CN101838440A - Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby - Google Patents
Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby Download PDFInfo
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Abstract
The invention relates to non-halogen, non-phosphorous and non-silicone epoxy resin compositions and a flexible copper clad laminate prepared thereby. The non-halogen, non-phosphorous and non-silicone epoxy resin composition comprises flexible benzoxazine resins, special type epoxy resins, carboxyl-terminated butadiene-acrylonitrile, carboxyl-terminated butadiene-acrylonitrile modified epoxy resin, nitrogen containing fire retardant, curing agent, curing promoter, antioxygen, ion trap, inorganic filler, and organic solvent; flexible copper clad laminate prepared by the composition comprises polymide insulation membrane, non-halogen, non-phosphorous and non-silicone epoxy resin compositions coating coated on the polymide insulation membrane and copper foil pressed on the coating of the non-halogen, non-phosphorous and non-silicone epoxy resin composition. The resin composition is non-halogen, non-phosphorous and non-silicone and has fire resistance, excellent heat resistance and flexibility while keeping good mechanical property; the flexible copper clad laminate prepared by the composition has fire resistance up to level UL94V-0, excellent heat resistance, stable size, flexibility, ion migration resistance and process property, suitable for use in various fields including the hard disc.
Description
Technical field
The present invention relates to a kind of composition epoxy resin of halogen-free phosphate-free silicon-free, and the 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 2006-70176, Chinese patent CN1847352A, CN 1865382A 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 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, phosphorus compound can be along with the addition increase the increase except the water-intake rate of itself, the phosphorous waste of its following final processing still may work the mischief to earth aquatic environment, because of it can hydrolysis cause the excellent oxidation in rivers and creeks or lake, another environment problem of deriving.
CN 1537906A is reported in hard disk equimagnetic header territory, and the existence of silicon is influential to electrical property, because silicon Si
+ 4Be active element, it produces absorption at the magnetic head magnetic field cathode, makes magnetic head produce data failure when high-speed cruising; In addition, the spy opens 2008-214598 and US2010/0063217 etc. and adopts dianhydride and the synthetic siliceous polyimide resin of siliceous diamines, then with flame retardant resistance preferably Resins, epoxy mix, and then can obtain a kind of FCCL of non-halogen non-phosphate, but this method mainly is with the fire-retardant related request that reaches of silicon.The present invention adopts nitrogen flame retardant and body flame-retarded technology to prepare a kind of FCCL of halogen-free phosphate-free silicon-free.
Summary of the invention
The object of the present invention is to provide a kind of composition epoxy resin of halogen-free phosphate-free silicon-free, this resin combination halogen-free phosphate-free silicon-free has flame retardant resistance, excellent thermotolerance, reliability and flexibility, keeps mechanical property preferably simultaneously.
Another object of the present invention is to, a kind of flexibility coat copper plate that uses the above-mentioned composition preparation is provided, its flame retardant resistance reaches the UL94V-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 composition epoxy resin of halogen-free phosphate-free silicon-free, said composition comprises that component and weight part content thereof are as follows: flexible benzoxazine colophony 10-50 part, specific epoxy resin 10-50 part, nbr carboxyl terminal 10-35 part, nbr carboxyl terminal modified epoxy 10-25 part, nitrogen flame retardant 1-30 part, solidifying agent 1-20 part, curing catalyst 0.01-1.0 part, oxidation inhibitor 0.01-1.0 part, ion capturing agent 0.01-2.0 part, mineral 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 flexibility coat copper plate of above-mentioned composition preparation is provided, composition epoxy resin with above-mentioned halogen-free phosphate-free silicon-free is main tackiness agent, comprise: polyimide insulative film, the Copper Foil that is coated on the composition epoxy resin coating of the halogen-free phosphate-free silicon-free on the polyimide insulative film and is pressed on the composition epoxy resin coating of halogen-free phosphate-free silicon-free, 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 the composition epoxy resin coating of halogen-free phosphate-free silicon-free is 5-45 μ m, preferred 5-20 μ m.
Beneficial effect of the present invention: resin combination halogen-free phosphate-free silicon-free of the present invention, adopt a kind of cardanol type benzoxazine colophony of high flexibility, can effectively reduce the consumption of nbr carboxyl terminal; The biphenyl epoxy resin that employing possesses special fire retardant mechanism improves flame retardant resistance, and use side carboxylic acrylonitrile butadiene rubber modified epoxy resin, the consistency of Reinforced Rubber and Resins, epoxy and benzoxazine colophony, make to obtain excellent thermotolerance and flexibility when resin system reaches flame retardant resistance, keep mechanical property preferably simultaneously.With the flexibility coat copper plate of said composition preparation, flame retardant resistance reaches UL94 V-0 level, has excellent thermotolerance, dimensional stability, flexibility, anti-ion transport and processing characteristics, applicable to comprising every field such as hard disk.
Embodiment
The composition epoxy resin of halogen-free phosphate-free silicon-free of the present invention comprises: flexible benzoxazine colophony, specific epoxy resin, nbr carboxyl terminal, nbr carboxyl terminal modified epoxy, nitrogen flame retardant, solidifying agent, curing catalyst, oxidation inhibitor, ion capturing agent, 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 10-50 part;
Specific epoxy resin 10-50 part;
Nbr carboxyl terminal 10-35 part;
Nbr carboxyl terminal modified epoxy 10-25 part;
Nitrogen flame retardant 1-30 part;
Solidifying agent 1-20 part;
Curing catalyst 0.01-1.0 part;
Oxidation inhibitor 0.01-1.0 part;
Ion capturing agent 0.01-2.0 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
Each feedstock detail is as follows:
(1) flexible benzoxazine colophony
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 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.
(2) specific epoxy resin
Above-mentioned specific epoxy resin is meant the high heat-stable Resins, epoxy that possesses special construction, NC-3000 series product such as Nippon Kayaku K. K, have the very strong biphenyl structural of rigidity in the main chain, make this resin possess stronger crystallinity, give its excellent thermotolerance and flame retardant resistance, this series comprises NC-3000-L, NC-3000 and NC-3000-H etc.; Similar extraordinary resin also has dicyclopentadiene Resins, epoxy, carbon yield under the Resins, epoxy high temperature of this structure is higher, also can reach flame retardant effect preferably, mainstream product is the HP-7200 series that Dainippon Ink. ﹠ Chemicals Inc produces, by epoxy equivalent (weight) series arrangement from small to large is HP-7200L, HP-7200, HP-7200H and HP-7200HH, the XD-1000 resene of Nippon Kayaku K. K is same as HP-7200H in addition, and is wider in the FCCL sector application.
These specific epoxy resins can use separately, perhaps being used in combination with two or more different resins.
(3) nbr carboxyl terminal
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.
(4) nbr carboxyl terminal modified epoxy
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 in 20-60% (weight ratio), preferred 20-40% (weight ratio).Commercially available nbr carboxyl terminal modified epoxy comprises Epon Resin58005 (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 nbr carboxyl terminal modified epoxy 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.
(5) nitrogen flame retardant
The nitrogen flame retardant that has obtained at present application mainly is a compound in triazine class, be trimeric cyanamide (MA) and salt thereof, the triazines fire retardant mainly plays a role with the dilution combustiblematerials by minute heat of desorption and generation 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 adopts melamine cyanurate to work in coordination with the very high biphenyl epoxy of charring rate and benzoxazine reaches fire-retardant requirement, nitrogen flame retardant of greatest concern is Ciba Melapur series product, and particle diameter has melapur MC50, melapur MC25 and melapur MC15 etc. from big to small; Domestic also have these series product of manufacturer production, reaches as Yueyang rubber maintenance company limited etc. is installed.
(6) solidifying agent
Solidifying agent adopts amine curing agent, and amine curing agent commonly used has 4,4-diaminodiphenylsulfone(DDS) (4,4-DDS), 3, the 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.
(7) 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.
(8) 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 SpeciallyChemicals 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.
(9) ion capturing agent
The purpose that adopts above-mentioned ion capturing agent is to utilize ion exchangeable, catches free ions, prevents the ion migration between copper cash, improves reliability of products.This trapping agent is the ultra micro ion, can select specific ion in coexisting ion, and a small amount of interpolation can reduce foreign ion, and the thermotolerance height, the chemical resistance excellence, thereby can not influence the physicals of product.Commercially available this series products has (Toagosei Co., Ltd's manufacturings) such as IXE-500, IXE-600, IXE-700.
(10) filler
Above-mentioned filler is mineral filler, can be aluminium hydroxide, magnesium hydroxide, magnesium oxide, lime carbonate etc., uses one or more mixture wherein.
(11) organic solvent
Above-mentioned 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 weight part 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 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 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 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 7.3 weight parts; Biphenyl epoxy resin NC-3000 42.7 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 11.24 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Embodiment 2
Cardanol type benzoxazine colophony 14.6 weight parts; Biphenyl epoxy resin NC-3000 35.4 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 10.88 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Embodiment 3
Cardanol type benzoxazine colophony 21.9 weight parts; Biphenyl epoxy resin NC-3000 28.1 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 10.52 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Embodiment 4
Cardanol type benzoxazine colophony 29.2 weight parts; Biphenyl epoxy resin NC-3000 20.8 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 10.17 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Embodiment 5
Cardanol type benzoxazine colophony 41.7 weight parts; Biphenyl epoxy resin NC-3000 8.3 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 9.56 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Comparative example 1
Bisphenol A-type benzoxazine colophony 21.9 weight parts; Biphenyl epoxy resin NC-3000 28.1 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 10.52 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Comparative example 2
Bisphenol F type benzoxazine colophony 21.9 weight parts; Biphenyl epoxy resin NC-3000 28.1 weight parts; Nbr carboxyl terminal 1072CG 15.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 10.52 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; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Comparative example 3
Bisphenol A-type benzoxazine colophony 21.9 weight parts; Biphenyl epoxy resin NC-3000 13.1 weight parts; Nbr carboxyl terminal 1072CG 30.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.12 weight part 1-cyanoethyl-2-ethyl-4-methylimidazoles (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.3 weight part; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Comparative example 4
Bisphenol F type benzoxazine colophony 21.9 weight parts; Biphenyl epoxy resin NC-3000 13.1 weight parts; Nbr carboxyl terminal 1072CG 30.0 weight parts; Nbr carboxyl terminal modified epoxy RF928 25.0 weight parts; Nitrogen flame retardant melapur MC15 18.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 27.0 weight parts; Diaminodiphenylsulfone(DDS) 8.12 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.72 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.3 weight part; Ion capturing agent (marque IXE-700, Toagosei Co., Ltd makes) 0.18 weight part.The solids content of regulating glue with butanone solvent is 40%, mixes the composition epoxy resin of making halogen-free phosphate-free silicon-free.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 flexibility coat copper plate by designing program.
Specifically see the following form:
The composition epoxy resin formulation Example of table 1. halogen-free phosphate-free silicon-free and the flexibility coat copper plate performance of preparation thereof
The composition epoxy resin prescription comparative example of table 2. halogen-free phosphate-free silicon-free and the performance of preparation flexibility coat copper plate 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 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 halogen-free phosphate-free silicon-free of the present invention adopts a kind of cardanol type benzoxazine colophony of high flexibility, can effectively reduce the consumption of nbr carboxyl terminal; The biphenyl epoxy resin that employing possesses special fire retardant mechanism improves flame retardant resistance, and use side carboxylic acrylonitrile butadiene rubber modified epoxy resin, the consistency of Reinforced Rubber and Resins, epoxy and benzoxazine colophony, make to obtain excellent thermotolerance and flexibility when resin system reaches flame retardant resistance, keep mechanical property preferably simultaneously.With the flexibility coat copper plate of said composition preparation, flame retardant resistance reaches UL94 V-0 level, has excellent thermotolerance, dimensional stability, flexibility, anti-ion transport and processing characteristics, applicable to comprising every field such as hard disk.
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 (10)
1. the composition epoxy resin of a halogen-free phosphate-free silicon-free, it is characterized in that, said composition comprises that component and weight part content thereof are as follows: flexible benzoxazine colophony 10-50 part, specific epoxy resin 10-50 part, nbr carboxyl terminal 10-35 part, nbr carboxyl terminal modified epoxy 10-25 part, nitrogen flame retardant 1-30 part, solidifying agent 1-20 part, curing catalyst 0.01-1.0 part, oxidation inhibitor 0.01-1.0 part, ion capturing agent 0.01-2.0 part, mineral filler 0-100 part, and 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.
2. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1, it is characterized in that described flexible benzoxazine colophony is a cardanol type benzoxazine colophony, adopt cardanol as one of monomer, acquisition has the benzoxazine of chain alkyl, and its chemical structural formula is:
3. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1, it is characterized in that, described specific epoxy resin is biphenyl epoxy resin or dicyclopentadiene Resins, epoxy, 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. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1, it is characterized in that, described nbr carboxyl terminal modified epoxy 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, and the rubber of employing is the acrylonitrile butadiene copolymer fluid rubber of end carboxyl, and the content of fluid rubber is 20-60 quality %.
5. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1, it is characterized in that, described nitrogen flame retardant is a compound in triazine class, 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 Resins, epoxy is 0.5-1.0.
6. the composition epoxy resin of halogen-free phosphate-free silicon-free 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.
7. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1 is characterized in that, described ion capturing agent is the ultra micro ion.
8. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1 is characterized in that, the mixture of one or more in described mineral filler employing aluminium hydroxide, magnesium hydroxide, magnesium oxide, the lime carbonate; 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. flexibility coat copper plate that uses the composition epoxy resin preparation of halogen-free phosphate-free silicon-free as claimed in claim 1, it is characterized in that, composition epoxy resin with described halogen-free phosphate-free silicon-free is main tackiness agent, comprise the polyimide insulative film, be coated on the composition epoxy resin coating of the halogen-free phosphate-free silicon-free on the polyimide insulative film, and be pressed on Copper Foil on the composition epoxy resin coating of this halogen-free phosphate-free silicon-free, 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 the composition epoxy resin coating of halogen-free phosphate-free silicon-free is 5-45 μ m.
10. flexibility coat copper plate as claimed in claim 9 is characterized in that, the dry thickness of the composition epoxy resin coating of halogen-free phosphate-free silicon-free is 5-20 μ m.
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| CN2010101800311A CN101838440B (en) | 2010-05-21 | 2010-05-21 | Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby |
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| CN2010101800311A CN101838440B (en) | 2010-05-21 | 2010-05-21 | Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby |
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| CN101838440A true CN101838440A (en) | 2010-09-22 |
| CN101838440B CN101838440B (en) | 2012-05-09 |
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| CN2010101800311A Expired - Fee Related CN101838440B (en) | 2010-05-21 | 2010-05-21 | Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby |
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Cited By (8)
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| CN103074019A (en) * | 2013-01-22 | 2013-05-01 | 浙江华正新材料股份有限公司 | Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same |
| CN103073844A (en) * | 2013-01-05 | 2013-05-01 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition and cover film produced by halogen-free flame-retardant epoxy resin composition |
| CN103131007A (en) * | 2011-11-22 | 2013-06-05 | 台光电子材料股份有限公司 | Thermosetting resin composition and laminated plate and circuit board employing same |
| CN107603552A (en) * | 2017-09-12 | 2018-01-19 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover layer and the method for preparing cover layer |
| CN109161194A (en) * | 2018-08-17 | 2019-01-08 | 巢湖市翔宇渔具有限公司 | A kind of fishing rod high-strength tenacity composite material |
| CN111154231A (en) * | 2019-12-31 | 2020-05-15 | 湖北宏洋电子股份有限公司 | Epoxy resin composition and flexible copper clad laminate prepared from same |
| CN112694719A (en) * | 2020-12-29 | 2021-04-23 | 浙江华正新材料股份有限公司 | Resin composition, preparation method thereof and metal substrate |
| WO2021120117A1 (en) * | 2019-12-19 | 2021-06-24 | 瑞声声学科技(深圳)有限公司 | Substrate plate having different copper foils on two surfaces thereof |
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| CN103131007A (en) * | 2011-11-22 | 2013-06-05 | 台光电子材料股份有限公司 | Thermosetting resin composition and laminated plate and circuit board employing same |
| CN103131007B (en) * | 2011-11-22 | 2015-06-17 | 台光电子材料股份有限公司 | Thermosetting resin composition and laminated plate and circuit board employing same |
| CN103073844A (en) * | 2013-01-05 | 2013-05-01 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition and cover film produced by halogen-free flame-retardant epoxy resin composition |
| CN103074019A (en) * | 2013-01-22 | 2013-05-01 | 浙江华正新材料股份有限公司 | Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same |
| CN107603552A (en) * | 2017-09-12 | 2018-01-19 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover layer and the method for preparing cover layer |
| CN107603552B (en) * | 2017-09-12 | 2020-07-28 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film and method for preparing cover film |
| CN109161194A (en) * | 2018-08-17 | 2019-01-08 | 巢湖市翔宇渔具有限公司 | A kind of fishing rod high-strength tenacity composite material |
| WO2021120117A1 (en) * | 2019-12-19 | 2021-06-24 | 瑞声声学科技(深圳)有限公司 | Substrate plate having different copper foils on two surfaces thereof |
| CN111154231A (en) * | 2019-12-31 | 2020-05-15 | 湖北宏洋电子股份有限公司 | Epoxy resin composition and flexible copper clad laminate prepared from same |
| CN112694719A (en) * | 2020-12-29 | 2021-04-23 | 浙江华正新材料股份有限公司 | Resin composition, preparation method thereof and metal substrate |
| CN112694719B (en) * | 2020-12-29 | 2024-01-09 | 浙江华正新材料股份有限公司 | Resin composition, preparation method thereof and metal substrate |
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