CN101851391B - Halogen-free phosphate-free silicon-free epoxy resin composition and cover layer prepared by using same - Google Patents
Halogen-free phosphate-free silicon-free epoxy resin composition and cover layer prepared by using same Download PDFInfo
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Abstract
The invention relates to a halogen-free phosphate-free silicon-free epoxy resin composition and a cover layer prepared by using the same. The composition comprises flexible benzoxazine resin, special type epoxy resin, carboxyl-terminated liquid nitrile rubber, acrylate modified epoxy resin, nitrogenated flame retardant, firming agent, curing accelerator, antioxidant, filler and organic solvent. The cover layer prepared by using the composition comprises a polyimide insulating film, a halogen-free phosphate-free silicon-free epoxy resin composition coating coated on the polyimide insulating film and release paper coated on the halogen-free phosphate-free silicon-free epoxy resin composition coating. The halogen-free phosphate-free silicon-free resin composition of the invention has flame retardant performance, excellent heat resistance and flexibility and better mechanical property; and the cover layer prepared by utilizing the composition has flame retardancy reaching UL94V-0 level, has excellent heat resistance, dimensional stability, flexibility, ion migration resistance and processability, and can be applied in fields of hard disks and the like.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, the mulch film that relates in particular to a kind of composition epoxy resin of halogen-free phosphate-free silicon-free and use its preparation.
Background technology
At present, the major technique approach that realizes the mulch film halogen-free flameproof is with thermoplastic resin or rubber toughened non-halogen Resins, epoxy, add mineral filler assisting flame-resistants such as a large amount of P contained compounds and aluminium hydroxide simultaneously, adopt DDS or resol as solidifying agent (open as CN 1847352A, CN 1891778, CN1670107, US 2008/0241452, spy 2005-248048, spy open 2006-332150, the spy opens 2006-70176 etc.).Owing to add a large amount of phosphorus flame retardants and other mineral filler, may cause the mechanical property of mulch film not good, 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 discloses a kind of preparation method who does not have silicon flame retardant type mulch film, thinks that the existence of silicon is influential to electrical property in hard disk equimagnetic header territory, because silicon Si
+ 4Be active element, it produces absorption at the magnetic head magnetic field cathode, make magnetic head produce data failure when high-speed cruising, but this preparation method adopts traditional halogen flame retardant to reach related request; 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 obtain a kind of mulch film 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 mulch film 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 and have flame retardant resistance, excellent thermotolerance, flexibility and mechanical property preferably.
Another object of the present invention is to, a kind of mulch film that uses the above-mentioned 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 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 5-50 part, specific epoxy resin 10-50 part, nbr carboxyl terminal 10-35 part, acrylate modified Resins, 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, filler 0-100 part, and 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 mulch film that uses the above-mentioned composition preparation is provided, 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 laminated with in the separate-type paper of the composition epoxy resin coating of halogen-free phosphate-free silicon-free, wherein, the thickness of polyimide insulative film is 10-100 μ m, separate-type paper thickness is 50-150 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 10-35 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 acrylate modified Resins, epoxy, improve the resin system adhesive property, adopt nitrogen flame retardant cooperative flame retardant, make to obtain excellent thermotolerance, flexibility and mechanical property preferably when resin system reaches flame retardant resistance; With the mulch film 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 every field such as hard disks.
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, acrylate modified Resins, epoxy, nitrogen 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;
Specific epoxy resin 10-50 part;
Nbr carboxyl terminal 10-35 part;
Acrylate modified Resins, 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;
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 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.
(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) acrylate modified Resins, epoxy
Acrylate modified Resins, epoxy and CTBN (nbr carboxyl terminal) is shared, adjustment by curing system, can bring into play two kinds of elastomeric advantages simultaneously, also has a certain amount of small molecules Resins, epoxy in addition in this resin, 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 mulch film.Commercially available acrylate modified Resins, epoxy comprises BPA 328 and BPF 307 (Nippon Shokubai Co., Ltd makes, elastomer content 20 quality %) etc. at present.
(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 0.01-1.0 weight %.
(9) filler
Filler adopts mineral filler, can be aluminium hydroxide, magnesium hydroxide, magnesium oxide, lime carbonate etc., uses one or more mixture wherein.
(10) 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 preparation, 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 preparation of mulch film.Utilize organic solvent to mix the liquid dispersion that required component forms the present composition, use coating equipment that this dispersion 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 separate-type paper compound, promptly obtain the mulch film of halogen-free phosphate-free silicon-free.
The dry thickness of composition coating film is usually in the 5-45 mu m range in the above-mentioned mulch film, preferred 10-35 μ m.
The thickness of above-mentioned used polyimide insulative film is 10-100 μ m, and separate-type paper thickness is 50-150 μ m, and gluing thickness is 10-35 μ m.
Test its excessive glue amount, flexibility, stripping strength, thermotolerance and flame retardant resistance at the mulch film of the above-mentioned halogen-free phosphate-free silicon-free 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 8.2 weight parts; Biphenyl epoxy resin NC-3000 46.8 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 10.39 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Embodiment 2
Cardanol type benzoxazine colophony 16.5 weight parts; Biphenyl epoxy resin NC-3000 38.5 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 10.05 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Embodiment 3
Cardanol type benzoxazine colophony 24.7 weight parts; Biphenyl epoxy resin NC-3000 30.3 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 9.70 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Embodiment 4
Cardanol type benzoxazine colophony 32.9 weight parts; Biphenyl epoxy resin NC-3000 22.1 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 9.35 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Embodiment 5
Cardanol type benzoxazine colophony 41.2 weight parts; Biphenyl epoxy resin NC-3000 13.9 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 9.01 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Comparative example 1
Bisphenol A-type benzoxazine colophony 24.7 weight parts; Biphenyl epoxy resin NC-3000 30.3 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 9.70 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Comparative example 2
Bisphenol F type benzoxazine colophony 24.7 weight parts; Biphenyl epoxy resin NC-3000 30.3 weight parts; Nbr carboxyl terminal 1072CG 20.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 9.70 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.2 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Comparative example 3
Bisphenol A-type benzoxazine colophony 24.7 weight parts; Biphenyl epoxy resin NC-3000 20.3 weight parts; Nbr carboxyl terminal 1072CG 30.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 8.31 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.3 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
Comparative example 4
Bisphenol F type benzoxazine colophony 24.7 weight parts; Biphenyl epoxy resin NC-3000 20.3 weight parts; Nbr carboxyl terminal 1072CG 30.0 weight parts; Acrylate modified Resins, epoxy BF30725.0 weight part; Nitrogen flame retardant melapur MC15 25.0 weight parts; Aluminium hydroxide (median size is 1 to 5 μ m, and purity is more than 99%) 30.0 weight parts; Diaminodiphenylsulfone(DDS) 8.31 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.15 weight part; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.3 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 15 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 separate-type paper are laminated with, rolling obtains the mulch film of halogen-free phosphate-free silicon-free.
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 flexibility coat copper plate performance of preparation thereof
The testing method of above characteristic is as follows:
(1) excessive glue amount is tested according to IPC-TM-650 2.3.17.1 method.
(2) stripping strength (PS) is tested after earlier mulch film and Copper Foil light face being posted, solidify according to IPC-TM-650 2.4.9 method test again.
(3) screen resilience can reflect the flexibility of mulch film quantitatively, and screen resilience is more little, and mulch film is soft more.Testing method is taken charge of enterprise's mark according to me and is carried out.
(4) incendivity (flame retardant resistance): measure according to UL 94 vertical combustion methods.
(5) anti-immersed solder is tested according to IPC-TM-650 2.4.13.
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 acrylate modified Resins, epoxy, improve the resin system adhesive property, adopt nitrogen flame retardant cooperative flame retardant, make to obtain excellent thermotolerance, flexibility and mechanical property preferably when resin system reaches flame retardant resistance; With the mulch film 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 every field such as hard disks.
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 (9)
1. the composition epoxy resin of a halogen-free phosphate-free silicon-free, it is characterized in that, comprise that component and weight part content thereof are as follows: flexible benzoxazine colophony 5-50 part, specific epoxy resin 10-50 part, nbr carboxyl terminal 10-35 part, acrylate modified Resins, 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, 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; Described specific epoxy resin adopts biphenyl epoxy resin or dicyclopentadiene Resins, epoxy.
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 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 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 Resins, epoxy is 0.5-1.0.
5. 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.
6. the composition epoxy resin of halogen-free phosphate-free silicon-free as claimed in claim 1 is characterized in that, described filler adopts mineral filler, is one or more the mixture in aluminium hydroxide, magnesium hydroxide, magnesium oxide, the lime carbonate.
7. the composition epoxy resin of halogen-free phosphate-free silicon-free 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.
8. mulch film that uses the composition epoxy resin preparation of halogen-free phosphate-free silicon-free as claimed in claim 1, it is characterized in that, 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 laminated with separate-type paper 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, separate-type paper thickness is 50-150 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.
9. mulch film as claimed in claim 8 is characterized in that, the dry thickness of the composition epoxy resin coating of halogen-free phosphate-free silicon-free is 10-35 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101800330A CN101851391B (en) | 2010-05-21 | 2010-05-21 | Halogen-free phosphate-free silicon-free epoxy resin composition and cover layer prepared by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101800330A CN101851391B (en) | 2010-05-21 | 2010-05-21 | Halogen-free phosphate-free silicon-free epoxy resin composition and cover layer prepared by using same |
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| CN101851391B true CN101851391B (en) | 2011-12-14 |
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| CN102020828B (en) * | 2010-11-16 | 2012-09-26 | 莱芜金鼎电子材料有限公司 | Phosphorus-nitrogen compound intumescence active flame retardant modified epoxy resin and preparation method and application thereof |
| CN102304272B (en) * | 2011-04-03 | 2013-08-14 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and cover film prepared from same |
| 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 |
| CN104449484B (en) | 2013-09-25 | 2018-06-15 | 3M创新有限公司 | Pressure sensitive adhesive, conducting resin composition and by its adhesive tape obtained and purposes |
| CN107116886B (en) * | 2017-04-20 | 2019-03-19 | 广东莱尔新材料科技股份有限公司 | A kind of preparation method of that resist warping printed wiring board cover film |
| JP6930482B2 (en) * | 2018-04-16 | 2021-09-01 | 味の素株式会社 | Resin composition |
| CN109021675B (en) * | 2018-08-17 | 2021-06-15 | 广州市红太电子科技有限公司 | PCB printing ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1548473A (en) * | 2003-05-09 | 2004-11-24 | 广州宏仁电子工业有限公司 | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process |
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| EP2133398B1 (en) * | 2007-03-08 | 2014-01-15 | Nippon Steel & Sumikin Chemical Co., Ltd. | Fire-retardant adhesive resin composition, and adhesive film using the same |
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| CN1548473A (en) * | 2003-05-09 | 2004-11-24 | 广州宏仁电子工业有限公司 | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process |
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