CN101851390B - Black halogen-free epoxy resin composition and cover film prepared by using same - Google Patents
Black halogen-free epoxy resin composition and cover film prepared by using same Download PDFInfo
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- CN101851390B CN101851390B CN201010177757XA CN201010177757A CN101851390B CN 101851390 B CN101851390 B CN 101851390B CN 201010177757X A CN201010177757X A CN 201010177757XA CN 201010177757 A CN201010177757 A CN 201010177757A CN 101851390 B CN101851390 B CN 101851390B
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- epoxy resin
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- free epoxy
- halogen
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000013039 cover film Substances 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 239000004642 Polyimide Substances 0.000 claims abstract description 18
- 229920001721 polyimide Polymers 0.000 claims abstract description 18
- 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 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- 239000005060 rubber Substances 0.000 claims abstract description 5
- 239000002362 mulch Substances 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004026 adhesive bonding Methods 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012764 mineral filler Substances 0.000 claims description 4
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 6
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- 239000011342 resin composition Substances 0.000 abstract 2
- 239000004408 titanium dioxide Substances 0.000 abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000003292 glue Substances 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- -1 acrylic ester Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 101001045744 Sus scrofa Hepatocyte nuclear factor 1-beta Proteins 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- NRZZLYODXDSLEK-UHFFFAOYSA-N (6-ethoxy-6-oxohexyl) 3,5-diacetamido-2,4,6-triiodobenzoate Chemical compound CCOC(=O)CCCCCOC(=O)C1=C(I)C(NC(C)=O)=C(I)C(NC(C)=O)=C1I NRZZLYODXDSLEK-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007905 drug manufacturing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004820 halides Chemical class 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
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a black halogen-free epoxy resin composition and a covering film prepared by using the same, wherein the black halogen-free epoxy resin composition comprises: epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, acrylate modified epoxy resin, a curing agent, a curing accelerator, carbon black powder, titanium dioxide, a phosphorus-containing flame retardant, an inorganic filler and an organic solvent; the covering film prepared by the composition comprises a polyimide insulating film, a black halogen-free epoxy resin composition coating coated on the polyimide insulating film, and release paper coated on the black halogen-free epoxy resin composition coating. The resin composition does not contain halogen, a small amount of carbon black powder is adopted to make the resin composition become black and play a role in shading, and titanium dioxide is adopted to play a role in enhancing shading; meanwhile, the acrylate modified epoxy resin is used, so that the resin system achieves flame retardance and keeps good mechanical property; the covering film prepared by the composition has the advantages of standard surface resistance and volume resistivity, UL 94V-0 level flame retardance, high peel strength, excellent dimensional stability, flexibility and processability.
Description
Technical field
The present invention relates to a kind of halogen-free epoxy resin composition, the mulch film that relates in particular to a kind of black halogen-free epoxy resin composition and use its preparation.
Background technology
The mulch film of flexible printed circuit (FPCB) usefulness not only plays resistance weldering effect, and makes FPCB not receive the erosion of dust, moisture, pharmaceutical chemicals and reduce stress influence in the BENDING PROCESS.Mulch film is on polyimide (PI) film, to apply one deck tackiness agent, and baking desolventizes then, is composited with separate-type paper again.Usually used tackiness agent has epoxy resin, acrylic ester, polyester system etc.; Open 2004-137437, WO2008/136096, CN 1847352A, CN 1670107A etc. like the spy; Wherein mainly contain two kinds of acrylic ester and epoxy resin; Both respectively have quality, and the mulch film shelf lives of acrylic ester is long, cementability good, but thermotolerance is relatively poor; The excellent heat resistance of epoxy resin, but the shelf lives is shorter, and two kinds of parallel development of glue system promote the lifting of mulch film performance jointly.Mulch film is main with halogen flame retardant glue system still at present, adopt the very high brominated resins of bromine content to reach fire-retardant purpose, but there is the hidden danger that produces the carcinogenic substance dioxin in product in discarded burning disposal process; And the enforcement of the RoHS of European Union instruction has proposed to contain the requirement of environmental management materials such as lead, mercury, cadmium, sexavalent chrome, PBBs, PBDE to electronic product.In order to satisfy the environmental protection trend of " leadless process " and " Halogen material ", each producer is all at active development Halogen product.Absatzvolumen according to Japanese market survey institute JMS prediction halogen-free flame-retardant flexibility coat copper plate and mulch film will be increased to 2010 from 800,000 square metres in 2003 7700000 square metres.The without halide Kapton mulch film of environmental management materials such as not halogen-containing and plumbous, mercury, cadmium, sexavalent chrome faces good opportunity to develop.
Recently; Market is more and more stronger to the demand of black mulch film, than common mulch film, and its opaque, no reflection events; Be mainly used in preparation LED lamp plate, auto lamp etc.; Backlight owing to not reflecting, therefore this opaque mulch film can strengthen the contrast gradient of photogen, helps to improve the working efficiency of photoelectric component; In addition, the black mulch film also is widely used in the manufacturing of mobile phone.With regard to the technology of preparing of black mulch film, two kinds of approach are arranged: the one, common mulch film is coated on the black PI film with glue; The 2nd, special a kind of black glue is coated in (like US 2004/0142191) on the common PI film.As far as batch process, first kind of approach only need be changed starting material, and be easy and simple to handle; Second kind of approach then will be started with from prescription, and brings certain puzzlement to production operation.But there is a problem; The black PI film of the above thickness of 25 μ m all has sale both at home and abroad, and 12.5 μ m only have Du Pont to produce (trade mark is Kapton-CB), and is for sale hardly; At present some producers are also arranged at the black PI of this specification of active development film; But all not mature enough and cost an arm and a leg, and the client often needs the black mulch film of 12.5 μ mPI films, forcedly only take second kind of technological approaches.The present invention does to set forth with regard to a kind of halogen-free epoxy resin composition of black and with the black mulch film of its preparation.
Summary of the invention
The object of the present invention is to provide a kind of black halogen-free epoxy resin composition, make its blackening and shading, use titanium oxide to play the enhancing interception simultaneously through adding carbon powder.
Another object of the present invention is to, a kind of mulch film that uses the above-mentioned compsn preparation is provided, it possesses excellent opacifying property, insulating property, thermotolerance, covers shape property, cementability and flame retardant resistance.
For realizing above-mentioned purpose; The present invention provides a kind of black halogen-free epoxy resin composition, and said composition comprises that component and weight part thereof are following: epoxy resin 30-60 part, nbr carboxyl terminal 20-40 part, acrylate modified epoxy resin 5-25 part, solidifying agent 1-10 part (per 100 gram resins and rubber proportions), curing catalyst 0.01-1.0 part, carbon powder 1-6 part, titanium oxide 1-20 part, phosphonium flame retardant 10-25 part, mineral filler 0-100 part, to reach 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 compsn preparation is provided; Comprise: the polyimide insulative film, be coated on the black halogen-free epoxy resin composition coating on the polyimide insulative film and be laminated with the separate-type paper on the black halogen-free epoxy resin composition coating, 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 black halogen-free epoxy resin composition coating is 5-45 μ m, preferred 10-35 μ m.
Beneficial effect of the present invention: resin combination of the present invention is not halogen-containing, adopts a small amount of carbon powder to make it to become black and has reached interception, adopts titanium oxide to play the enhancing interception; Use acrylate modified epoxy resin simultaneously, make to keep mechanical property preferably when resin system reaches flame retardant resistance.With the black mulch film of said composition preparation, surface resistivity and volume specific resistance are up to standard, and flame retardant resistance reaches the UL94V-0 level, have high-peeling strength, excellent size stability, flexibility and processing characteristics.
Embodiment
Halogen-free epoxy resin composition of the present invention comprises: epoxy resin, nbr carboxyl terminal, acrylate modified epoxy resin, solidifying agent, curing catalyst, carbon powder, titanium oxide, phosphonium flame retardant, filler, oxidation inhibitor and organic solvent.
The weight proportion of above-mentioned raw materials (by the listed as parts by weight of constituent) is:
Epoxy resin 30-60 part;
Nbr carboxyl terminal 20-40 part;
Acrylate modified epoxy resin 5-25 part;
Solidifying agent 1-10 part;
Curing catalyst 0.01-1.0 part;
Carbon powder 1-6 part;
Titanium oxide 1-20 part;
Phosphonium flame retardant 10-25 part;
Filler 0-100 part;
Oxidation inhibitor 0.01-1.0 part;
Organic solvent is an amount of.
Each feedstock detail is following:
(1) epoxy resin
Above-mentioned epoxy resin mainly is some not halogen-containing resins that possess special construction, or has excellent thermotolerance or have special fire retardant mechanism, and requires this resin and nbr carboxyl terminal to possess good consistency.NC-3000, NC-3000-H, NC-2000, XD-1000 that the epoxy resin of this type special construction has Nippon Kayaku K. K to make; Also have HP-7200L that Dainippon Ink. & Chemicals Inc makes, HP-7200, HP-7200H, HP-7200HH, EXA-4816, EXA-4840 etc., also have epoxy resin such as SEN-100 that star Co., Ltd. of Korea S elder generation makes, SE-110 in addition.
These halogen-free epoxy resins can use separately, perhaps use with the combination of two or more different resins.
(2) 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 like the monomer of methylacrylic 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 ionic product XER-32 (JSR Corporation manufacturing).
(3) acrylate modified epoxy resin
Acrylate modified epoxy resin and CTBN is shared; Adjustment through curing system; Can bring into play two kinds of elastomeric advantages simultaneously, also have a certain amount of small molecules epoxy resin 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 epoxy resin comprises that (Nippon Shokubai Co., Ltd makes BPA 328, elastomer content 20 quality % etc. with BPF 307 at present.
(4) 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), 4,4-diaminodiphenyl oxide, Dyhard RU 100 etc.; Wherein the temperature of reaction of DDS cured epoxy resin is higher, but can help to improve the thermotolerance of product.
(5) curing catalyst
Above-mentioned curing catalyst is the imidazoles curing catalyst, can be in glyoxal ethyline, 1-Methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, the 2-phenyl-4-methylimidazole one or more.
(6) carbon powder
The present invention mainly uses carbon powder to reach that mulch film turns black and the shading purpose.Carbon powder is divided into graphitized carbon black and colour carbon black, in order to guarantee the insulating property of product, can only adopt colour carbon black.Commercially available colour carbon black powder has 2808 (the refreshing painted sculptures glue of Dongguan City Products Co., Ltd makes), HI-Black 50L (Korea S KCB manufacturing) etc.
Carbon powder is one of black pigment of using always, and the present invention uses colour carbon black, selects the thermally oxidized black that blackness is high, particle diameter is little to be advisable, and coordinates the blackness of composition epoxy resin and the contradiction between the insulating property to the full extent; In addition, carbon black is one of the most difficult dispersive pigment, whether is distributed to the micropartical state that meets optical property and directly has influence on sooty blackness, form and aspect and covering power.Comprehensive blackness and insulating property, the carbon black usage quantity is the best with the 3-5 weight part.
(7) titanium oxide
Titanium oxide possesses very strong refractive power effect, adds to make that on a small quantity mulch film can printing opacity, strengthens the contrast gradient of light source effectively.Commodity have two kinds: a kind of is rutile titanium dioxide, proportion 4.26, and refractive index 2.72, photostabilization is very strong, is applicable to exterior product; A kind of is anatase titanium dioxide, and thermotolerance is poor slightly, is prone to yellowing, not weather resistance, is suitable for indoor product.In order to improve reliability of products and weathering resistance, adopt the titanium oxide of rutile-type, commercially available product has R-706, R-7060, R-900, R-902, R-960 (Du Pont's manufacturing) etc.
Though titanium oxide possesses very strong shaded effect, itself is white in color, if addition is little, possibly not reach the shading requirement; If addition is big, then can offset the blackness of the composition epoxy resin that carbon black brings, present brown even grey, so the usage quantity of titanium oxide will be weighed colourity and shaded effect and decide.Take all factors into consideration shaded effect and blackness, the titanium oxide usage quantity is the best with the 5-15 weight part.
(8) phosphonium flame retardant
Phosphonium flame retardant commonly used has SPB-100 (manufacturing of Ri Ben Otsuka Chemical Co., Ltd), OP-935 (German Clariant manufactured), SP-703H (four countries change into Co., Ltd. and make) etc.Whether except considering flame retarding efficiency, whether influencing the glue amount of overflowing, whether influencing the shelf lives, be heated to surface transport etc. for a long time all is the factor that must consider when being used to prepare mulch film.
(9) filler
Above-mentioned filler is mineral filler, can be white lake, Marinco H, zeolite, wollastonite, silicon-dioxide, Natural manganese dioxide, Calucium Silicate powder, lime carbonate, clay, boehmite, talcum and mica etc., uses one or more mixture wherein.
(10) oxidation inhibitor
The main purpose of oxidation inhibitor in resin combination is to reduce epoxy resin and the oxidation situation of acrylonitrile-butadiene rubber in hot setting and following process process.Employed oxidation inhibitor can be 1010,1222,1076 (CIBA GEIGY Co. manufacturings) and 399,312,210 (GE Specially Chemicals manufacturings) etc., and home-made oxidation inhibitor such as commodity are called DNP (production of the triumphant source of Qujiang District, Quzhou City, Zhejiang Fine Chemical Works) etc.More than the oxidation inhibitor of these different names of an article can optionally select for use a kind of separately or mix two or more uses.The interpolation scope that oxidation inhibitor is formed at compsn is the 0.01-1.0 weight part.
(11) organic solvent
Above-mentioned organic solvent can be one or more in acetone, butanone, pimelinketone, EGME, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ETHYLE ACETATE etc.In the compsn of preparation, the preferred 30-40 weight of amount of solid content %, the viscosity that can obtain to suit provides good workability, guarantees in coating procedure, not occur visual defects.
Use similar devices such as ball mill, jar mill, sand mill, and be used high-shear dispersed with stirring equipment, can the inoganic solids component and the organic solvent of organic solid component in the present composition and interpolation be mixed.
Above-mentioned compsn can be used for the preparation of mulch film.Utilize organic solvent to mix the black liquid state dispersion-s that required component forms the present composition, use coating equipment that this dispersion-s is coated on the polyimide insulative film.Make the insulating film that is coated with dispersion-s through online drying oven; 80-160 ℃ of heating 2 to 8 minutes, remove organic solvent and drying compsn thus, contain the said composition layer of semicure attitude with formation; Next 80-100 ℃ down and separate-type paper compound, rolling promptly obtains the black mulch film.
The dry thickness of composition coating film is 5-45 μ m 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.
Observe its color and luster and light transmission to the above-mentioned black mulch film of processing, test its excessive glue amount, thermotolerance, flame retardant resistance and stripping strength, further give to explain in detail and describe like following embodiment.
Now the embodiment of the invention is specified as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
Epoxy resin (marque NC-3000-H, epoxy equivalent (weight) 290g/eq, Japanese chemical drug manufacturing) 35 weight parts; Nbr carboxyl terminal (Zeon Corporation makes for marque Nipol 1072CG, acrylonitrile content 27 quality %) 21 weight parts; Acrylate modified epoxy resin (Nippon Shokubai Co., Ltd makes for marque BPF307, elastomer content 20 quality %) 9.1 weight parts; Diaminodiphenylsulfone(DDS) (DDS) 6.63 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.163 weight part; Carbon powder (marque HI-Black 50L, Korea S KCB makes) 1.95 weight parts; Titanium oxide (marque R-706, Du Pont makes) 6.5 weight parts; Phosphonium flame retardant (marque OP-935, German Clariant manufacturing) 13 weight parts; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.05 weight part.The solids content of using butanone solvent to regulate glue is 38%, mixes and processes black halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m through 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 through roll-in, rolling obtains the mulch film of black.
Embodiment 2: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 4.0 parts of carbon powders, 5.0 parts of titanium oxide.
Embodiment 3: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 4.0 parts of carbon powders, 10.0 parts of titanium oxide.
Embodiment 4: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 5.0 parts of carbon powders, 5.0 parts of titanium oxide.
Embodiment 5: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 5.0 parts of carbon powders, 10.0 parts of titanium oxide.
Comparative example 1: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 1.0 parts of carbon powders, 15.0 parts of titanium oxide.
Comparative example 2: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 1.0 parts of carbon powders, 20.0 parts of titanium oxide.
Comparative example 3: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 2.0 parts of carbon powders, 10.0 parts of titanium oxide.
Comparative example 4: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 2.0 parts of carbon powders, 15.0 parts of titanium oxide.
Comparative example 5: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 6.0 parts of carbon powders, 5.0 parts of titanium oxide.
Specifically see the following form:
The performance of the formulation Example of table 1. halogen-free epoxy resin composition and the flexibility coat copper plate of preparation thereof
The performance of the prescription comparative example of table 2. halogen-free epoxy resin composition and the flexibility coat copper plate of preparation thereof
The testing method of above characteristic is following:
(1) testing method of printing opacity: with sample facing to high light, visual whether printing opacity.
(2) surface resistivity and volume specific resistance after damp and hot are tested according to IPC-TM-650 2.5.17 method.
(3) excessive glue amount is tested according to IPC-TM-650 2.3.17.1 method.
(4) stripping strength (PS) is tested the stripping strength of crown cap according to IPC-TM-650 2.4.9 method.
(5) anti-immersed solder property is tested according to IPC-TM-650 2.4.13.
(6) incendivity (flame retardant resistance): measure according to UL 94 vertical combustion methods.
In sum, resin combination of the present invention is not halogen-containing, adopts a small amount of carbon powder to make it to become black and has reached interception, adopts titanium oxide to play the enhancing interception; Use acrylate modified epoxy resin simultaneously, make to keep mechanical property preferably when resin system reaches flame retardant resistance.With the black mulch film of said composition preparation, surface resistivity and volume specific resistance are up to standard, and flame retardant resistance reaches UL94 V-0 level, have high-peeling strength, excellent size stability, flexibility and processing characteristics.
The above; Be merely 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 (6)
1. the mulch film of black halogen-free epoxy resin composition preparation; It is characterized in that; Comprise: the polyimide insulative film, be coated on the black halogen-free epoxy resin composition coating on the polyimide insulative film and be laminated with the separate-type paper on the black halogen-free epoxy resin composition coating, 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 black halogen-free epoxy resin composition coating is 5-45 μ m;
Said black halogen-free epoxy resin composition comprises that component and weight part thereof are following: epoxy resin 30-60 part, nbr carboxyl terminal 20-40 part, acrylate modified epoxy resin 5-25 part, solidifying agent 1-10 part, curing catalyst 0.01-1.0 part, carbon powder 1-6 part, titanium oxide 5-15 part, phosphonium flame retardant 10-25 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; Said solidifying agent is an amine curing agent, adopts 4,4-diaminodiphenylsulfone(DDS), 3,3-diaminodiphenylsulfone(DDS), 4,4-diaminodiphenyl oxide or Dyhard RU 100; Said carbon powder adopts colour carbon black, and titanium oxide adopts the titanium oxide of rutile-type.
2. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1 is characterized in that the dry thickness of black halogen-free epoxy resin composition coating is 10-35 μ m.
3. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that; Said nbr carboxyl terminal is an acrylonitrile butadiene copolymer; Wherein acrylonitrile content is 18-50 quality %, and the copolymer molecule chain end is by carboxylated, and vinyl cyanide, divinyl and carboxylic monomeric copolymer rubber.
4. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that; Said 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.
5. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that the mixture of one or more in said mineral filler employing white lake, Marinco H, zeolite, wollastonite, silicon-dioxide, Natural manganese dioxide, Calucium Silicate powder, lime carbonate, clay, boehmite, talcum and the mica.
6. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that said organic solvent is one or more in acetone, butanone, pimelinketone, EGME, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ETHYLE ACETATE.
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| 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 |
| CN102311613B (en) * | 2011-04-03 | 2013-09-18 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and adhesive film prepared from same |
| CN103101265A (en) * | 2011-11-11 | 2013-05-15 | 松扬电子材料(昆山)有限公司 | Colored cover film |
| CN102529262B (en) * | 2011-12-30 | 2014-07-16 | 常熟市富邦胶带有限责任公司 | High temperature resistant coating-type black matt polyimide film |
| CN102731743B (en) * | 2012-06-26 | 2014-05-07 | 华烁科技股份有限公司 | Preparation of white thermosetting resin used for LED light having encapsulating film |
| CN103525086B (en) * | 2012-07-04 | 2015-12-16 | 合正科技股份有限公司 | High heat-resisting, low rigidity, nonflammable resin and composition thereof |
| CN103483586B (en) * | 2013-09-25 | 2016-04-06 | 广东生益科技股份有限公司 | Modified polyimide resin, the Adhesive composition containing this modified polyimide resin and the mulch film containing this Adhesive composition |
| CN103554844B (en) | 2013-10-29 | 2016-02-17 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and uses thereof |
| CN106398654A (en) * | 2016-08-30 | 2017-02-15 | 广东永创鑫电子有限公司 | Heat conduction material for LED (light-emitting diode) flexible circuit board and preparation method of heat conduction material |
| CN106221613A (en) * | 2016-08-30 | 2016-12-14 | 广东永创鑫电子有限公司 | A kind of glue for many colors coverlay and preparation method thereof |
| CN106398590A (en) * | 2016-09-13 | 2017-02-15 | 深圳市海纳泰兴电子有限公司 | Halogen-free cover film adhesion agent |
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| CN109554149B (en) * | 2018-10-18 | 2021-04-27 | 哈尔滨工业大学无锡新材料研究院 | Epoxy adhesive for flexible circuit board and preparation method and application thereof |
| CN110305445A (en) * | 2019-05-16 | 2019-10-08 | 浙江华正新材料股份有限公司 | A kind of black-colored resin composition, prepreg and laminate |
| CN113844130A (en) * | 2021-09-13 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of high-Tg high-frequency copper-clad plate |
| CN115926576A (en) * | 2022-12-13 | 2023-04-07 | 东莞市毅联电子科技有限公司 | Shading coating for flexible circuit board and preparation method and use method thereof |
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