CN101280093A - Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate - Google Patents
Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate Download PDFInfo
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Abstract
The invention relates to a halogen-free flame-retardant epoxy resin composite, the flexible copper clad laminate made from the epoxy resin composite and the production method. The halogen-free flame-retardant epoxy resin composite is composed of solid components and organic solvents, wherein, the solid components include: phosphorus epoxy resin, synthetic rubber, rubber-modified epoxy resin and composite curing agent. The flexible copper clad laminate made from the halogen-free flame-retardant epoxy resin composite is a three-layer flexible copper clad laminate, including a polyimide insulation film, a coating of halogen-free flame-retardant epoxy resin composite coated on the polyimide insulation film, and a copper foil pressed on the coating of halogen-free flame-retardant epoxy resin composite. The resin composite of the invention is halogen-free and dispenses with other organic phosphorus flame retardants; the flexible copper clad laminate made from the composite has the flame retardancy up to UL94 V-0-level and has the advantages of high peeling strength, excellent dimensional stability, softness, good ion migration resistance and processing performance.
Description
Technical field
The present invention relates to a kind of halogen-free flame retardant epoxy resin composition, the flexibility coat copper plate that uses halogen-free flame retardant epoxy resin composition to make, and the method for making this flexibility coat copper plate.
Background technology
All the time, three-layer process flexibility coat copper plate (FCCL) adopts the very high brominated resins of bromine content to reach fire-retardant purpose, though possess the good flame effect, but combustion processes can produce corrodibility and toxic hydrogen halide, and the amount of being fuming is big, may have the hidden danger that produces the carcinogenic substance dioxin during incomplete combustion; In addition, the thermal expansivity of brominated resins (CTE) big than non-brominated resins all.In order to satisfy the environmental protection trend of " leadless process " and " Halogen baseplate material ", producer is all at the product of active development halogen-free and lead-free, the most frequently used non-bromine series flame retardant systems is mainly organic phosphorus flame retardant now, because the inorganic phosphorus flame retardant just makes an addition in the system, and need to add a large amount of fire retardants and just can reach the UL94V-0 level, the pollution of this reduction for substrate property, processing procedure and the destruction of ecotope are all serious than response type organic phosphorus flame retardant, so the response type organic phosphorus flame retardant is the important directions of developing at present.
At present, the major technique approach that realizes the flexibility coat copper plate halogen-free flameproof is with thermoplastic resin or rubber toughened phosphorous epoxy resin, add mineral filler assisting flame-resistants such as other P contained compounds and a certain amount of aluminium hydroxide simultaneously, adopt diaminodiphenylsulfone(DDS) (DDS) or resol as the solidifying agent of phosphorous epoxy resin (open as the spy 2005-248048, spy open 2006-332150, the spy opens 2006-70176, CN 1847352A, CN1865382A etc.).Owing to add a large amount of organic phosphorus flame retardants and other mineral filler, the potential risk that in the process of preparation resin combination, has the fillers dispersed inequality on the one hand, not good with the mechanical property of the sheet material of this made on the other hand, water-absorbent is big, and the harm that exists processing or the medium and small molecular stuffing of follow-up use to ooze out or move to the surface.
Summary of the invention
Therefore the object of the present invention is to provide a kind of halogen-free flame retardant epoxy resin composition, not halogen-containing element, and need not to add other organic phosphorus flame retardant, it has excellent flame-retardant performance and mechanical property.
Another object of the present invention is to provide the above-mentioned use flexibility coat copper plate that this halogen-free flame retardant epoxy resin composition is made, its flexibility is better, and has high-peeling strength, flame retardant resistance and good processing properties.
A further object of the present invention is to provide the method for making above-mentioned flexibility coat copper plate, and is with strong points and technology is simple.
According to above-mentioned purpose of the present invention, a kind of halogen-free flame retardant epoxy resin composition is proposed, to form by solid ingredient and organic solvent, solid ingredient (calculating by solid weight part) comprising:
Phosphorous epoxy resin 30-60 part;
Synthetic rubber 15-30 part;
Rubber modified epoxy resin 10-25 part;
Composite curing agent 20-50 part, composite curing agent is made up of phosphorus containing phenolic resin and diaminodiphenylsulfone(DDS);
Also comprise:
Curing catalyst 0.01-1.0 part;
Oxidation inhibitor 0.01-1.0 part;
Mineral filler 0-100 part.
Solid ingredient is dissolved in organic solvent, and the weight percent that solid ingredient accounts for gross weight is 30%～40%.
Simultaneously, a kind of flexibility coat copper plate that uses aforesaid halogen-free flame retardant epoxy resin composition to make is proposed, be three layers of flexibility coat copper plate, with described halogen-free flame retardant epoxy resin composition is main tackiness agent, comprise: the polyimide insulative film, the Copper Foil that is coated on the halogen-free flame retardant epoxy resin composition coating on the polyimide insulative film and is pressed on the halogen-free flame retardant epoxy resin composition coating, wherein, the thickness of polyimide insulative film is 10-100 μ m, Copper Foil is rolled copper foil or electrolytic copper foil, thickness is 9-70 μ m, and the dry thickness of halogen-free flame retardant epoxy resin composition coating is 5-45 μ m.
In addition, also propose to make the method for aforesaid flexibility coat copper plate, comprise the steps:
Step 1 is mixed the liquid dispersion that described solid ingredient forms halogen-free flame retardant epoxy resin composition by described organic solvent, uses coating equipment that this dispersion single or double is coated on the polyimide insulative film, and gluing thickness is 10-35 μ m;
Step 2, make the polyimide insulative film that is coated with this dispersion through drying oven, remove organic solvent and drying composition, contain this halogen-free flame retardant epoxy resin composition layer of semicure attitude with formation, drying temperature is 80-160 ℃, 2～8 minutes heat-up times;
Step 3, compound with the Copper Foil roll-in under 80-100 ℃ temperature, the composition layer with this semicure attitude carries out after fixing again, makes the single or double flexibility coat copper plate, and the after fixing temperature is 120-170 ℃.
Beneficial effect of the present invention: resin combination of the present invention is not halogen-containing, need not to add other organic phosphorus flame retardant, and the use rubber modified epoxy resin, the consistency of Reinforced Rubber and phosphorous epoxy resin makes to keep mechanical property preferably when resin system reaches flame retardant resistance.With the flexibility coat copper plate that said composition is made, flame retardant resistance reaches the UL94V-0 level, has high-peeling strength, excellent size stability, flexibility, anti-ion transport and processing characteristics.
Embodiment
Halogen-free flame retardant epoxy resin composition of the present invention is made up of solid ingredient and organic solvent, and solid ingredient (calculating by solid weight part) comprising:
Phosphorous epoxy resin 30-60 part;
Synthetic rubber 15-30 part;
Rubber modified epoxy resin 10-25 part;
Composite curing agent 20-50 part, composite curing agent is made up of phosphorus containing phenolic resin and diaminodiphenylsulfone(DDS);
Curing catalyst 0.01-1.0 part;
Oxidation inhibitor 0.01-1.0 part;
Mineral filler 0-100 part.
After solid ingredient was dissolved in organic solvent, the weight percent that solid ingredient accounts for gross weight was 30%～40%.
Each raw material choose that details are as follows:
(1) phosphorous epoxy resin
Above-mentioned phosphorous epoxy resin is to make by using the reactive phosphorus compound that phosphorus atom is bonded to ordinary epoxy resin.The example of this reactive phosphorus compound comprises DOPO (9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound), and DOPO-HQ (being bonded in the compound that the active hydrogen atom on the phosphorus atom of this compound has been replaced by Resorcinol).The example of the commercially available product of the phosphorous epoxy resin of gained, comprise and choose XZ92530 (Dow Chemical Company manufacturing, phosphorus content is 3.0 quality %), (rivers and mountains Jiang Huanhua learns Industrial Co., Ltd to G24, phosphorus content is 2.4 quality %), FX305 (Tohto Kasei Co., Ltd. make, phosphorus content is 3.0 quality %) and Epiclon EXA9710 (Dainippon Ink andChemicals, Incorporated makes, phosphorus content 3.0%).
These halogen-free epoxy resins can use separately, or being used in combination with two or more different resins.
(2) synthetic rubber
Synthetic rubber is acrylonitrile butadiene copolymer normally, wherein acrylonitrile content can be at 18-50 quality %, preferably at 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 the product XER-32 (JSR Corporation manufacturing) that chooses Nipol 1072 (Zeon Corporation manufacturing) and high purity, hangs down ionic impurity.
(3) rubber modified epoxy resin
The affixture of elastomer-modified Resins, epoxy normally, the Resins, epoxy that uses comprises bisphenol A epoxide resin, bisphenol F epoxy resin and their hydride, the rubber that uses is the acrylonitrile butadiene copolymer fluid rubber of end carboxyl, Resins, epoxy and fluid rubber heating are mixed,, disappear as initiator with triphenyl phosphorus etc. at 80-120 ℃ of reaction certain hour to carboxyl.Wherein the content of fluid rubber can be at 20-60 quality %, preferred 30-50 quality %.Commercially available rubber modified epoxy resin comprises Epon Resin58005 (Hexion Specialty Chemicals, Inc. make, elastomer content 40 quality %) and HyRK84 (CVC Specialty Chemicals Inc., make elastomer content 32 quality %).
With DOPO is that basic phosphorous epoxy resin molecular chain skeleton rigidity of making is stronger, relatively poor with elastomeric consistency, utilize rubber modified epoxy resin can strengthen matrix resin and elastomeric consistency, also has a certain amount of small molecules Resins, epoxy in the rubber modified epoxy resin simultaneously, also can increase the cross-linking density of cured article, improve the cohesive strength of finished product glue-line, help to improve the stripping strength of flexibility coat copper plate.
(4) composite curing agent
Above-mentioned composite curing agent is to be made up of phosphorus containing phenolic resin and diaminodiphenylsulfone(DDS).Phosphorus containing phenolic resin can strengthen the flame retardant resistance of resin combination in cured epoxy resin; The use of diaminodiphenylsulfone(DDS) can improve the thermotolerance of resin combination.In the solidification process of rubber-toughened epoxy resin, the rubber particle of separating out is generally between 0.5-5 μ m, the rubber domain that obtains best toughening effect is of a size of 1-3 μ m, and volume fraction can be between 5%-30%, reach the influence that this result must take all factors into consideration the composition and the curing process of system, biphase is formed on the curing initial stage by kinetic control, and the later stage is then by diffusion control, through shakiness formation " island " structure that is separated, and then play good toughening effect.Utilize this composite curing system, can be so that the rubber domain size be between the scope of best toughening effect in the solidification process, it is more even to make that also microfacies distributes.Commercially available phosphorus containing phenolic resin has XZ92741 (Dow Chemical Company makes, and phosphorus content is 9.0 quality %) etc.
Be used the two total yield and the equivalence ratio of Resins, epoxy between 0.7-0.8.
(5) curing catalyst
Above-mentioned 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.
(6) oxidation inhibitor
The main purpose of oxidation inhibitor in resin combination is to reduce Resins, epoxy and acrylonitrile-butadiene rubber in the oxidation situation of resin combination in hot setting and following process process.Employed oxidation inhibitor can be 1010,1222,1076 (CIBA GEIGY Co. manufacturings) and 399,312,210 (GE Specially Chemicals manufacturings) etc., and home-made oxidation inhibitor such as commodity are called DNP (production of the triumphant source of Qujiang District, Quzhou City, Zhejiang Fine Chemical Works) etc.More than the oxidation inhibitor of these different names of an article can optionally select for use a kind of separately or mix two or more uses.The interpolation scope that oxidation inhibitor is formed at composition is 0.01-1.0 weight %.
(7) filler
Above-mentioned filler can be aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, lime carbonate, clay, talcum and mica etc., uses one or more mixture wherein.
(8) organic solvent
Above-mentioned organic solvent can be one or more in acetone, butanone, pimelinketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ethyl acetate etc.In the composition of making, the preferred 30-40 weight of amount of solid content %, the viscosity that can obtain to suit provides good workability, guarantees not occur in coating procedure visual defects.
Use similar devices such as ball mill, jar mill, sand mill, and be used high-shear dispersed with stirring equipment, the inoganic solids component and the organic solvent of organic solid component in the present composition and interpolation can be mixed.
Above-mentioned composition can be used for the making of flexibility coat copper plate.By utilizing organic solvent to mix the liquid dispersion that required component forms the present composition, use coating equipment that this dispersion single or double is coated on the polyimide insulative film.Make the insulating film that is coated with dispersion through online drying oven, 80-160 ℃ of heating 2 to 8 minutes, remove organic solvent and drying composition thus, the said composition layer that contains the semicure attitude with formation, next 80-100 ℃ down and the Copper Foil roll-in compound, this semicure state combination thing is carried out after fixing, get single or double flexibility coat copper plate to the end.After fixing preferably carries out at temperature 120-170 ℃.
The dry thickness of composition coating film is usually in the 5-45 mu m range in the above-mentioned flexible copper-clad panel material, preferred 5-20 μ m.
The above-mentioned used thin thickness of polyimide insulative is 10-100 μ m, and Copper Foil can be rolled copper foil or electrolytic copper foil, and thickness is 9-70 μ m, and gluing thickness is 10-35 μ m.
Survey its thermotolerance, flame retardant resistance, stripping strength and folding resistance at the above-mentioned flexibility coat copper plate of making, further give to illustrate in detail and describe as following embodiment.
The embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
Phosphorous epoxy resin (marque G-24, epoxy equivalent (weight) 340g/eq, phosphorus content 2.4 quality %, rivers and mountains Jiang Huanhua learns Industrial Co., Ltd and makes) 39 weight parts; Synthetic rubber (Zeon Corporation makes for marque Nipol 1072, acrylonitrile content 27 quality %) 20 weight parts; Rubber modified epoxy resin (marque Epon Resin 58005, elastomer content 40 quality %, Hexion Specialty Chemicals, Inc. makes) 13 weight parts; Phosphorus containing phenolic resin (DowChemical Company makes for marque XZ 92741, phosphorus content 9 quality %) 28 weight parts; Diaminodiphenylsulfone(DDS) 2.5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight part; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30 weight parts; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.20 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m by spreadometer, gluing thickness is 13 μ m, put in 160 ℃ the baking oven heating again into 3 minutes, on the polyimide thin dielectric membrane, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are closed by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make flexibility coat copper plate by designing program.
Embodiment 2:
Phosphorous epoxy resin (marque XZ 92530, epoxy equivalent (weight) 340g/eq, phosphorus content 3.0 quality %, Dow Chemical Company makes) 38 weight parts; Synthetic rubber (Zeon Corporation makes for marque Nipol 1072, acrylonitrile content 27 quality %) 20 weight parts; Rubber modified epoxy resin (CVC Specialty Chemicals Inc. makes for marque Hy RK84, elastomer content 32 quality %) 16 weight parts; Phosphorus containing phenolic resin (Dow ChemicalCompany makes for marque XZ92741, phosphorus content 9 quality %) 26 weight parts; Diaminodiphenylsulfone(DDS) 2.0 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight part; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30 weight parts; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.20 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m by spreadometer, gluing thickness is 13 μ m, put in 160 ℃ the baking oven heating again into 3 minutes, on the polyimide thin dielectric membrane, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are closed by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make flexibility coat copper plate by designing program.
Comparative example 1: phosphorous epoxy resin (marque G-24, epoxy equivalent (weight) 340g/eq, phosphorus content 2.4 quality %, rivers and mountains Jiang Huanhua learns Industrial Co., Ltd and makes) 37 weight parts; Synthetic rubber (Zeon Corporation makes for marque Nipol1072, acrylonitrile content 27 quality %) 20 weight parts; Rubber modified epoxy resin (marque Epon Resin 58005, elastomer content 40 quality %, Hexion SpecialtyChemicals, Inc. makes) 12 weight parts; Nitrogenous resol (marque PS 6313, nitrogen content 20%, hydroxyl equivalent 148, Japanese Gunsaka Chem. Industry Co., Ltd. produces) 9 weight parts; Diaminodiphenylsulfone(DDS) 2.4 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.20 weight part; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30 weight parts; Oxidation inhibitor (marque 1010, CIBAGEIGY Co. makes) 0.20 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m by spreadometer, gluing thickness is 13 μ m, put in 160 ℃ the baking oven heating again into 3 minutes, on the polyimide thin dielectric membrane, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are closed by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make flexibility coat copper plate by designing program.
Comparative example 2: phosphorous epoxy resin (marque XZ 92530, epoxy equivalent (weight) 340g/eq, phosphorus content 3.0 quality %, Dow Chemical Company makes) 51 weight parts; Synthetic rubber (Zeon Corporation makes for marque Nipol 1072, acrylonitrile content 27 quality %) 28 weight parts; Rubber modified epoxy resin (CVC Specialty ChemicalsInc. makes for marque Hy RK84, elastomer content 32 quality %) 22 weight parts; Diaminodiphenylsulfone(DDS) 7.5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight part; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30 weight parts; Organic phosphorus flame retardant (the big tomb chemical company of Japan makes for marque SPB-100, phosphorus content 13 quality %) 20 weight parts; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.20 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m by spreadometer, gluing thickness is 13 μ m, put in 160 ℃ the baking oven heating again into 3 minutes, on the polyimide thin dielectric membrane, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are closed by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make flexibility coat copper plate by designing program.
Specifically see the following form:
The performance of the prescription of table 1 halogen-free epoxy resin composition and the flexibility coat copper plate of making thereof
The testing method of above characteristic is as follows:
1) stripping strength (PS) is tested the stripping strength of metal cap rock according to the IPC-TM-6502.4.9 method.
2) screen resilience can reflect the flexibility of flexibility coat copper plate quantitatively, and screen resilience is more little, and flexible sheet is soft more.Testing method is taken charge of enterprise's mark according to me and is carried out.
3) incendivity (flame retardant resistance): measure according to UL 94 vertical combustion methods.
4) anti-immersed solder is tested according to IPC-TM-6502.4.13.
5) folding resistance carries out with reference to JIS C-6471, and test condition is 0.5Kg/0.8R, no mulch film.Size of sample is that PI insulating film/13 μ m compositions of 12.5 μ m apply bed thickness/18 μ m rolled copper foils.
As seen from the above table, the present invention has following beneficial effect: resin combination of the present invention is not halogen-containing, need not to add other organic phosphorus flame retardant, and use rubber modified epoxy resin, the consistency of Reinforced Rubber and phosphorous epoxy resin makes to keep mechanical property preferably when resin system reaches flame retardant resistance.With the flexibility coat copper plate that said composition is made, flame retardant resistance reaches the UL94V-0 level, has high-peeling strength, excellent size stability, flexibility, anti-ion transport and processing characteristics.
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, a kind of halogen-free flame retardant epoxy resin composition is characterized in that, is made up of solid ingredient and organic solvent, and solid ingredient (calculating by solid weight part) comprising:
Phosphorous epoxy resin 30-60 part;
Synthetic rubber 15-30 part;
Rubber modified epoxy resin 10-25 part;
Composite curing agent 20-50 part, composite curing agent is made up of phosphorus containing phenolic resin and diaminodiphenylsulfone(DDS);
Solid ingredient is dissolved in organic solvent, and the weight percent that solid ingredient accounts for gross weight is 30%40%.
2, halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, solid ingredient (calculating by solid weight part) also comprises:
Curing catalyst 0.01-1.0 part;
Oxidation inhibitor 0.01-1.0 part;
Mineral filler 0-100 part.
3, halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described phosphorous epoxy resin is by the reactive phosphorus compound phosphorus atom to be bonded to ordinary epoxy resin to make, and this reactive phosphorus compound is DOPO or DOPO-HQ.
4, halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described synthetic rubber is an acrylonitrile butadiene copolymer, and wherein, acrylonitrile content is 18-50% (weight ratio), and the copolymer molecule chain end is by carboxylated; Or be vinyl cyanide, divinyl and carboxylic monomeric copolymer rubber.
5, halogen-free flame retardant epoxy resin composition as claimed in claim 1, it is characterized in that, described rubber modified epoxy resin is the affixture of elastomer-modified Resins, epoxy, mix by Resins, epoxy and fluid rubber heating, with triphenyl phosphorus etc. as initiator, make after carboxyl disappears at 80-120 ℃ of reaction certain hour, wherein, the Resins, epoxy that is adopted comprises bisphenol A epoxide resin, bisphenol F epoxy resin and their hydride, the rubber that is adopted is the fluid rubber of the acrylonitrile butadiene copolymer of end carboxyl, and the content of fluid rubber is 20-60% (weight ratio).
6, halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, composite curing agent, and promptly the equivalence ratio of the total yield of phosphorous-containing phenolic resin and diaminodiphenylsulfone(DDS) and phosphorous epoxy resin is 0.7～0.8.
7, halogen-free flame retardant epoxy resin composition as claimed in claim 1, it is characterized in that, described curing catalyst is the imidazoles curing catalyst, is 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 one or more the mixture in aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, lime carbonate, clay, talcum and the mica.
8, halogen-free flame retardant epoxy resin composition as claimed in claim 1 is characterized in that, described organic solvent is one or more in acetone, butanone, pimelinketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ethyl acetate.
9, a kind of flexibility coat copper plate that uses halogen-free flame retardant epoxy resin composition as claimed in claim 1 to make, it is characterized in that, be three layers of flexibility coat copper plate, with described halogen-free flame retardant epoxy resin composition is main tackiness agent, comprise the polyimide insulative film, the Copper Foil that is coated on the coating of this halogen-free flame retardant epoxy resin composition on the polyimide insulative film and is pressed on the halogen-free flame retardant epoxy resin composition coating, wherein, the thickness of polyimide insulative film is 10-100 μ m, Copper Foil is rolled copper foil or electrolytic copper foil, thickness is 9-70 μ m, and the dry thickness of halogen-free flame retardant epoxy resin composition coating is 5-45 μ m.
10, a kind of method of making flexibility coat copper plate as claimed in claim 9 is characterized in that, its making comprises the steps:
Step 1 is mixed the liquid dispersion that described solid ingredient forms halogen-free flame retardant epoxy resin composition by described organic solvent, uses coating equipment that this dispersion single or double is coated on the polyimide insulative film, and gluing thickness is 10-35 μ m;
Step 2, make the polyimide insulative film that is coated with this dispersion through drying oven, remove organic solvent and drying composition, contain this halogen-free flame retardant epoxy resin composition layer of semicure attitude with formation, drying temperature is 80-160 ℃, 2～8 minutes heat-up times;
Step 3, compound with the Copper Foil roll-in under 80-100 ℃ temperature, the composition layer with this semicure attitude carries out after fixing again, makes the single or double flexibility coat copper plate, and the after fixing temperature is 120-170 ℃.
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-
2008
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