CN102250447B - Halogen-free flame-retardant epoxy resin composition and prepreg and printed circuit board made therefrom - Google Patents
Halogen-free flame-retardant epoxy resin composition and prepreg and printed circuit board made therefrom Download PDFInfo
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- CN102250447B CN102250447B CN201010184744.5A CN201010184744A CN102250447B CN 102250447 B CN102250447 B CN 102250447B CN 201010184744 A CN201010184744 A CN 201010184744A CN 102250447 B CN102250447 B CN 102250447B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 37
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 7
- GQOUGABZQVSVHX-UHFFFAOYSA-N 3-hydroxy-2,4-dioxa-3lambda5-phosphabicyclo[3.3.1]nona-1(9),5,7-triene 3-oxide Chemical compound C1=CC(OP(O)(=O)O2)=CC2=C1 GQOUGABZQVSVHX-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims description 24
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 12
- -1 1,3-phenylene ester Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- 238000010030 laminating Methods 0.000 claims 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- 229910052736 halogen Inorganic materials 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 22
- 239000010452 phosphate Substances 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 16
- 239000002966 varnish Substances 0.000 description 15
- 150000002367 halogens Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 10
- 229940015043 glyoxal Drugs 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229960001866 silicon dioxide Drugs 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003351 stiffener Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 1
- HRCSALDOULKIIP-UHFFFAOYSA-N 3-methyl-2,4-dioxa-3$l^{5}-phosphabicyclo[3.3.1]nona-1(9),5,7-triene 3-oxide Chemical compound C1=CC(OP(C)(=O)O2)=CC2=C1 HRCSALDOULKIIP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A halogen-free flame retardant epoxy resin composition comprising: a halogen-free epoxy resin; (b) styrene-maleic anhydride copolymer as hardener; (c) polymethyl phosphate 1, 3-phenylene ester is used as a flame retardant; (d) a hardening accelerator; and (e) an inorganic filler.
Description
Technical field
The present invention is relevant a kind of composition epoxy resin, especially a kind of flame-retardant epoxy resin omposition of halogen and prepreg (Prepreg) and the printed circuit board (PCB) be made up of it.In the course of processing this prepreg being cut or this printed circuit board (PCB) is holed etc., the amount of dropping of buffings or dust obviously reduces.
Background technology
Along with the consideration of electronic material flame retardant resistance, known electronic element can utilize brominated raw material to increase its flame retardant effect, but along with the new line of industry environmental consciousness, materials of electronic components also starts requirement and adopts halogen environment-friendly materials, for example, change nitrogenous or phosphorous epoxy resin into by brominated epoxy resin for the manufacture of the resin raw material of printed circuit board (PCB).
The main substrate of general printed circuit board (PCB) is Copper Foil coating substrate (Copper clad laminate, be called for short CCL), and Copper Foil coating substrate is to make base material with the reinforcing material such as fibrous paper or woven fiber glass, and in this base material impregnation resol or epoxy resin, and through toasting, cut, laminated, hot pressing forms laminated board, then be covered with Copper Foil at the single or double of this laminated board, under heating and pressurizing condition be shaped and make.Follow scientific and technological evolution, print circuit plates making is complicated, for improving, thermotolerance or the prepreg of glass tansition temperature (Tg) or the demand of laminated board product are day by day urgent, and be the glass tansition temperature that improves prepreg, containing on the formula of resin pickup, known novolac epoxy is collocation styrene-maleic anhydride copolymer (Styrene-Maleic anhydride Copolymer further, be called for short SMA), for example No. 455613rd, Taiwan patent, to improve the glass tansition temperature of the made prepreg of this class novolac epoxy, but easily some shortcoming existence of the product of the high glass tansition temperature of this class, need further to improve, wherein for example fragility uprises, and in course of processing prepreg being cut or printed circuit board (PCB) is holed etc., easily produce the problem that buffings or filling powder etc. drop, therefore all easily pollute and be badly in need of improving for processing procedure or product.
Be known as and solve substrate the problem that buffings or filling powder drop occurs for example cutting, in the course of processing such as boring, a kind of practice is in containing resin pickup, further to add macromolecular thermoplastic resin (molecular weight is greater than 5000), for example nbr carboxyl terminal (Carboxyl-terminated butadiene acrylonitrile, or phenoxy resin (Phenoxy) etc. CTBN), to improve the generation of buffings or dust, and the toughness of prepreg is also improved simultaneously.But add this type of macromolecular thermoplastic resin and can reduce significantly the resistance to immersed solder of made substrate, and the such as dissipation factor of electrical specification (Df), specific inductivity (Dk) etc. are all had to bad impact, also can make Copper Foil reduce the sticking power of base material simultaneously.
How to solve known easy the to be crisp problem being produced during using styrene-maleic anhydride copolymer as epoxy resin hardener in the course of processing, and avoid the known problems that macromolecular thermoplastic resin produces of adding in this resin, become research topic of the present invention.
Summary of the invention
Accordingly, the object of the invention is is providing a kind of flame-retardant epoxy resin omposition of halogen, can be produced prepreg or the printed circuit board (PCB) with good resistance to immersed solder, mechanicalness, toughness and electrical insulating property by this composition epoxy resin, for example, and the problem of the generation such as buffings or dust more can be improved in the course of processing (prepreg is cut or printed circuit board (PCB) is holed), made laminated board also can reach the fire-retardant specification of V-0 level simultaneously.
Another object of the present invention is that a kind of prepreg is being provided, it is in solvent, dissolve or disperse the flame-retardant epoxy resin omposition of above-mentioned halogen and make composition epoxy resin varnish, then the above-mentioned composition epoxy resin varnish of impregnation in the reinforcing material of glass fabric etc., bakes and makes.
Another object of the present invention is that a kind of printed circuit board (PCB) is being provided, it is utilize following method and make, the method comprises: the above-mentioned prepreg of certain number of plies is given laminated, and in the laminated tinsel of outermost layer of at least one side of this prepreg and form metal coating laminated board, and this metal coating laminated board pressurized, heated is shaped, then remove the tinsel of the part on above-mentioned metal coating laminated board surface, to form certain circuit pattern, so can obtain printed circuit board (PCB).
In order to achieve the above object, the invention provides a kind of composition epoxy resin, comprising: (a) halogen-free epoxy resin; (b) styrene-maleic anhydride copolymer is as stiffening agent; (c) poly-methyl acid phosphate 1,3-stretches phenylester (Poly (1,3-phenylene methylphosphonate) is called for short PMP) as fire retardant; (d) hardening accelerator; And (e) inorganic filler, wherein, poly-methyl acid phosphate 1, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight, and is preferably 2.7: 1.0.
The present invention is using styrene-maleic anhydride copolymer as stiffening agent and to gather methyl acid phosphate 1,3-stretches phenylester as fire retardant, and by above-mentioned both carry out crosslinking reaction according to specified proportion and epoxy resin, can obtain the epoxy composite material of the high glass transition temp of tool, especially the prepreg of making or printed circuit board (PCB) have good resistance to immersed solder, mechanicalness, toughness and electrical specification (for example Dk, Df), easy the to be crisp problem being produced in the course of processing can avoid using styrene-maleic anhydride copolymer as hardening of resin agent time simultaneously.
For making above and other objects of the present invention, feature and advantage can be more clear, below will, especially exemplified by preferred embodiment, be described in detail below.
Embodiment
Composition epoxy resin of the present invention comprises: (a) halogen-free epoxy resin of 100 weight parts; (b) styrene-maleic anhydride copolymer of 10.0～20.0 weight parts is as stiffening agent; (c) the poly-methyl acid phosphate 1 of 25.0～70.0 weight parts, 3-stretches phenylester as fire retardant; (d) hardening accelerator of 0.01～1.0 weight part; And (e) inorganic filler of 5.0～30.0 weight parts, it is that halogen-free epoxy resin taking 100 weight parts is as benchmark that each composition weight part forms, and poly-methyl acid phosphate 1 wherein, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight, and is preferably 2.7: 1.0.
Composition (a) in the flame-retardant epoxy resin omposition of halogen of the present invention is halogen-free epoxy resin, comprise (1) nitrogen-containing epoxy thermoset, for example benzoxazine (Benzoxazine, be called for short BZ)/phenol aldehyde type epoxy resin multipolymer or containing the novolac epoxy of triazine ring structure; And (2) phosphorous epoxy resin, for example phosphorus-containing phenolic aldehyde type epoxy resin, it is the phosphorus-containing phenolic aldehyde type epoxy resin for a kind of side chain type, jointly uses and above-mentioned resin can be used alone or can combine more than two kinds person simultaneously.In this specific embodiment, this phenol aldehyde type epoxy resin is to be o-cresol formaldehyde type epoxy resin (o-Cresol Novolac Epoxy Resin, be called for short CNE) (label CCP330), and by organic ring-type phosphide, for example 9, mix-10-phosphorus phenanthrene-10-oxide compound (9 of 10-dihydro-9-oxy, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, be called for short DOPO, label Kolon5138), be directed in the structure of this o-cresol formaldehyde type epoxy resin, the o-cresol formaldehyde type epoxy resin (it is a kind of phosphorus-containing phenolic aldehyde type epoxy resin of side chain type) of phosphorous to form (DOPO), DOPO structure is as follows:
The composition (b) of the flame-retardant epoxy resin omposition of halogen of the present invention is stiffening agent, be for example styrene-maleic anhydride copolymer (label Sartomer EF40), it can further mix supports by the arm for example one-level amine type hardeners of other stiffening agent, as Dicyanodiamide (Dicyandiamide, be called for short DICY), two amido sulfobenzides (Diamino diphenyl sulfone, be called for short DDS) etc.The molecular weight of the styrene-maleic anhydride copolymer using can be between 1400 to 50,000, and its structural formula is as follows:
Wherein, m is 1 to 6 integer, and n is 2 to 12 integer.
Composition (c) flame retardant in the flame-retardant epoxy resin omposition of halogen of the present invention, for example, be poly-methyl acid phosphate 1, and 3-stretches phenylester.The poly-methyl acid phosphate 1 using, the molecular weight that 3-stretches phenylester is to be less than 1000, its structural formula is as follows:
Wherein, m=0 or 1, n=0 or 1, p are integer.
Poly-methyl acid phosphate 1 of the present invention, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight, and is preferably 2.7: 1.0.
Composition (d) in the flame-retardant epoxy resin omposition of halogen of the present invention is hardening accelerator, comprise glyoxal ethyline (2-Methyl-Imidazole, 2MI), 2-ethyl-4-methylimidazole (2-Ethyl-4-Methyl-Imidazole, 2E4MI), 2-phenylimidazole (2-Phenyl-Imidazole, 2PI), N, N-dimethyl benzene methylamine (Benzyldimethylamine, BDMA) and 3,5-dimethylphenyl amine, jointly use and above-mentioned hardening accelerator can be used alone or can combine more than two kinds person simultaneously.Those hardening accelerators can accelerate the setting time of prepreg.
Added ingredients (e) inorganic filler in composition epoxy resin of the present invention, comprises calcium carbonate (CaCO
3), talcum (Mg
3si
4o
10(OH)
2), glass powder, silicon-dioxide, kaolin, mica, aluminium hydroxide and aluminium sesquioxide, use jointly and above-mentioned inorganic filler can be used alone or can combine more than two kinds person simultaneously.Those inorganic fillers can be given the characteristics such as epoxy resin workability, flame retardant resistance, thermotolerance or wet fastness.
The solvent that the flame-retardant epoxy resin omposition varnish of halogen of the present invention is used comprises acetone (Acetone), methylethylketone (MEK), propylene glycol monomethyl ether (PM), pimelinketone, 1-Methoxy-2-propyl acetate (Propylene GlycolMethyl Ether Acetate, and dimethyl formamide (Dimethyl Formamide PMA),, and above-mentioned solvent can be used alone or can combine more than two kinds person simultaneously jointly uses DMF).Taking the halogen-free epoxy resin of 100 weight parts as benchmark, the consumption of solvent is 20～50 weight parts.
The flame-retardant epoxy resin omposition of halogen of the present invention is can be by evenly mixing and modulate with agitator (mixer) by mentioned component (a), (b), (c), (d) and (e).Then, by modulated composition epoxy resin is dissolved or dispersed in solvent, and the viscosity of adjustment ring epoxy resins slurry, and make the flame-retardant epoxy resin omposition varnish of halogen.
Then, the above-mentioned made varnish of impregnation in the reinforcing material that is used to form prepreg, and within 2～10 minutes, be dried and react with 150～180 DEG C of heating in drying machine, made thereby goes out the prepreg of semi-harden state.Wherein, the reinforcing material using for example, for the glasscloth of glass fabric, glassine paper, glassmat etc., in addition also can use kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc.
The prepreg obtaining according to this is laminated and form laminated board with certain number of plies, more at the laminated Copper Foil of outermost layer of at least one side of this laminated board, and its pressurized, heated is shaped, obtain whereby the laminated board of Copper Foil coating.Then, by subtractive process such as etchings, make the only part of residual formation circuit pattern of Copper Foil on the laminated board surface of Copper Foil coating, and the part of removing other is to form circuit pattern, so just can obtain the printed circuit board (PCB) with circuit.
The embodiment that below provided is only setting forth technique means of the present invention, not in order to limit technology category of the present invention.
Embodiment mono-to six and comparative example one to two are taking halogen-free epoxy resin weight as 100 parts, and other each composition all represents with relative parts by weight.
Embodiment mono-
The o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 40 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment bis-
The o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 30 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment tri-
The o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 60 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment tetra-
Two amido sulfobenzides (DDS) of the o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 20 weight parts, 10 weight parts, the poly-methyl acid phosphate 1 of 54 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment five
The o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 10 weight parts, the poly-methyl acid phosphate 1 of 27 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.25 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Embodiment six
Two amido sulfobenzides (DDS) of the o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 10 weight parts, 5 weight parts, the poly-methyl acid phosphate 1 of 30 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Comparative example one
The o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the glyoxal ethyline of 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Comparative example two
The o-cresol formaldehyde type epoxy resin of phosphorous (DOPO) of 100 weight parts, the styrene-maleic anhydride copolymer of 15 weight parts, the poly-methyl acid phosphate 1 of 70 weight parts, 3-stretches the glyoxal ethyline of phenylester, 0.5 weight part and the silicon-dioxide of 15 weight parts, under room temperature, use agitator to mix 60 minutes, then add the methylethylketone of 30 weight parts.Above-mentioned material is stirred under room temperature after 120 minutes, form the flame-retardant epoxy resin omposition varnish of halogen.
Utilize cylinder coating machine, the flame-retardant epoxy resin omposition varnish of embodiment mono-to six and comparative example one to two prepared halogen is coated on 7628 (R/C:43%) glasscloth, then, be placed in drying machine, and at 180 DEG C heat drying 2～10 minutes, made thereby goes out the prepreg of semi-harden state.Then four prepregs are given laminated, and the Copper Foil of the each laminated loz of outermost layer in its both sides.Then, its pressurized, heated is carried out to pressing, obtain whereby Copper Foil coating laminated board, the wherein condition of pressurized, heated, is the heat-up rate with 2.0 DEG C/min, reaches 180 DEG C, and at 180 DEG C, total head 15kg/cm
2(first pressing 8kg/cm
2) descend pressurized, heated 60 minutes, and make Copper Foil coating laminated board.Then, by subtractive process such as etchings, make the only part of residual formation circuit pattern of Copper Foil on Copper Foil coating laminated board surface, and remove other part, form whereby circuit pattern.According to this, just can obtain the printed circuit board (PCB) on top layer with circuit.
Resistance to immersed solder (Solder Floating) to prepared Copper Foil coating laminated board, tearing strength (Peeling Strength), glass transfer temperature (Glass Transition Temperature, Tg), heat decomposition temperature (Tg (5%)), flame retardancy, toughness, specific inductivity, the dissipation factor and the amount of dropping measure, and the flame-retardant epoxy resin omposition of the halogen of embodiment mono-to six and comparative example one to two and evaluation result thereof are as shown in Table 1.
Property detection:
[resistance to immersed solder test]
The laminated board being dried is soaked after certain hour in the soldering of 288 DEG C is bathed, observe defect and whether occur, for example, determine with layering or the puff of laminated board.
[tearing strength test]
Tearing strength refers to the sticking power of Copper Foil for base material, conventionally vertically tears up on plate face with the Copper Foil of per inch (25.4mm) width, expresses the power of sticking power with the size of its required strength.MIL-P-55110E specifies that its qualifying standard of substrate of loz Copper Foil is 4lb/in.
[glass transfer temperature test]
Utilize dynamic mechanical analysis instrument (DMA) to measure glass transfer temperature (Tg).The test specification of glass transfer temperature is interconnected IPC-TM-650.2.4.25C and the 24C detection method with encapsulating association (The Institute for Interconnecting and PackagingElectronic Circuits, IPC) of electronic circuit.
[heat decomposition temperature test]
Utilize thermogravimetric analyzer (TGA) to measure compared with initial stage quality, the temperature in the time that quality reduces 5%, is heat decomposition temperature.
[flame retardancy test]
Utilize UL 94V: vertical combustion testing method, laminated board is fixed with vertical position, with Bunsen burner burning, relatively its spontaneous combustion is extinguished and combustion-supporting characteristic, and its report the test is divided into UL 94V-0 (the best) to the resistance to combustion grade of UL94V-2.
[toughness test]
Laminated board is lain against on plane tool, vertical and the laminated board Surface Contact with cross metal fixture, grant again vertical pressure, after remove this cross tool, observe cross shape vestige on substrate, inspect this laminate surface, occur to be judged to be good without white scrimp, show slightly lineae ablicantes for general, it is bad that crackle or fracture person occur.[specific inductivity and the dissipation factor measure]
According to ASTM D150 specification, under operating frequency 1GHz, calculate specific inductivity (Dk) and the dissipation factor (Df).
[drop and measure examination]
Get after the laminated board weighing of 4 inches of squared magnitude, form the circle of 3.192 inches squares with stamping machine punching press, remove the break flour weighing again that punching press forms, so weight loss amount is the break flour amount of dropping.
Lower molecular weight used in the present invention is gathered methyl acid phosphate 1,3-stretches the advantage that phenylester modulates on processing procedure: molecular weight is lower than 1000 poly-methyl acid phosphate 1,3-stretch phenylester be in a liquid state and be easy to modulation, the sclerous reaction time that does not affect styrene-maleic anhydride copolymer and halogen-free epoxy resin, resin composition Chinese varnish is easily concocted.The condition of embodiment mono-is best.Embodiment bis-, three represents respectively poly-methyl acid phosphate 1, and the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is the enforcement aspect of 2.0: 1 and 4.0: 1 by weight.Embodiment tetra-, five is illustrated in poly-methyl acid phosphate 1, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is under the condition of 2.7: 1 by weight, adopt respectively the enforcement aspect of the styrene-maleic anhydride copolymer of higher amount and lower amount, wherein, the stiffening agent that embodiment tetra-and embodiment six use not is single styrene-maleic anhydride copolymer composition, but using the composite hardener being combined by styrene-maleic anhydride copolymer and two amido sulfobenzides to come and poly-methyl acid phosphate 1,3-stretches phenylester collocation modulation.As shown in Table 1, embodiment mono-to six and comparative example one to two demonstration, by flame-retardant epoxy resin omposition (the poly-methyl acid phosphate 1 wherein of halogen of the present invention, the ratio that 3-stretches phenylester and styrene-maleic anhydride copolymer is 2.0: 1 to 4.0: 1 by weight) made laminated board meets the specification that printed circuit board (PCB) requires, and especially embodiment mono-, two, three, five, six is more presented at the thing that drops producing while cutting the effect of obvious minimizing.Embodiment tetra-and embodiment six represent that the made laminated board of flame-retardant epoxy resin omposition of the halogen that contains composite hardener (for example, by further mixed other one-level amine of supporting by the arm of styrene-maleic anhydride copolymer) by the present invention still meets the specification that printed circuit board (PCB) requires.And with reference to comparative example one, its fragility that shows made laminated board is larger, toughness is not good, cut the Shi Yiyou thing that drops, and with reference to comparative example two, it shows resistance to immersed solder, the equal variation of tearing strength specific inductivity of made laminated board.
The present invention is with the styrene-maleic anhydride copolymer of specified proportion and low-molecular-weight poly-methyl acid phosphate 1, the combination that 3-stretches phenylester is applied to halogen-free epoxy resin composition, to manufacture prepreg or printed circuit board (PCB), easy the to be crisp problem being produced in the course of processing while improving whereby using styrene-maleic anhydride copolymer as epoxy resin hardener, the thing that for example drops in the time cutting, hole can increase, simultaneously all be not subject to adding the impact of fire retardant in the heat-resistant quality of laminated board or electrical specification on as Dk, Df etc., and can promote the flame-retarding characteristic of made laminated board.
For all those of skill in the art, the present invention can make various modifications and changes significantly and not depart from the spirit and scope of the present invention.Therefore, the present invention includes those amendments and variation, and it is all included in lower attached claim scope and impartial person thereof.
Claims (9)
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| CN103724936B (en) * | 2012-10-10 | 2016-08-03 | 慧智科技（中国）有限公司 | Improve the Halogen-free low dielectric epoxy resin composition of shock resistance |
| CN103881059A (en) * | 2012-12-21 | 2014-06-25 | 台光电子材料(昆山)有限公司 | Low dielectric resin composition and application thereof |
| SG11201900686XA (en) * | 2016-07-25 | 2019-02-27 | Isola Usa Corp | Improved sma resin formulation |
| CN109929219A (en) * | 2017-12-19 | 2019-06-25 | 洛阳尖端技术研究院 | Modified flame-retardant epoxy resin, prepreg and respective preparation method |
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| CN1317031A (en) * | 1998-08-28 | 2001-10-10 | 陶氏化学公司 | Fire resistant styrene polymer foams with reduced brominated fire ratartant |
| CN1423678A (en) * | 1999-12-13 | 2003-06-11 | 陶氏环球技术公司 | Flame retardant phosphorus element-containing epoxy resin compositions |
| CN101602881A (en) * | 2009-05-12 | 2009-12-16 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and application thereof |
| CN101679675A (en) * | 2007-06-14 | 2010-03-24 | 巴斯夫欧洲公司 | Flame retardant compositions |
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|---|---|---|---|---|
| CN1317031A (en) * | 1998-08-28 | 2001-10-10 | 陶氏化学公司 | Fire resistant styrene polymer foams with reduced brominated fire ratartant |
| CN1423678A (en) * | 1999-12-13 | 2003-06-11 | 陶氏环球技术公司 | Flame retardant phosphorus element-containing epoxy resin compositions |
| CN101679675A (en) * | 2007-06-14 | 2010-03-24 | 巴斯夫欧洲公司 | Flame retardant compositions |
| CN101602881A (en) * | 2009-05-12 | 2009-12-16 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and application thereof |
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