcinol correspondence, and 9, the Resins, epoxy of 10-dihydro-9-oxy-10-phospho hetero phenanthrene naphthoquinones correspondence, it selects above-mentioned phosphorous one or more of luxuriant and rich with fragrance type compound of having for use; Phosphorus containing phenolic resin is the phosphorous luxuriant and rich with fragrance type compound that has, and comprises the resol of dihydro 9-oxo-10-phospho hetero phenanthrene correspondence, specifically selects in the following structural formula one or more for use:
Commercially available phosphorous modified epoxy has YEP-250, YEP-300 (wide mountain chemical industry company limited makes) and XZ92530 (manufacturing of DOW chemical company) etc.; Commercially available phosphorus containing phenolic resin has XZ92741 (manufacturing of Dow chemical company), LC-950 (manufacturing of Korea S Shin-A company) etc.Phosphorous modified epoxy or phosphorus containing phenolic resin can a kind of separately or any two uses that mutually combine.
Phosphorus content is 1.0-2.5wt% in the described phosphorous resin, when phosphorus content is lower than 1.0wt%, the flame retardant resistance of resin combination descends serious, at this moment need to add more that polynitrogen system fire retardant and hydrated metal oxide filler just can make the incendivity of resin combination reach UL 94V-0 level, but too much amount of filler can reduce the over-all properties of resin combination; And when phosphorus content was higher than 2.5wt%, the flame retardant resistance of resin combination had bigger guarantee, became very difficult but CTI reaches 400V.
Described nitrogen flame retardant mainly is a compound in triazine class, is trimeric cyanamide (MA) and salt thereof; The fire retardant of compound in triazine class mainly plays a role with the dilution combustiblematerials by minute heat of desorption and production non-flammable gas, and their major advantage is Halogen, low toxicity, low cigarette, does not produce etchant gas; Main drawback is that flame retarding efficiency is not good enough.The present invention adopt melamine cyanurate work in coordination with charring rate very high get phenyl ring oxygen and benzoxazine reaches fire-retardant requirement, nitrogen flame retardant of greatest concern is Ciba Meplapur series product, and particle diameter has Melapur MC50, Melapur MC25 and Melapur MC15 etc. from big to small; Domestic also have manufacturer production this be the type product, reaches as Yueyang rubber maintenance company limited etc. is installed.
Described amine curing agent is Dyhard RU 100 (DICY), diaminodiphenylsulfone(DDS) (DDS) or two amido ditanes (DDM), above-mentioned solidifying agent can be that one or more mix use separately, and the equivalence ratio of amine curing agent equivalent and Resins, epoxy is 0.5-1.0.The effect of this amine curing agent is that halogen-free flame retardant epoxy resin composition of the present invention is fully solidified, and realizes optimum properties.
Described curing catalyst is the imidazoles curing catalyst, can be in glyoxal ethyline, 1-Methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, the 2-phenyl-4-methylimidazole one or more.
Described filler is hydrated metal oxide or metal sulfate, can use one or more mixture wherein; The preferred aluminium hydroxide of hydrated metal oxidation wherein, the metal sulfate preferably barium sulfate, amount of filler is preferably 20-45 part.Above-mentioned filler can pass through the coupling agent surface treatment, and the consumption of coupling agent is the 0-1% of filler weight.Increase the usage ratio of filler, can improve the proof tracking and the CTI value of halogen-free flame retardant epoxy resin composition, simultaneously can give better flame retardant resistance, but amount of filler should be suitable, too much use will cause some counter productives, and fillers dispersed is evenly difficult, reunite easily, and reduce the cohesive strength of halogen-free flame retardant epoxy resin composition, influence over-all properties.
Described organic solvent is one or more in dimethyl formamide, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, acetone, butanone, the pimelinketone etc., its effect is components such as dissolving resin and solidifying agent, regulate in this halogen-free flame retardant epoxy resin composition solids content in the 40-60wt% scope, make it have suitable viscosity, improve apparent mass with the glued membrane of its making.
The copper-clad plate that the above-mentioned halogen-free flame retardant epoxy resin composition of use of the present invention is made, use described halogen-free, flame-retardant composition to make, be used to make printed circuit board, this copper-clad plate comprises: veneer sheet, be located at the halogen-free flame retardant epoxy resin composition layer of veneer sheet one or both sides and be overlaid on Copper Foil on the halogen-free flame retardant epoxy resin composition layer, this halogen-free flame retardant epoxy resin composition layer is formed by the halogen-free flame retardant epoxy resin composition coating.Wherein veneer sheet comprises the bonding sheet that several pieces are bonding, and various types of bonding sheets during bonding sheet can adopt and have now also can be various types of prepregs etc.
When halogen-free flame retardant epoxy resin composition of the present invention is made copper-clad plate, use similar devices such as ball mill, jar mill, sand mill, and be used high-shear dispersed with stirring equipment, solidifying agent, curing catalyst and solvent with described ratio, fully dissolving, after with addings such as bisphenol A type epoxy resin, nbr carboxyl terminal, phosphorous resin, nitrogen flame retardant and fillers, fully be dissolved in and be uniformly dispersed, making solids content is the halogen-free flame retardant epoxy resin composition glue of 40-60wt%; Adopt epoxy glass cloth prepreg (FR-4) bonding sheet on demand, independent one or both of epoxy glass paper prepreg (CEM-3) core material or epoxy wood pulp paper prepreg (CEM-1) core material become the core material veneer sheet by the thickness requirement combination collocation, as veneer sheet, use coating equipment that the halogen-free flame retardant epoxy resin composition glue that makes is coated on the one or both sides of veneer sheet equably, pass through drying oven again, heat 2-6min down at 80-160 ℃, to remove organic solvent and to carry out drying, can on veneer sheet, form just layer of the uniform halogen-free flame retardant epoxy resin composition of thickness.But formed halogen-free flame retardant epoxy resin composition layer full wafer uncovered, and flexibility is good, and flexible and dry linting not, and its CTI 〉=400V are not halogen-containing, have over-all propertieies such as good thermotolerance, flame retardant resistance, alkali resistance.And then on the halogen-free flame retardant epoxy resin composition layer, be covered with Copper Foil, and this being combined put into thermocompressor and carry out hot pressing, curing molding, hot pressing pressure is 10-50kgf/cm
2, be preferably 20-30kgf/cm
2, the forming and hardening temperature is 150-210 ℃, is preferably 170-180 ℃, and the forming and hardening time is 30-120min, and preferred 50-70min is prepared into epoxy glass cloth copper-clad plate (FR-4), compound basic copper-clad plate (CEM-3 or CEM-1).Prepared copper-clad plate has excellent anti creepage trace characteristic, and CTI 〉=400V has excellent comprehensive performances simultaneously, is applicable to make single, double the printed circuit board that requires CTI 〉=400V.
In addition, the present invention also can make glued membrane with halogen-free flame retardant epoxy resin composition and release film etc. earlier, makes copper-clad plate again, and this glued membrane also has characteristics such as storage-life is long, manageable and easy to use.
At the copper-clad plate that above-mentioned halogen-free flame retardant epoxy resin composition is made, test its CTI, flame retardant resistance, stripping strength etc., further give to illustrate in detail and describe as following embodiment.
Now the embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
The preparation of halogen-free flame retardant epoxy resin composition glue
(median size is 1 to 5um to take by weighing 44 parts of bisphenol A type epoxy resins (Epikote 1002), 30 parts of nbr carboxyl terminals (Nipol1072CG), 26 parts of phosphorus containing phenolic resins (XZ92741), 20 parts of nitrogen flame retardants (melapurMC15), aluminium hydroxide, purity is more than 99%) 0.1 part of 30 parts, 0.7 part of Dyhard RU 100 and 2-ethyl-4-methylimidazole, form glue with solvent dimethylformamide dissolving said components, the solids content of regulating glue is 50%, makes the halogen-free flame retardant epoxy resin composition glue.
The preparation of copper-clad plate
With 8 big stack neatly for flaky FR-4 prepreg of 300mm * 300mm or bonding sheet for a short time, upper and lower surface is applied to the glue that makes on the veneer sheet by coating machine, gluing thickness is 50 μ m, put into again in 155 ℃ the baking oven and heat 5min, glue forms partly solidified halogen-free flame retardant epoxy resin composition layer on veneer sheet, on composition layer, mix 35 μ m electrolytic copper foils again, after finishing batching, to fold combo closes and puts into thermocompressor and do vacuum hotpressing, hot pressing temperature 170-180 ℃, the about 25kgf/cm of pressure
2, about 90min of time promptly gets copper-clad plate after hot-forming.
Embodiment 2:
Repeat embodiment 1 preparation, different is in the halogen-free flame retardant epoxy resin composition glue system, adopt 35 parts of bisphenol A type epoxy resins (Epikote 1002), 30 parts of nbr carboxyl terminals (Nipol1072CG), 13 parts of phosphorous epoxy resins (YEP-250), 22 parts of phosphorus containing phenolic resins (XZ92741), 10 parts of nitrogen flame retardants (melapur MC15), (median size is 1 to 5 μ m to aluminium hydroxide, purity is more than 99%) 0.1 part of 30 parts, 0.45 part of Dyhard RU 100 and 2-ethyl-4-methylimidazole, other each step preparation and embodiment 1 with.
Embodiment 3:
Repeat embodiment 1 preparation, different is in the halogen-free flame retardant epoxy resin composition glue system, adopt bisphenol A-type NOVOLAC Resins, epoxy (EPR627, the manufacturing of Hexion company) 19 part, 25 parts of bisphenol A type epoxy resins (Epikote 1002), 30 parts of nbr carboxyl terminals (Nipol 1072CG), 26 parts of phosphorus containing phenolic resins (XZ92741), 10 parts of nitrogen flame retardants (melapur MC15), (median size is 1 to 5 μ m to aluminium hydroxide, purity is more than 99%) 30 parts, 0.1 part of 0.75 part of Dyhard RU 100 and 2-ethyl-4-methylimidazole, other each step preparation and embodiment 1 are together.
Comparative example 1:
Repeat embodiment 1 preparation, different is in the resin combination composition glue liquid system, adopt 44 parts of bisphenol A type epoxy resins (Epikote 1002), 30 parts of nbr carboxyl terminals (Nipol 1072CG), 26 parts of phosphorus containing phenolic resins (XZ92741), 10 parts of nitrogen flame retardants (melapur MC15), (median size is 1 to 5 μ m to aluminium hydroxide, purity is more than 99%) 0.1 part of 30 weight parts, 0.7 part of Dyhard RU 100 and 2-ethyl-4-methylimidazole, other each step preparation and embodiment 1 with.
Comparative example 2:
Repeat embodiment 1 preparation, different is in the resin combination composition glue liquid system, adopt 60 parts of bisphenol A type epoxy resins (Epikote 1002), 15 parts of nbr carboxyl terminals (Nipol 1072CG), 25 parts of phosphorus containing phenolic resins (XZ92741), 20 parts of nitrogen flame retardants (melapur MC15), (median size is 1 to 5 μ m to aluminium hydroxide, purity is more than 99%) 0.1 part of 30 parts, 1.0 parts of Dyhard RU 100s and 2-ethyl-4-methylimidazole, other each step preparation and embodiment 1 with.
Comparative example 3:
Repeat embodiment 1 preparation, different is in the resin combination composition glue liquid system, adopt 0.1 part of 20 parts of bisphenol A type epoxy resins (Epikote 1002), 30 parts of nbr carboxyl terminals (Nipol 1072CG), 20 parts of phosphorous epoxy resins (YEP-250), 30 parts of phosphorus containing phenolic resins (XZ92741), 20 parts of nitrogen flame retardants (melapur MC15), 1.2 parts of Dyhard RU 100s and 2-ethyl-4-methylimidazole, other each step preparation and embodiment 1 with.
The performance of the prescription of each embodiment of table 1. and comparative example and the copper-clad plate that makes
The testing method of above performance, the testing method of CTI (relative discharge tracking index) adopt the CTI tester of AG5101A (manufacturing of Zhuhai safety testing apparatus company limited) to measure based on IEC-60112 standard (International Electrotechnical Commission Standard); Incendivity (flame retardant resistance) testing method is according to U.S. UL (American insurance merchant laboratory) standard testing, and the testing method of stripping strength adopts American I PC-TM-652.4.8 standard; Digital micrometer is adopted in thickness measurement; The digital display electronic balance is adopted in weight measurement.
In sum, halogen-free flame retardant epoxy resin composition of the present invention, has high creepage trace characteristic, but the halogen-free flame retardant epoxy resin composition layer full wafer with its formation uncovered, flexible, dry linting not, CTI 〉=400V has over-all propertieies such as good thermotolerance, flame retardant resistance, alkali resistance, is convenient to make not halogen-containing slim copper-clad plate and multilayer printed wiring board; Copper-clad plate of the present invention has excellent comprehensive performances such as high CTI and flame retardancy, and has good processing properties, has avoided defectives such as dried flower or war proclamation line, is applicable to make single, double the printed circuit board that requires CTI 〉=400V.
Above embodiment, be not that content to composition of the present invention imposes any restrictions, every foundation technical spirit of the present invention or composition composition or content all still belong in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (10)
1. halogen-free flame retardant epoxy resin composition, it is characterized in that, press solid weight part and calculate, it comprises that component and weight part thereof are as follows: bisphenol A type epoxy resin 20-50 part, nbr carboxyl terminal 20-40 part, phosphorous resin 10-30 part, nitrogen flame retardant 5-30 part, amine curing agent 1-10 part, curing catalyst 0.01-1.0 part, filler 15-50 part and organic solvent are an amount of.
2. halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described bisphenol A type epoxy resin is meant that number-average molecular weight is the bisphenol A type epoxy resin of 600-4000.
3. halogen-free flame retardant epoxy resin composition as claimed in claim 1, it is characterized in that, described nbr carboxyl terminal is an acrylonitrile butadiene copolymer, wherein acrylonitrile content is 18-50 quality %, the copolymer molecule chain end is by carboxylated, and vinyl cyanide, divinyl and carboxylic monomeric copolymer rubber.
4. halogen-free flame retardant epoxy resin composition as claimed in claim 1, it is characterized in that, described phosphorous resin is phosphorous modified epoxy or phosphorus containing phenolic resin, wherein phosphorous modified epoxy is the phosphorous luxuriant and rich with fragrance type compound that has, comprise 9, the Resins, epoxy, 9 of 10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound correspondence, the Resins, epoxy of 10-dihydro-9-oxy-10-phospho hetero phenanthrene Resorcinol correspondence, and 9, the Resins, epoxy of 10-dihydro-9-oxy-10-phospho hetero phenanthrene naphthoquinones correspondence, it selects above-mentioned phosphorous one or more of luxuriant and rich with fragrance type compound of having for use; Phosphorus containing phenolic resin is the phosphorous luxuriant and rich with fragrance type compound that has, and comprises the resol of dihydro 9-oxo-10-phospho hetero phenanthrene correspondence, specifically selects in the following structural formula one or more for use:
5. halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described nitrogen flame retardant comprises compound in triazine class, is trimeric cyanamide and salt thereof.
6. halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described amine curing agent is Dyhard RU 100, diaminodiphenylsulfone(DDS) or two amido ditanes.
7. halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described filler is one or more in hydrated metal oxide or the metal sulfate.
8. halogen-free flame retardant epoxy resin composition as claimed in claim 7 is characterized in that, the preferred aluminium hydroxide of described hydrated metal oxide; The metal sulfate preferably barium sulfate.
9. copper-clad laminate that uses halogen-free flame retardant epoxy resin composition as claimed in claim 1 to make, it is characterized in that, it comprises: veneer sheet, be located at the halogen-free flame retardant epoxy resin composition layer of veneer sheet one or both sides and be overlaid on Copper Foil on the halogen-free flame retardant epoxy resin composition layer, this halogen-free flame retardant epoxy resin composition layer is formed by described halogen-free flame retardant epoxy resin composition coating.
10. copper-clad plate as claimed in claim 9 is characterized in that described veneer sheet comprises the bonding sheet that several pieces are bonding.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102127289A (en) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, and adhesive film and copper-clad plate prepared from same |
-
2010
- 2010-12-23 CN CN 201010602875 patent/CN102093670B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102127289A (en) * | 2010-12-23 | 2011-07-20 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, and adhesive film and copper-clad plate prepared from same |
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| CN102127289B (en) * | 2010-12-23 | 2013-05-01 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, and adhesive film and copper-clad plate prepared from same |
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