CN101831144B - Halogen-free epoxy resin composition and high-flexibility flexible copper clad laminate prepared from same - Google Patents
Halogen-free epoxy resin composition and high-flexibility flexible copper clad laminate prepared from same Download PDFInfo
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Abstract
The invention relates to a halogen-free epoxy resin composition and a high-flexibility flexible copper clad laminate prepared from the same. The halogen-free epoxy resin composition comprises flexible benzoxazine resin, phosphorus-containing epoxy resin, terminal carboxyl nitrile rubber, terminal carboxyl nitrile rubber-modified epoxy resin, a phosphorus fire retardant, a curing agent, a curing accelerator, an antioxidant, a filler and an organic solvent. The high-flexibility flexible copper clad laminate prepared from the composition comprises a polyimide insulating film, a halogen-free epoxy resin composition coating coated on the polyimide insulating film, and a copper foil laminated on the halogen-free epoxy resin composition coating. The halogen-free epoxy resin composition does not contain halogen, has excellent heat resistance and flexibility, and maintains good mechanical property simultaneously. The high-flexibility flexible copper clad laminate (FCCL) prepared from the composition has the fire retardance in UL94 V-0 level, and has the advantages of excellent heat resistance, dimensional stability, flexibility, ion migration resistance, and machinability.
Description
Technical field
The present invention relates to a kind of halogen-free epoxy resin composition, and the high flexibility flexibility coat copper plate that uses the said composition preparation.
Background technology
At present, the major technique approach that realizes flexibility coat copper plate (FCCL) 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 DDS or resol as the solidifying agent of phosphorous epoxy resin (as TOHKEMY 2005-248048, spy open 2006-332150, the spy opens the solidifying agent that 2006-70176, Chinese patent CN1847352A, CN1865382A etc. disclose).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 this prepared sheet material 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; In addition, the flexibility of flexibility coat copper plate is one of performance of relatively paying attention to of FPC always, and whether soft operability to FCCL has very big influence to product, and especially when being used for the module plate, this performance seems even more important.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free epoxy resin composition, this resin combination is not halogen-containing, has thermotolerance, reliability and the flexibility of flame retardant resistance, excellence, keeps mechanical property preferably simultaneously.
Another object of the present invention is to, a kind of high flexibility flexibility coat copper plate that uses the halogen-free epoxy resin composition preparation is provided, its flame retardant resistance reaches UL94 V-0 level, has excellent thermotolerance, dimensional stability, flexibility, anti-ion transport and processing characteristics.
For achieving the above object, the invention provides a kind of halogen-free epoxy resin composition, said composition comprises that component and weight part content thereof are as follows: flexible benzoxazine colophony 5-50 part, phosphorous epoxy resin 10-50 part, nbr carboxyl terminal 10-35 part, nbr carboxyl terminal modified epoxy 10-25 part, phosphorus flame retardant 1-30 part, solidifying agent 1-20 part, curing catalyst 0.01-1.0 part, oxidation inhibitor 0.01-1.0 part, filler 0-100 part, and organic solvent an amount of.Wherein, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 30-40% of total weight percent.
Simultaneously, a kind of high flexibility flexibility coat copper plate that uses the above-mentioned composition preparation is provided, with above-mentioned halogen-free epoxy resin composition is main tackiness agent, comprise: polyimide insulative film, the Copper Foil that is coated on the halogen-free epoxy resin composition coating on the polyimide insulative film and is pressed on the halogen-free epoxy resin composition coating, wherein, the thickness of polyimide insulative film is 10-100 μ m, and Copper Foil can be rolled copper foil or electrolytic copper foil, thickness is 9-70 μ m, and gluing thickness is 10-35 μ m; The dry thickness of halogen-free epoxy resin composition coating is 5-45 μ m, preferred 5-20 μ m.
Beneficial effect of the present invention: resin combination of the present invention is not halogen-containing, adopts a kind of cardanol type benzoxazine colophony of high flexibility, can effectively reduce elastomeric consumption; Adopt phosphorous epoxy resin to improve flame retardant resistance, and use rubber modified epoxy resin, the consistency of Reinforced Rubber and Resins, epoxy and benzoxazine colophony makes to obtain excellent thermotolerance and flexibility when resin system reaches flame retardant resistance, keeps mechanical property preferably simultaneously; With the high flexibility FCCL of said composition preparation, flame retardant resistance reaches the UL94V-0 level, has excellent thermotolerance, dimensional stability, flexibility, anti-ion transport and processing characteristics.
Embodiment
Halogen-free epoxy resin composition of the present invention comprises: flexible benzoxazine colophony, phosphorous epoxy resin, synthetic rubber, rubber modified epoxy resin, phosphorus flame retardant, solidifying agent, curing catalyst, oxidation inhibitor, filler and organic solvent.
The weight proportion of above-mentioned raw materials (by the listed as parts by weight of constituent) is:
Flexible benzoxazine colophony 5-50 part;
Phosphorous epoxy resin 10-50 part;
Nbr carboxyl terminal 10-35 part;
Nbr carboxyl terminal modified epoxy 10-25 part;
Phosphorus flame retardant 1-30 part;
Solidifying agent 1-20 part;
Curing catalyst 0.01-1.0 part;
Oxidation inhibitor 0.01-1.0 part;
Filler 0-100 part;
Organic solvent is an amount of.
Wherein, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 30-40% of total weight percent
Described flexible benzoxazine colophony is a cardanol type benzoxazine colophony, some performance performance of bisphenol A-type benzoxazine commonly used at present and Bisphenol F type benzoxazine is excellent, and other performances still dislike not enough, be better than ordinary epoxy resin as its thermotolerance, but fragility is also bigger, is difficult to be applied among the FCCL.The present invention adopts a kind of benzoxazine colophony of novel high flexibility, maximizes favourable factors and minimizes unfavourable ones in the hope of obtaining isostatic performance and even more ideal effect.This benzoxazine colophony selects for use the cardanol of high flexibility as one of monomer, obtains to have the benzoxazine of chain alkyl, and its structural formula is as follows:
The synthetic method of this flexibility benzoxazine colophony is referring to the patent CN1259530A of Sichuan University's application, promptly by the synthetic under certain condition flexible benzoxazine colophony that obtains this structure of cardanol, monoamine compound and formaldehyde solution.Take all factors into consideration thermotolerance, flame retardant resistance, flexibility and adhesiveproperties, the usage quantity of this resin is advisable with the 10-30 weight part.
Described phosphorous epoxy resin is to prepare by using the reactive phosphorus compound that phosphorus atom is bonded to ordinary epoxy resin.The example of this reactive phosphorus compound comprises 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) and be bonded in the compound (DOPO-HQ) 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 comprises that (Dow Chemical Company makes XZ92530, 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 %), with Epiclon EXA9710 (Dainippon Ink andChemicals, Incorporated makes, phosphorus content 3.0%).
These halogen-free epoxy resins can use separately, perhaps being used in combination with two or more different resins.
Described nbr carboxyl terminal 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 Nipol 1072CG (ZeonCorporation manufacturing) and high purity, hangs down the product XER-32 (JSR Corporation manufacturing) of ionic impurity.
Described nbr carboxyl terminal modified epoxy is 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, wherein the content of fluid rubber can be at 20-60 quality %, preferred 20-40 quality %.Commercially available rubber modified epoxy resin comprises Epon Resin 58005 (Hexion Specialty Chemicals, Inc. make, elastomer content 40 quality %), also has HyPox RK84 (CVC Specialty Chemicals Inc., make elastomer content 32 quality %) and HyPox RF928 (CVC Specialty Chemicals Inc. makes elastomer content 20 quality %).
Utilize the nbr carboxyl terminal modified epoxy 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 high flexibility flexibility coat copper plate.
Described phosphonium flame retardant commonly used has SPB-100 (manufacturing of Ri Ben Otsuka Chemical Co., Ltd), OP-930 (German Clariant company make), SP-703H (Japanese four countries change into Co., Ltd. and make) etc.Whether except considering flame retarding efficiency, being heated to surface transport etc. for a long time all is the factor that must consider when being used to prepare FCCL.
Described solidifying agent adopts amine curing agent, amine curing agent commonly used has 4,4-diaminodiphenylsulfone(DDS) (4,4-DDS), 3,3-diaminodiphenylsulfone(DDS) (3,3-DDS) and diphenylmethane diamine (DDM) etc., wherein the temperature of reaction of DDS and Resins, epoxy is higher, but can help to improve the thermotolerance of product.
The equivalence ratio of amine curing agent equivalent and Resins, epoxy is 0.5-1.0.
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.
The main purpose of described 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 (GESpecially 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 the 0.01-1.0 weight part.
Described filler is mineral 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.
Described organic solvent can adopt one or more in acetone, butanone, pimelinketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ethyl acetate.In the composition of preparation, the preferred 30-40 quality 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 preparation of high flexibility 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 high flexibility flexibility coat copper plate to the end.After fixing preferably carries out at temperature 120-170 ℃.
The dry thickness of composition coating film is in the 5-45 mu m range in the above-mentioned high flexibility flexible copper-clad panel material, preferred 5-20 μ m.
The thickness of above-mentioned used polyimide insulative film 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 high flexibility flexibility coat copper plate of making, 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
Cardanol type benzoxazine colophony 6.8 weight parts; Phosphorous epoxy resin FX-305 43.3 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF92825.0 weight part; Phosphorus flame retardant SPB-100 9.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.33 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBAGEIGY Co. makes) 0.15 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Embodiment 2
Cardanol type benzoxazine colophony 13.5 weight parts; Phosphorous epoxy resin FX-305 36.5 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Phosphorus flame retardant SPB-100 9.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.46 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.15 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Embodiment 3
Cardanol type benzoxazine colophony 20.3 weight parts; Phosphorous epoxy resin FX-305 30.0 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Phosphorus flame retardant SPB-100 9.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.59 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.15 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Embodiment 4
Cardanol type benzoxazine colophony 27.0 weight parts; Phosphorous epoxy resin FX-305 23.0 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Phosphorus flame retardant SPB-100 13.5 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 22.5 weight parts; Diaminodiphenylsulfone(DDS) 8.71 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.15 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Embodiment 5
Cardanol type benzoxazine colophony 40.5 weight parts; Phosphorous epoxy resin FX-305 9.5 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF92825.0 weight part; Phosphorus flame retardant SPB-100 16.2 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 19.8 weight parts; Diaminodiphenylsulfone(DDS) 8.97 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBAGEIGY Co. makes) 0.15 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Comparative example 1
Bisphenol A-type benzoxazine colophony 20.3 weight parts; Phosphorous epoxy resin FX-305 30.0 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF928 25 weight parts; Phosphorus flame retardant SPB-100 9.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.59 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.15 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Comparative example 2
Bisphenol F type benzoxazine colophony 20.3 weight parts; Phosphorous epoxy resin FX-305 30.0 weight parts; Nbr carboxyl terminal 1072CG 15 weight parts; Nbr carboxyl terminal modified epoxy RF928 25 weight parts; Phosphorus flame retardant SPB-100 9.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.59 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.15 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 laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Comparative example 3
Bisphenol A-type benzoxazine colophony 14.9 weight parts; Phosphorous epoxy resin FX-305 30.1 weight parts; Nbr carboxyl terminal 1072CG 30 weight parts; Nbr carboxyl terminal modified epoxy RF928 25 weight parts; Phosphorus flame retardant SPB-100 10.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 8.02 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.80 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.30 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Comparative example 4
Bisphenol F type benzoxazine colophony 14.9 weight parts; Phosphorous epoxy resin FX-305 30.1 weight parts; Nbr carboxyl terminal 1072CG 30 weight parts; Nbr carboxyl terminal modified epoxy RF928 25 weight parts; Phosphorus flame retardant SPB-100 10.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 8.02 weight part 1-cyanoethyl-2-ethyl-4-methylimidazoles (2E4MZ-CN) 0.80 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.30 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 insulative film, to form partly solidified composition layer, then itself and 18 μ m rolled copper foils are laminated with by roll-in, put 120-170 ℃ baking oven into and carry out after fixing being laminated with thing, make the high flexibility flexibility coat copper plate by designing program.
Specifically see the following form:
The performance of the high flexibility flexibility coat copper plate of the formulation Example of table 1. halogen-free epoxy resin composition and preparation thereof
| Component | The starting material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Benzoxazine colophony | The cardanol type | 6.8 | 13.5 | 20.3 | 27.0 | 40.5 |
| Phosphorous epoxy resin | FX-305 | 43.3 | 36.5 | 30.0 | 23.0 | 9.5 |
| Nbr carboxyl terminal | 1072CG | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 |
The performance of the prescription comparative example of table 2. halogen-free epoxy resin composition and the high flexibility flexibility coat copper plate of preparation 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 IPC-TM-650 2.4.9 method.
(2) screen resilience can reflect the flexibility of flexibility coat copper plate quantitatively, and screen resilience is more little, and FCCL 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-650 2.4.13.
(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.
In sum, resin combination of the present invention is not halogen-containing, adopts a kind of cardanol type benzoxazine colophony of high flexibility, can effectively reduce the consumption of nbr carboxyl terminal; Adopt phosphorous epoxy resin to improve flame retardant resistance, and use rubber modified epoxy resin, the consistency of Reinforced Rubber and Resins, epoxy and benzoxazine colophony makes to obtain excellent thermotolerance and flexibility when resin system reaches flame retardant resistance, keeps mechanical property preferably simultaneously.With the high flexibility FCCL of said composition preparation, flame retardant resistance reaches UL94 V-0 level, has excellent thermotolerance, dimensional stability, flexibility, anti-ion transport and processing characteristics.
The above; it only is preferred embodiment of the present invention; for the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection domain of claim of the present invention according to technical scheme of the present invention and technical conceive.
Claims (5)
1. halogen-free epoxy resin composition, it is characterized in that, comprise that component and weight part content thereof are as follows: flexible benzoxazine colophony 5-50 part, phosphorous epoxy resin 10-50 part, nbr carboxyl terminal 10-35 part, nbr carboxyl terminal modified epoxy 10-25 part, phosphorus flame retardant 1-30 part, solidifying agent 1-20 part, curing catalyst 0.01-1.0 part, oxidation inhibitor 0.01-1.0 part, filler 0-100 part, and organic solvent an amount of, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 30-40% of total weight percent;
Described flexible benzoxazine colophony is a cardanol type benzoxazine colophony, adopts cardanol as one of monomer, obtains to have the benzoxazine of chain alkyl, and its chemical structural formula is:
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;
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 nbr carboxyl terminal rubber modified epoxy resin is the affixture of elastomer-modified Resins, epoxy, make by Resins, epoxy and fluid rubber, wherein, the Resins, epoxy that adopts comprises bisphenol A epoxide resin, bisphenol F epoxy resin and their hydride, the rubber that adopts is the acrylonitrile butadiene copolymer fluid rubber of end carboxyl, and the content of fluid rubber is 20-60 quality %;
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.
2. halogen-free epoxy resin composition as claimed in claim 1 is characterized in that, described solidifying agent is an amine curing agent, adopt 4,4-diaminodiphenylsulfone(DDS), 3,3-diaminodiphenylsulfone(DDS) or diphenylmethane diamine, the equivalence ratio of solidifying agent equivalent and phosphorous epoxy resin is 0.5-1.0.
3. halogen-free 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.
4. halogen-free epoxy resin composition as claimed in claim 1, it is characterized in that, described filler adopts mineral 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.
5. high flexibility flexibility coat copper plate that uses halogen-free epoxy resin composition preparation as claimed in claim 1, it is characterized in that, with described halogen-free epoxy resin composition is main tackiness agent, comprise the polyimide insulative film, be coated on the halogen-free epoxy resin composition coating on the polyimide insulative film and be pressed on Copper Foil on this halogen-free 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 gluing thickness is 10-35 μ m; The dry thickness of halogen-free epoxy resin composition coating is 5-45 μ m.
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| CN101831144B true CN101831144B (en) | 2011-12-21 |
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| US20140154939A1 (en) * | 2011-10-18 | 2014-06-05 | Qianping Rong | Halogen-free low-dielectric resin composition, and prepreg and copper foil laminate made by using same |
| CN103030786B (en) * | 2012-12-03 | 2014-08-20 | 浙江大学 | Preparation method of modified epoxy resin/flame-retardant glass cloth paper composite-base copper clad plate |
| CN103013046B (en) * | 2012-12-13 | 2014-07-16 | 广东生益科技股份有限公司 | Halogen-free flame retardant resin composition and use thereof |
| CN104448718B (en) * | 2014-12-08 | 2017-02-22 | 陕西生益科技有限公司 | Resin composition and application thereof |
| CN104804377B (en) * | 2015-01-28 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free resin composition, and prepreg and laminated boards which are prepared from halogen-free resin composition |
| CN105482371B (en) * | 2015-12-30 | 2018-09-11 | 陕西生益科技有限公司 | A kind of fill composition and its application |
| CN113370617A (en) * | 2021-06-21 | 2021-09-10 | 拓楚(江苏)电子科技有限公司 | Novel halogen-free flexible copper-clad plate |
| CN115488986B (en) * | 2022-09-26 | 2023-07-21 | 徐州安联木业有限公司 | Fire-retardant waterproof type recoverable environmental protection panel |
Citations (2)
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| CN101280093A (en) * | 2008-05-13 | 2008-10-08 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate |
| CN101578334A (en) * | 2007-01-09 | 2009-11-11 | 住友电气工业株式会社 | Non-halogen flame retardant resin composition and electric wire/cable using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578334A (en) * | 2007-01-09 | 2009-11-11 | 住友电气工业株式会社 | Non-halogen flame retardant resin composition and electric wire/cable using the same |
| CN101280093A (en) * | 2008-05-13 | 2008-10-08 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate |
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