CN109266284A - A kind of halogen-free resin composition, cover film prepared therefrom and copper-clad plate and printed circuit board - Google Patents
A kind of halogen-free resin composition, cover film prepared therefrom and copper-clad plate and printed circuit board Download PDFInfo
- Publication number
- CN109266284A CN109266284A CN201811031885.6A CN201811031885A CN109266284A CN 109266284 A CN109266284 A CN 109266284A CN 201811031885 A CN201811031885 A CN 201811031885A CN 109266284 A CN109266284 A CN 109266284A
- Authority
- CN
- China
- Prior art keywords
- halogen
- parts
- combination
- resin composition
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013039 cover film Substances 0.000 title claims abstract description 53
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 150000002118 epoxides Chemical class 0.000 claims abstract description 34
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 claims abstract description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- 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 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 239000012790 adhesive layer Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 23
- 239000011889 copper foil Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000004642 Polyimide Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 229920001721 polyimide Polymers 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010030 laminating Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- UPUZGXILYFKSGE-UHFFFAOYSA-N quinoxaline-2-carboxylic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CN=C21 UPUZGXILYFKSGE-UHFFFAOYSA-N 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000002927 oxygen compounds Chemical class 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- QMQZIXCNLUPEIN-UHFFFAOYSA-N 1h-imidazole-2-carbonitrile Chemical compound N#CC1=NC=CN1 QMQZIXCNLUPEIN-UHFFFAOYSA-N 0.000 claims description 2
- INQXGZFDGDSRIF-UHFFFAOYSA-N 1h-quinoxaline-2-thione Chemical compound C1=CC=CC2=NC(S)=CN=C21 INQXGZFDGDSRIF-UHFFFAOYSA-N 0.000 claims description 2
- RSNQVABHABAKEZ-UHFFFAOYSA-N 2,3-diphenylquinoxaline Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 RSNQVABHABAKEZ-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-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
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-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
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 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 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005496 phosphonium group Chemical group 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- 150000002148 esters Chemical class 0.000 claims 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 229920000305 Nylon 6,10 Polymers 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- AAPVVURPIAJQDU-UHFFFAOYSA-N octadecyl 2-(4-hydroxyphenyl)-2-methylhexanoate Chemical group C(CCCCCCCCCCCCCCCCC)OC(C(C)(C1=CC=C(C=C1)O)CCCC)=O AAPVVURPIAJQDU-UHFFFAOYSA-N 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 15
- 238000003860 storage Methods 0.000 abstract description 14
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 9
- 238000004026 adhesive bonding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- GXYBXMMQTFXLPW-UHFFFAOYSA-N octadecyl 3-phenylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC=CC=C1 GXYBXMMQTFXLPW-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The present invention provides a kind of halogen-free resin composition, cover film prepared therefrom and copper-clad plate and printed circuit board.The halogen-free resin composition comprises the following components in parts by weight: 60~90 parts of polyurethane containing carboxyl, 5~35 parts of epoxide, 1~10 part of blocked isocyanate and 0.5~5 part of nitrogen-containing heterocycle compound.The present invention is using carboxylic polyurethane resin as matrix resin, cooperate epoxide, blocked isocyanate, nitrogen-containing heterocycle compound, it is capable of forming co-crosslinking network structure, crosslink density is high, improve the semi-solid preparation state storage stability of composition, there is excellent flexibility, heat resistance, chemical-resistance and flame retardant property simultaneously, the cover film be prepared by it and copper-clad plate have excellent acid resistance, heat resistance, anti-flammability and higher peel strength.
Description
Technical field
The invention belongs to printed-board technology field, it is related to a kind of halogen-free resin composition, cover film prepared therefrom
With copper-clad plate and printed circuit board.
Background technique
With the development of flexible printed-circuit board industry, market to the flexibility of cover film and copper-clad plate, chemical resistance and
The requirement of the performances such as anti-flammability is higher and higher.Traditional cover film adhesive use epoxide/nitrile rubber for mainly at
Point, collocation curing agent, fire retardant and other auxiliary agents composition, wherein nitrile rubber be toughening element, dosage is very few, and flexibility is poor；
Dosage is excessive, and the initial bonding strength of glue-line is big, not easy to operate；And ageing-resistant performance and chemical-resistance are poor, it is difficult to answer high-end
With middle use.
JP2009-96940A, CN105482442A, CN102822304B etc. use resin based on polyurethane, ring of arranging in pairs or groups
Other resins such as oxygen compound, phenolic resin and fire retardant, are prepared for cover film, the flexibility and peel strength of product compared with
It is good, but its chemical-resistance, ageing-resistant performance are still not excellent enough.
The CN101687980B of Showa electrician discloses a kind of compositions of thermosetting resin, the compositions of thermosetting resin
Comprising polyurethane, the strong basicity nitrogen-containing heterocycle compound that pKa value is 10.0-14.0, the products such as solder resist, protective film tool has been made
There are the excellent properties such as non cohesive gel, low warpage and high insulation, but since the nitrogen-containing heterocycle compound reactivity of use is high, resin group
Close the poor storage stability of object semi-solid preparation state.
Therefore, in this field, the in order to balance storage of flexibility, chemical resistance, resistance to ag(e)ing, anti-flammability and semi-solid preparation state
The performance requirements such as stability are deposited, need to develop new resin combination to make cover film.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of halogen-free resin compositions, prepared therefrom
Cover film and copper-clad plate and printed wiring board.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of halogen-free resin composition, and the halogen-free resin composition includes following parts by weight
Component:
60~90 parts of polyurethane containing carboxyl, 5~35 parts of epoxide, 1~10 part of blocked isocyanate and nitrogen-containing hetero
0.5~5 part of cycle compound.
In the present invention, by cooperating epoxide, enclosed type using carboxylic polyurethane resin as matrix resin
Isocyanates, nitrogen-containing heterocycle compound.The semi-solid preparation state storage stability of composition is improved, crosslink density is high, and heat resistance increases
By force.
In the present invention, epoxide and blocked isocyanate can cooperate with solidification carboxyl polyurethane resin；It is nitrogenous
Heterocyclic compound can promote the autohemagglutination of epoxide and reacting for epoxide and the polyurethane containing carboxyl, and can be improved
The flame retardant property of resin cured matter.
In the present invention, the dosage of the polyurethane containing carboxyl can for 60 parts, 63 parts, 65 parts, 68 parts, 70 parts, 73 parts,
It 75 parts, 78 parts, 80 parts, 83 parts, 85 parts, 88 parts or 90 parts, when the dosage of the polyurethane resin containing carboxyl is too many, will lead to described
The crosslink density of resin combination is lower, declines so as to cause the heat resistance of the cover film formed by the resin combination；When
When the dosage of the polyurethane resin containing carboxyl is very little, the flexibility decline of the cover film formed by the resin combination will lead to,
And increased with the cover film glue overflow amount of its production.
Preferably, the polyurethane resin containing carboxyl is selected from type polyurethane resin containing carboxyl polyester or polyether-type containing carboxyl is poly-
In urethane resin any one or at least two combination.
Preferably, the number-average molecular weight of the polyurethane resin containing carboxyl be 10000~50000, such as 10000,
13000、15000、18000、20000、23000、25000、28000、30000、33000、35000、38000、40000、
42000,45000,48000 or 50000.
Preferably, the glass transition temperature of the polyurethane resin containing carboxyl be -10 DEG C~120 DEG C, such as -10 DEG C,
0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C or 120 DEG C.
Preferably, the acid value of the polyurethane resin containing carboxyl is 20mg KOH/g~50mg KOH/g, such as 20mg
KOH/g、23mg KOH/g、25mg KOH/g、28mg KOH/g、30mg KOH/g、33mg KOH/g、35mg KOH/g、38mg
KOH/g, 40mg KOH/g, 43mg KOH/g, 45mg KOH/g, 48mg KOH/g or 50mg KOH/g.
In the present invention, the dosage of the epoxide can be 5 parts, 7 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20
Part, 23 parts, 25 parts, 28 parts, 30 parts, 33 parts or 35 parts；When the dosage of the epoxide is very little, cause by the resin
The crosslink density for the cover film that composition is formed is lower；When the dosage of the epoxide is too many, cause by the resin
The flexibility for the cover film that composition is formed is poor.
Preferably, the epoxide equivalent of the epoxy resin is in 100~500 grams/equivalent, for example, 100 grams/equivalent, 120 grams/
Equivalent, 150 grams/equivalent, 180 grams/equivalent, 200 grams/equivalent, 230 grams/equivalent, 250 grams/equivalent, 280 grams/equivalent, 300 grams/
Equivalent, 330 grams/equivalent, 350 grams/equivalent, 380 grams/equivalent, 400 grams/equivalent, 420 grams/equivalent, 450 grams/equivalent, 480 grams/
Equivalent or 500 grams/equivalent.When the epoxide equivalent of the epoxide used in the present invention is lower than 100 grams/equivalent, shape
At crosslink density it is excessively high, the flexibility of cover film is poor；When the epoxide equivalent of the epoxide used in the present invention is high
When 500 grams/equivalent, reactivity is poor, and the adhesive gel time is long.
Preferably, the number-average molecular weight of the epoxy resin be less than or equal to 8000, such as 8000,7800,7500,7000,
6500,6000,5500,5000,4500,4000,3000,2400,2000,1000 etc..In the present invention, if epoxide
Molecular weight is higher than 8000, then the glass transition temperature of the epoxide is excessively high.Preferably, the number of the epoxide
Average molecular weight is less than or equal to 6000.It is further preferred that the number-average molecular weight of the epoxide is 400~6000.
Preferably, the epoxide be selected from phenol type novalac epoxy, o-cresol type novalac epoxy,
Bisphenol A type epoxy compound, bisphenol F type epoxy compound, dicyclopentadiene type epoxy compound, biphenyl type epoxy compound,
In naphthalene type ring oxygen compound, phosphorous epoxide or nitrogenous epoxide any one or at least two combination.?
In the present invention, the solidification crosslink density of resin combination is can be improved in the epoxide, and then improves by the resin group
Close the heat resistance for the cover film that object is formed.
Preferably, the epoxide is the bisphenol A-type novalac epoxy that number-average molecular weight is less than or equal to 6000.
In the present invention, the dosage of the blocked isocyanate can for 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts,
8 parts, 9 parts or 10 parts；Dosage is very few, and the crosslink density of formation is lower；Dosage is excessive, and the heat resistance that will lead to solidfied material is deteriorated.
Preferably, the blocked isocyanate is blocked diisocyanates and/or blocked polyisocyanate.It is preferred that
Ground, the sealer that the blocked isocyanate uses can be but not limited to the change of the types such as phenol, ketoxime, imidazoles, amide
Close object.Preferably, the blocked diisocyanates include but is not limited to enclosed type toluene di-isocyanate(TDI), enclosed type diphenyl
Methane diisocyanate, enclosed type 1,5- naphthalene diisocyanate, enclosed type hexamethylene diisocyanate or the different Fo Er of enclosed type
In ketone diisocyanate any one or at least two combination.Preferably, the blocked polyisocyanate includes but not
It is limited to enclosed type triphenylmethane triisocyanate, enclosed type trimerization toluene di-isocyanate(TDI), enclosed type thiophosphoric acid triphenyl
In triisocyanate any one or at least two combination.Blocked isocyanate room temperature does not have reactivity, through high temperature solution
The curing reaction of the polyurethane containing carboxyl and the epoxide containing hydroxyl and epoxy group, formationization can be participated in after closing
Learn the stable solidfied material of property.Non-close type isocyanates then in room temperature and can contain hydroxyl, carboxyl, amido, epoxy group etc.
The compound of active function groups reacts, and can react with the moisture in air, poor storage stability, resin combination
Performance is unstable.
In the present invention, the dosage of the nitrogen-containing heterocycle compound can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3
Part, 3.5 parts, 4 parts, 4.5 parts or 5 parts；Dosage is excessive, curing reaction rate can be made too fast, process window shortens.
Preferably, the pKa value of the nitrogen-containing heterocycle compound be 0~9.9, such as 0,0.5,0.8,1,1.3,1.5,1.8,
2,2.3,2.5,2.8,3,3.5,4,4.5,5,5.5,6.2,6.8,7.1,7.5,8.4,8.8,9,9.9 etc., preferably 0~8.5.
PKa value is too low, and nitrogen-containing heterocycle embodies stronger acidity, it is difficult to play the role of promoting cross-linking reaction and improve chemical resistance；
PKa value is too high, too strong to the reaction facilitation of epoxide, the poor storage stability of resin combination.
Preferably, the nitrogen-containing heterocycle compound is nitrogen azole compounds, thiazole compound or quinoxaline compound
In any one or at least two combination.Preferably, the nitrogen azole compounds include but is not limited to benzotriazole, first
In base benzotriazole, carboxy benzotriazole or hydroxy benzo triazole any one or at least two combination；It is preferred that
Ground, the thiazole compound include but is not limited to 2-mercaptobenzothiazole and/or 2-thioxo-4-thiazolidinone.Preferably, institute
Stating quinoxaline compound includes but is not limited to 2- quinoxaline carboxylic acid, 2,3- diphenylquinoxaline, 3- phenyl 2- (2- hydroxy benzenes)
In quinoxaline or 2- mercaptoquinoxaline any one or at least two combination.
In the present invention, the effects of nitrogenous compound can be by adsorbing, being complexed is attached to metal surface, is formed to metal
Protective effect has excellent corrosion inhibition especially to copper.So with the cured resin combination of such curing agent to it
The metal surface of contact has significant protective effect, embodies excellent chemical resistance, especially acid resistance.
Preferably, the halogen-free resin composition further includes the antioxidant of 0.1~2 parts by weight, such as the antioxidant
Dosage can be 0.1 part, 0.5 part, 0.8 part, 1 part, 1.3 parts, 1.5 parts, 1.8 parts or 2 parts.
Preferably, the antioxidant includes but is not limited to 2,6- di-tert-butyl-4-methy phenol (BHT, abbreviation antioxidant
264), four (4- hydroxyl -3,5- tert-butyl-phenyl propionic acid) pentaerythritol esters (abbreviation antioxidant 1010), the tertiary butyl- 4- hydroxyl of 3,5- bis-
Base benzenpropanoic acid octadecyl ester (abbreviation antioxidant 1076), bis- (2,2,6,6- tetramethyl -4- piperidines) sebacates (Tinuvin770),
In triphenyl phosphite (TTP), phosphorous acid three (nonyl phenyl ester) (TNP) or phenthazine any one or at least two group
It closes.In the present invention, the antioxidant can restrain or delay curing agent and its cured resin combination manufacture, processing and
Oxidative degradation in use process.
Preferably, the halogen-free resin composition further includes the fire retardant of 10~40 parts by weight, such as the fire retardant
Dosage can be 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts or 40 parts.
Preferably, the fire retardant is phosphonium flame retardant.In the present invention, fire retardant is added in halogen-free resin composition
The resin combination after solidifying can be made to achieve the effect that halogen-free flameproof, when being used to prepare cover film, the additive amount of fire retardant
Other than influencing flame retarding efficiency, also have an impact to glue overflow amount, peel strength, Storage period.Contain to what can be used in the present invention
The specific type of phosphorus fire retardant is not particularly limited, as long as it can provide flame retardant effect and not influence the Halogen resin group
It closes the effect in object between each component and does not influence the engineering properties of the cover film formed by the halogen-free resin composition
?.
Crosslink density for the halogen-free resin composition further increased, the halogen-free resin composition can be with
Preferably include in curing accelerator or amine curing agent any one or at least two combination.
Preferably, the curing accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 11
In alkyl imidazole or cyanoimidazole any one or at least two combination.
Preferably, the amine curing agent is selected from dicyandiamide, 4,4'- diaminodiphenylsulfone or 4,4'- diaminodiphenyl ether
In any one or at least two combination.
Preferably, content of the curing accelerator in halogen-free resin composition is 0~2 parts by weight, such as 0.3 weight
Part, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight or 2 parts by weight.
Preferably, content of the amine curing agent in halogen-free resin composition is 0~2 parts by weight, such as 0.3 weight
Part, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight or 2 parts by weight.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is by Halogen resin group as described above
Conjunction object, which is dissolved or dispersed in solvent, to be obtained.
In the present invention, solvent is added in halogen-free resin composition of the invention, to dissolve each component, and adjusts tree
The solid content of oil/fat composition, to adjust the viscosity of prepared resin adhesive liquid.Tool to the solvent that can be used in the present invention
Body type is not particularly limited, as long as it can dissolve or disperse each component and do not influence effect of the invention.It is excellent
Selection of land, the solvent are selected from acetone, butanone, cyclohexanone, toluene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate
Any one in dimethylformamide or at least two combination.
Preferably, the solid content of the resin adhesive liquid be 30%~50%, such as 30%, 33%, 35%, 38%, 40%,
43%, 45%, 48% or 50%.
On the other hand, the present invention provides a kind of cover film, the cover film includes polyimide layer, the polyimides
The release paper on adhesive layer and the adhesive layer on layer, the adhesive layer is by halogen-free resin composition shape as described above
At.
Preferably, the polyimide layer with a thickness of 5~100 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μ
M, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm etc..
Preferably, the adhesive layer with a thickness of 5~50 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μ
M, 40 μm, 45 μm, 50 μm etc..
Preferably, the release paper with a thickness of 50~200 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm,
35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm or
200μm。
The production method of cover film of the present invention includes the following steps: to dissolve the halogen-free resin composition or divide
It dissipates and obtains resin adhesive liquid in a solvent, resin adhesive liquid is coated on the surface of the Kapton, then by the coating
There is the polyimides of resin combination to be placed on 120~160 DEG C of (such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145
DEG C, 150 DEG C, 155 DEG C or 160 DEG C) high-temperature test chamber toasts 2~6 minutes (such as 2 minutes, 3 minutes, 4 minutes, 5 minutes or 6 points
Clock) semi-solid preparation is carried out, then release paper is laminating on the adhesive layer of semi-solid preparation.
On the other hand, the present invention provides a kind of copper-clad plate, the copper-clad plate includes polyimide layer, the polyimides
Adhesive layer on layer and laminating in the copper foil on the adhesive layer, the adhesive layer is by halogen-free resin composition as described above
It is formed.
Preferably, the copper-clad plate is three-layer process single sided board or dual platen, i.e. single sided board or dual platen containing adhesive,
Three-layer process single sided board be polyimide layer, gluing oxidant layer and copper foil it is successively compound, three-layer process dual platen be copper foil, gluing oxidant layer,
Polyimide layer, gluing oxidant layer and copper foil are successively compound.
In the present invention, by taking single sided board as an example, the copper-clad plate includes Kapton and by the Halogen resin group
It closes object and is formed in the adhesive layer of the Kapton side and laminating in the copper foil on the adhesive layer.
Preferably, the adhesive layer with a thickness of 5~45 μm, such as 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μ
M, 25 μm, 28 μm, 30 μm, 33 μm, 35 μm, 38 μm, 40 μm or 45 μm.
Preferably, the Kapton with a thickness of 10~100 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm,
30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
Preferably, the copper foil is electrolytic copper foil or rolled copper foil, the copper foil with a thickness of 6~70 μm, such as 6 μ
m、8μm、10μm、14μm、18μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm、55μm、60μm、65μm、70μm
Deng.
In the present invention, the three-layer process single-side coated copper plate the production method is as follows: by the resin composition in
In the wherein one side of the Kapton, which is placed in 120~160 DEG C
(such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C or 160 DEG C) high-temperature test chamber baking 2~
6 minutes (such as 2 minutes, 3 minutes, 4 minutes, 5 minutes or 6 minutes) progress semi-solid preparations, then by the laminating glue in semi-solid preparation of copper foil
Adhesion coating solidifies after carrying out this semi-solid preparation state composition by design program, obtains the single-side coated copper plate.
On the other hand, the present invention provides a kind of printed circuit board, the printed circuit board includes covering as described above
Film or copper-clad plate.
Compared with the existing technology, the invention has the following advantages:
The present invention using carboxylic polyurethane resin as matrix resin, cooperation epoxide, blocked isocyanate,
Nitrogen-containing heterocycle compound is capable of forming co-crosslinking network structure, and crosslink density is high, and the semi-solid preparation state storage for improving composition is steady
It is qualitative, while there is excellent flexibility, heat resistance, chemical-resistance and flame retardant property.The cover film being prepared by it, has
Excellent acid resistance, the resistance to soldering dip temperature of the limit reach 320 DEG C or more, and peel strength reaches 1.1N/mm or more, and normal temperature storage 15 days
Peel strength still is able to guarantee that anti-flammability reaches V-0 grades in 1.0N/mm or more afterwards；The copper-clad plate being prepared by it equally has
There is excellent acid resistance, the resistance to soldering dip temperature of the limit reaches 320 DEG C or more, and peel strength reaches 1.2N/mm or more, normal temperature storage 15
Peel strength still is able to guarantee that anti-flammability reaches V-0 grades in 1.1N/mm or more after it.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1-6:
Assignment system resin combination (amounts of components is in parts by weight) is organized by shown in table 1, and using toluene and butanone as molten
Dilution agent obtains glue, according to the production method production covering membrane sample of following cover film.
Resin adhesive liquid is coated in a thickness of on 12.5 μm of Kapton using coating machine, is controlled gluing (dry glue)
With a thickness of 15 μm, then toasted 2 minutes in 140 DEG C of high-temperature test chamber, it is partial cross-linked to be formed on Kapton
Cured adhesive layer, then that release paper and the adhesive layer is laminating, obtained flexible printed-circuit board cover film.
Embodiment 7-12:
By group assignment system resin combination shown in table 1, (i.e. embodiment 7 is identical as the composition composition of embodiment 1, embodiment
8 is same as Example 2, embodiment 9 is same as Example 3, embodiment 10 is same as Example 4, embodiment 11 and 5 phase of embodiment
Together, embodiment 12 is same as Example 6), and diluted using toluene and butanone as solvent, glue is obtained, is covered according to following single side
The production method of copper sheet makes copper-clad plate sample.
By resin composition on 12.5 μm of Kapton, control gluing (dry glue), will with a thickness of 15 μm
The Kapton for being coated with resin combination is placed in 140 DEG C of high-temperature test chambers and toasts 2 minutes progress semi-solid preparations, then by copper
The laminating adhesive layer in semi-solid preparation of foil is crossed for 90~120 DEG C and is moulded, and 180 DEG C/100kg pressure presses 60s fastly, by design program Solidification, is obtained
To the single-side coated copper plate.
Comparative example 1-6:
It is diluted by group assignment system resin combination shown in table 2, and using toluene and butanone as solvent, obtains glue, according to
The production method production covering membrane sample of cover film described in embodiment 1-6.
Comparative example 7-12:
By group assignment system resin combination shown in table 2, (composition of comparative example 7-12 forms the group with comparative example 1-6 respectively
It is identical to close object composition), and diluted using toluene and butanone as solvent, glue is obtained, is covered according to single side described in embodiment 7-12
The production method of copper sheet makes copper-clad plate sample.
The resin combination component of 1 embodiment 1-14 of table
The resin combination component of 2 comparative example 1-4 of table
Embodiment 1-12 and comparative example the 1-12 cover film being prepared and single-side coated copper plate are tested for the property, surveyed
Method for testing is as follows:
(1) cover film acid resistance
Measurement circuit is chosen, the figure comprising 100mm ± 10mm long straight line, semicircle and right angle, route copper thickness is 25 μm, line
Wide and line-spacing is 100 μm.
By the cover film patch of 5cm × 5cm size and in the centre of above-mentioned measurement circuit, existed with the fast press of EWEDO-KY04C
180 DEG C, 100Kgf presses 80s fastly, and 170 DEG C solidify 1 hour.Solidified sample is placed in 5% dilute sulfuric acid and impregnates 5min, after taking out drying
It is placed in the micro- sem observation of 200 multiplying powers, acid solution is judged whether there is along measurement circuit and penetrates into cover film overlay area.If so, being considered as not
It is qualified；If nothing is considered as qualification.
(2) the resistance to soldering dip temperature of the limit
Cover film: the release paper of the cover film obtained in the following examples and comparative examples is removed, and by the covering
The smooth surface of the adhesive layer and the copper foil having a size of 5cm × 5cm of layer is laminating, with the fast press of EWEDO-KY04C in 180 DEG C, 100kgf
Fast pressure is placed in 170 DEG C of common Homothermal Proof Box and solidifies 1 hour copper foil for obtaining being pasted with cover film after 1 minute.It prepares multiple
Sample is impregnated into 20s in the tin liquor of 280+10n DEG C (n=1,2,3,4,5,6,7 and 8) respectively, take out, seen whether layering,
Melting or foaming phenomena, the maximum temperature that qualification passes through are the resistance to soldering dip temperature of the limit.
Copper-clad plate: the copper-clad plate obtained in the following examples and comparative examples is cut into 5cm × 5cm after 170 DEG C of solidification 2h
Sample, according to cover film wicking method method test.
(3) peel strength
Cover film: the release paper of each removing for the cover film that following example 1-4 and comparative example 1-5 are obtained, and
And respectively by the adhesive layer of the cover film with having a size of 20cm (length) × smooth surface of the copper foil of 20cm (width) × 18 μm (thickness)
It is laminating, with the fast press of EWEDO-KY04C after 180 DEG C, 100kgf press 1 minute fastly, it is placed in 170 DEG C of common Homothermal Proof Box admittedly
Change 1 hour, solidifies according to the above method, to be pasted with the sample of the cover film corresponding to embodiment 1-4 and comparative example 1-5 respectively
Product.According to IPC-TM-6502.4.9 method, test according to being pasted with respectively of obtaining of above method corresponding to embodiment 1-6 and
The sample of the cover film of comparative example 1-6.
Copper-clad plate: according to IPC-TM-650 2.4.9 method, the cover film of testing example 7-12 and comparative example 7-12
Sample.
(4) anti-flammability
It is tested according to UL94 vertical combustion, cover film will be bonded solid that 18 μm of rolled copper foils of moral and be surveyed after solidifying
Examination.
The performance test results of flexible printed-circuit board cover film are as shown in Table 3 and Table 4.
3 cover film embodiment test result of table
4 cover film comparative example test result of table
Using the cover film of halogen-free resin composition of the present invention preparation with excellent it can be seen from the comparison of table 3 and table 4
Acid resistance, heat resistance, anti-flammability and higher peel strength.Lack epoxide, blocked isocyanate and nitrogen-containing hetero
Any one component in cycle compound, the comprehensive performance of cover film can be all decreased obviously；Nitrogenous heterocyclic pKa value is too
Height, peel strength fall off rate becomes larger during will lead to cover film storage；In addition, the component for the composition that comparative example 5 uses
Type meets the requirement of invention, but the dosage of polyurethane containing carboxyl is very little, the dosage mistake of blocked isocyanate and nitrogenous compound
It is more, it can be found that its heat resistance, peel strength are performed poor.Comparative example 6 using non-close type isocyanates as curing agent,
Obtained covering film heat resistance, acid resistance and storage stability is poor.Therefore, resin combination of the invention, which does not require nothing more than, contains
The collocation of carboxyl polyurethane, epoxide, blocked isocyanate and nitrogen-containing heterocycle compound etc., is also required to meet each component
Proportion, resin combination and cover film with excellent properties could be made.
The performance test results of single-side coated copper plate are as shown in table 5 and table 6.
5 copper-clad plate embodiment test result of table
6 copper-clad plate comparative example test result of table
Using the copper-clad plate of halogen-free resin composition of the present invention preparation with excellent it can be seen from the comparison of table 5 and table 6
Acid resistance, heat resistance, anti-flammability and higher peel strength.Lack epoxide, blocked isocyanate and nitrogen-containing hetero
Any one component in cycle compound, the comprehensive performance of copper-clad plate can be all decreased obviously；Nitrogenous heterocyclic pKa value is too
Height, peel strength fall off rate becomes larger during will lead to cover film storage；Wherein, the resin types that comparative example 11 uses meet
Requirement of the invention, but the dosage of blocked isocyanate and nitrogenous compound is excessive, it can be found that its heat resistance, peel strength
Perform poor.Comparative example 12 using non-close type isocyanates as curing agent, obtained copper-clad plate heat resistance, acid resistance and
Storage stability is poor.Therefore, resin combination of the invention does not require nothing more than polyurethane containing carboxyl, epoxide, closing
The collocation of type isocyanates and nitrogen-containing heterocycle compound etc., is also required to meet the proportion of each component, could be made has superiority
The copper-clad plate of energy.
The Applicant declares that the present invention is explained by the above embodiments halogen-free resin composition of the invention, by its preparation
Cover film and copper-clad plate and printed circuit board, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention
Above-described embodiment, which must be relied on, to be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of halogen-free resin composition, which is characterized in that the halogen-free resin composition comprises the following components in parts by weight:
60~90 parts of polyurethane containing carboxyl, 5~35 parts of epoxide, 1~10 part of blocked isocyanate and nitrogen-containing hetero cyclisation
Close 0.5~5 part of object.
2. halogen-free resin composition according to claim 1, which is characterized in that the polyurethane resin containing carboxyl, which is selected from, to be contained
In carboxyl polyester type polyurethane resin or the resin of polyether polyurethane containing carboxyl any one or at least two combination；
Preferably, the number-average molecular weight of the polyurethane resin containing carboxyl is 10000~50000；
Preferably, the glass transition temperature of the polyurethane resin containing carboxyl is -10 DEG C~120 DEG C；
Preferably, the acid value of the polyurethane resin containing carboxyl is 20mg KOH/g~50mg KOH/g.
3. halogen-free resin composition according to claim 1 or 2, which is characterized in that the epoxide equivalent of the epoxy resin
In 100~500 grams/equivalent；
Preferably, the number-average molecular weight of the epoxy resin is less than or equal to 8000, is preferably smaller than equal to 6000, further preferably
400~6000；
Preferably, the epoxide is selected from phenol type novalac epoxy, o-cresol type novalac epoxy, bis-phenol
A type ring oxygen compound, bisphenol F type epoxy compound, dicyclopentadiene type epoxy compound, biphenyl type epoxy compound, naphthalene type
In epoxide, phosphorous epoxide or nitrogenous epoxide any one or at least two combination, preferably count
Average molecular weight is less than or equal to 6000 bisphenol A-type novalac epoxy.
4. halogen-free resin composition according to any one of claim 1-3, which is characterized in that the enclosed type isocyanic acid
Ester is blocked diisocyanates and/or blocked polyisocyanate；
Preferably, the sealer that the blocked isocyanate uses is in the compound of phenol, ketoxime, imidazoles or amide type
Any one or at least two combination；
Preferably, the blocked diisocyanates include that enclosed type toluene di-isocyanate(TDI), enclosed type diphenyl methane two are different
Cyanate, two isocyanide of enclosed type 1,5- naphthalene diisocyanate, enclosed type hexamethylene diisocyanate or enclosed type isophorone
In acid esters any one or at least two combination；
Preferably, the blocked polyisocyanate includes enclosed type triphenylmethane triisocyanate, three polymethyl benzene of enclosed type
In diisocyanate, enclosed type thiophosphoric acid triphenyl triisocyanate any one or at least two combination.
5. halogen-free resin composition described in any one of -4 according to claim 1, which is characterized in that the nitrogen-containing heterocycle chemical combination
The pKa value of object is 0~9.9, preferably 0~8.5；
Preferably, the nitrogen-containing heterocycle compound is in nitrogen azole compounds, thiazole compound or quinoxaline compound
Any one or at least two combination；
Preferably, the nitrogen azole compounds include benzotriazole, methyl benzotriazazole, carboxy benzotriazole or hydroxyl
In benzotriazole any one or at least two combination；
Preferably, the thiazole compound includes 2-mercaptobenzothiazole and/or 2-thioxo-4-thiazolidinone；
Preferably, the quinoxaline compound includes 2- quinoxaline carboxylic acid, 2,3- diphenylquinoxaline, 3- phenyl 2- (2- hydroxyl
Base benzene) in quinoxaline or 2- mercaptoquinoxaline any one or at least two combination.
6. halogen-free resin composition according to any one of claims 1-5, which is characterized in that the Halogen resin combination
Object further includes the antioxidant of 0.1~2 parts by weight；
Preferably, the antioxidant includes 2,6- di-tert-butyl-4-methy phenol, four (4- hydroxyl -3,5- tert-butyl-phenyls third
Acid) pentaerythritol ester, the tertiary butyl- 4- hydroxy phenylpropionic acid octadecyl ester of 3,5- bis-, bis- (2,2,6,6- tetramethyl -4- piperidines) decanedioic acid
In ester, triphenyl phosphite, phosphorous acid three (nonyl phenyl ester) or phenthazine any one or at least two combination；
Preferably, the halogen-free resin composition further includes the fire retardant of 10~40 parts by weight；
Preferably, the fire retardant is phosphonium flame retardant；
Preferably, the halogen-free resin composition further includes any one in curing accelerator or amine curing agent or at least two
The combination of kind；
Preferably, the curing accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, undecyl
In imidazoles or cyanoimidazole any one or at least two combination；
Preferably, the amine curing agent is in dicyandiamide, 4,4'- diaminodiphenylsulfone or 4,4'- diaminodiphenyl ether
Any one or at least two combination；
Preferably, content of the curing accelerator in halogen-free resin composition is 0~2 parts by weight；
Preferably, content of the amine curing agent in halogen-free resin composition is 0~2 parts by weight.
7. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by Halogen such as of any of claims 1-6
Resin combination is dissolved or dispersed in solvent and obtains；
Preferably, the solid content of the resin adhesive liquid is 30%~50%.
8. a kind of cover film, which is characterized in that the cover film includes polyimide layer, the adhesive layer on the polyimide layer
And the release paper on the adhesive layer, the adhesive layer is by Halogen resin combination such as of any of claims 1-6
Object is formed；
Preferably, the polyimide layer with a thickness of 5~100 μm；
Preferably, the adhesive layer with a thickness of 5~50 μm；
Preferably, the release paper with a thickness of 50~200 μm.
9. a kind of copper-clad plate, which is characterized in that the copper-clad plate includes polyimide layer, the adhesive layer on the polyimide layer
And it is laminating in the copper foil on the adhesive layer, the adhesive layer is by Halogen resin such as of any of claims 1-6
Composition is formed；
Preferably, the copper-clad plate is three-layer process single sided board or dual platen；
Preferably, the three-layer process single sided board includes Kapton and by nothing such as of any of claims 1-6
Halogen resin combination is formed in the adhesive layer of the Kapton side and laminating in the copper foil on the adhesive layer；
Preferably, the adhesive layer with a thickness of 5~45 μm；
Preferably, the Kapton with a thickness of 10~100 μm；
Preferably, the copper foil be electrolytic copper foil or rolled copper foil, the copper foil with a thickness of 6~70 μm.
10. a kind of printed circuit board, which is characterized in that the printed circuit board includes cover film according to any one of claims 8 or power
Benefit require 9 described in copper-clad plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811031885.6A CN109266284B (en) | 2018-09-05 | 2018-09-05 | Halogen-free resin composition, cover film prepared from same, copper-clad plate and printed circuit board |
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| CN201811031885.6A CN109266284B (en) | 2018-09-05 | 2018-09-05 | Halogen-free resin composition, cover film prepared from same, copper-clad plate and printed circuit board |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110205075A (en) * | 2019-05-14 | 2019-09-06 | 福建省南铝板带复合材料有限公司 | A kind of Metal Substrate covers thermosetting resin adhesive and its application of the compound coiled sheet production of copper |
| CN110505767A (en) * | 2019-07-08 | 2019-11-26 | 苏州固泰新材股份有限公司 | A kind of copper foil base material and preparation method thereof |
| CN111040709A (en) * | 2019-12-28 | 2020-04-21 | 广东生益科技股份有限公司 | Resin composition and flexible copper-clad plate using same |
| CN116200160A (en) * | 2022-11-16 | 2023-06-02 | 深圳市励高表面处理材料有限公司 | Non-microetching organic copper surface bonding agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1182239A2 (en) * | 2000-08-22 | 2002-02-27 | Eastman Kodak Company | Ink Jet Ink composition |
| CN101687980A (en) * | 2007-07-18 | 2010-03-31 | 昭和电工株式会社 | Heat curable resin compositon |
| CN102504675A (en) * | 2011-11-08 | 2012-06-20 | 老虎粉末涂料制造（太仓）有限公司 | Weather-resistant hydrogenated bisphenol A-type epoxy powder coating and preparation method and application thereof |
| WO2016101540A1 (en) * | 2014-12-26 | 2016-06-30 | 广东生益科技股份有限公司 | Halogen-free epoxy resin composition, prepreg and laminate using same |
| CN107674388A (en) * | 2017-09-12 | 2018-02-09 | 广东生益科技股份有限公司 | Halogen-free resin composition and glued membrane prepared therefrom, cover layer and copper-clad plate |
| CN107880530A (en) * | 2017-12-25 | 2018-04-06 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover layer and preparation method thereof |
-
2018
- 2018-09-05 CN CN201811031885.6A patent/CN109266284B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1182239A2 (en) * | 2000-08-22 | 2002-02-27 | Eastman Kodak Company | Ink Jet Ink composition |
| CN101687980A (en) * | 2007-07-18 | 2010-03-31 | 昭和电工株式会社 | Heat curable resin compositon |
| CN102504675A (en) * | 2011-11-08 | 2012-06-20 | 老虎粉末涂料制造（太仓）有限公司 | Weather-resistant hydrogenated bisphenol A-type epoxy powder coating and preparation method and application thereof |
| WO2016101540A1 (en) * | 2014-12-26 | 2016-06-30 | 广东生益科技股份有限公司 | Halogen-free epoxy resin composition, prepreg and laminate using same |
| CN107674388A (en) * | 2017-09-12 | 2018-02-09 | 广东生益科技股份有限公司 | Halogen-free resin composition and glued membrane prepared therefrom, cover layer and copper-clad plate |
| CN107880530A (en) * | 2017-12-25 | 2018-04-06 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover layer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 魏文德: "四(邻甲氧基)苯基卟啉钴(Ⅱ)轴向配位反应的热力学研究", 《南开大学学报（自然科学版）》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110205075A (en) * | 2019-05-14 | 2019-09-06 | 福建省南铝板带复合材料有限公司 | A kind of Metal Substrate covers thermosetting resin adhesive and its application of the compound coiled sheet production of copper |
| CN110205075B (en) * | 2019-05-14 | 2021-05-11 | 福建省南铝板带复合材料有限公司 | Thermosetting resin adhesive for producing metal-based copper-clad composite board coil and application thereof |
| CN110505767A (en) * | 2019-07-08 | 2019-11-26 | 苏州固泰新材股份有限公司 | A kind of copper foil base material and preparation method thereof |
| CN110505767B (en) * | 2019-07-08 | 2021-03-30 | 苏州固泰新材股份有限公司 | Flexible copper foil base material and preparation method thereof |
| CN111040709A (en) * | 2019-12-28 | 2020-04-21 | 广东生益科技股份有限公司 | Resin composition and flexible copper-clad plate using same |
| CN116200160A (en) * | 2022-11-16 | 2023-06-02 | 深圳市励高表面处理材料有限公司 | Non-microetching organic copper surface bonding agent and preparation method thereof |
| CN116200160B (en) * | 2022-11-16 | 2024-04-09 | 深圳市励高表面处理材料有限公司 | Non-microetching organic copper surface bonding agent and preparation method thereof |
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