CN1930219A - Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same - Google Patents
Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same Download PDFInfo
- Publication number
- CN1930219A CN1930219A CN200580006947.2A CN200580006947A CN1930219A CN 1930219 A CN1930219 A CN 1930219A CN 200580006947 A CN200580006947 A CN 200580006947A CN 1930219 A CN1930219 A CN 1930219A
- Authority
- CN
- China
- Prior art keywords
- resin
- imide
- prepreg
- general formula
- carbon number
- 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
- 229910052751 metal Inorganic materials 0.000 title abstract description 6
- 239000002184 metal Substances 0.000 title abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 297
- 239000011347 resin Substances 0.000 claims abstract description 297
- 239000000463 material Substances 0.000 claims abstract description 37
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 229920002312 polyamide-imide Polymers 0.000 claims description 95
- 239000004962 Polyamide-imide Substances 0.000 claims description 79
- -1 siloxane structure Chemical group 0.000 claims description 73
- 239000011120 plywood Substances 0.000 claims description 62
- 230000015572 biosynthetic process Effects 0.000 claims description 46
- 150000003949 imides Chemical group 0.000 claims description 43
- 239000004593 Epoxy Substances 0.000 claims description 35
- 238000012360 testing method Methods 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000008247 solid mixture Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 150000004985 diamines Chemical class 0.000 claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- 239000011574 phosphorus Substances 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 23
- 229920001721 polyimide Polymers 0.000 claims description 23
- 239000009719 polyimide resin Substances 0.000 claims description 21
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 230000026030 halogenation Effects 0.000 claims description 16
- 238000005658 halogenation reaction Methods 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000005822 methylenation reaction Methods 0.000 claims description 4
- DAKZLOJXUDPQIL-UHFFFAOYSA-N 2-butyl-4-ethylphenol Chemical group CCCCC1=CC(CC)=CC=C1O DAKZLOJXUDPQIL-UHFFFAOYSA-N 0.000 claims description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000006208 butylation Effects 0.000 claims description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 3
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 3
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 abstract description 6
- 239000011888 foil Substances 0.000 abstract description 3
- 125000005462 imide group Chemical group 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 47
- 238000003786 synthesis reaction Methods 0.000 description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000011889 copper foil Substances 0.000 description 38
- 239000002966 varnish Substances 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 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 class 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 description 28
- 150000001412 amines Chemical class 0.000 description 27
- 239000003063 flame retardant Substances 0.000 description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 21
- 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 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000008859 change Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 13
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 13
- 230000035939 shock Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 125000003368 amide group Chemical group 0.000 description 12
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 11
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 11
- 150000004984 aromatic diamines Chemical class 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229920002545 silicone oil Polymers 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000011152 fibreglass Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 6
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 3
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 3
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical class C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- AJAZMOFONMJGNP-WMZOPIPTSA-N n-[(2s)-4-methyl-1-oxo-1-[[(2s)-3-oxo-4-(pyridin-2-ylsulfonylamino)butan-2-yl]amino]pentan-2-yl]-1-benzofuran-2-carboxamide Chemical compound O=C([C@H](C)NC(=O)[C@@H](NC(=O)C=1OC2=CC=CC=C2C=1)CC(C)C)CNS(=O)(=O)C1=CC=CC=N1 AJAZMOFONMJGNP-WMZOPIPTSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- LNUNQPLCXRMOJK-UHFFFAOYSA-N 2,4-dibutyl-5-methylphenol Chemical compound CCCCC1=CC(CCCC)=C(O)C=C1C LNUNQPLCXRMOJK-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- UYSMAOBANNZEAT-UHFFFAOYSA-N 3-(2,4-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O UYSMAOBANNZEAT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- BHMDNHIWCXQHCM-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCCCC1 BHMDNHIWCXQHCM-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229950001336 bromamide Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical group C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- HDLRSIQOZFLEPK-UHFFFAOYSA-N naphthalene-1,2,5,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(=O)O)=CC=C21 HDLRSIQOZFLEPK-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
This invention provides a prepreg which can yield printed circuit boards with excellent dimensional stability and heat resistance and the ability to be bent and housed at high density in electronic device packages, by impregnating a thin fiber base material with a resin having excellent adhesion with metal foils or fiber base materials, excellent heat resistance and high pliability, as well as a metal foil-clad laminate and printed circuit board employing it. The prepreg of the invention is obtained by impregnating a resin composition containing a resin with an imide structure and a thermosetting resin into a fiber base material with a thickness of 5-50 [mu]m.
Description
Technical field
The present invention is relevant for prepreg and the subsides tinsel plywood and the printed circuit board (PCB) that use it.
Background technology
The printing distributing board plywood be with the resin combination of electrical insulating property as the stacked given number of the prepreg of matrix, heating and pressurizing makes its integrated forming.Use the genus plywood of gilding when forming printed wiring by elimination method (subtractivemethod).This gilds, and to belong to plywood be the tinsel that overlapping Copper Foil etc. is gone up on surface (single face or two sides) at prepreg, makes by pressurized, heated again.General using always is used as the electrical insulating property resin as thermosetting resins such as resol, Resins, epoxy, polyimide resin, bismaleimides-cyanate resins.In addition, also can use as thermoplastic resins such as fluorine resin or poly (phenylene ether) resins.
On the other hand, be accompanied by popularizing of intelligent terminal machines such as Personal Computer and portable phone, the printed circuit board (PCB) that is equipped on these machines changes miniaturization, densification gradually into.Its encapsulation form develops into the surface encapsulation type by the bolt insert type, and then develops into the area array type headed by the BGA (BGA Package) that uses plastic base.With regard to the substrate of direct installation such as BGA bare chip, chip generally is to be undertaken by the terminal conjunction method that utilizes hot ultrasonic wave crimping with being connected of substrate.At this moment, will be exposed under the high temperature more than the 150C, because of the substrate that bare chip is installed so the electrical insulating property resin need have thermotolerance to a certain degree.
From the viewpoint of environment protection, the unleaded research of scolding tin is paid attention to by the people gradually and is carried out energetically, thus the melt temperature of scolding tin high temperatureization little by little.For this reason, higher thermotolerance will be required aspect substrate.In addition, the requirement of the halogenization of material improves year by year, so the use of brominated flame retardant also becomes difficult gradually.
More the person for printed circuit board (PCB), also requires so-called reparation (Repair characteristics) of detachably chip being installed sometimes.At this moment, the heat of equal extent when substrate is subjected to Chip Packaging when repairing implements to be used for carrying out once more the thermal treatment that chip is installed thereafter.If impose such processing, with regard to employed electrical insulating property resin system in the past, may produce at fiber base material and interlaminar resin and to peel off.Therefore, with regard to the substrate that reparation property is required, recycle required resistance to sudden heating under the high temperature and also be required.
Have the superior heat resistance impact in order to improve, the formation of the fine distribution of anti-backflow, crack resistance, proposed in fiber base material, to soak contain with the polyamidoimide be must composition the prepreg (opening the 2003-55486 communique) that forms of resin combination with reference to the spy.
In addition, be accompanied by miniaturization, the high performance of e-machine, need in restriceted envelope, take in the printed circuit board (PCB) of having implemented component packages.To this, adopt with a plurality of printed circuit board (PCB)s be distributed into multistage after, come interconnective method by wirning harness or elasticity wiring board again.In addition, also use with polyimide and be the elastic base plate of main component and the formed rigidity-flexible substrate of rigid substrates multiple stratification in the past.
Summary of the invention
In view of above-mentioned existing in prior technology problem, the object of the present invention is to provide by will and tinsel or fiber base material between cementability flexible high resin good, excellent heat resistance contain and be dipped in the thin fiber base material, can obtain dimensional stability and excellent heat resistance, flexible and the subsides tinsel plywood and the printed circuit board (PCB) that can be contained in the prepreg of the intravital printed circuit board (PCB) of e-machine basket and use this prepreg with high-density.
To achieve these goals, the feature of prepreg of the present invention is, the resin combination that will contain resin with imide structure and thermosetting resin soaks to be contained in the fiber base material that thickness is 5～50 μ m and forms.
With regard to this prepreg, if the resin with imide structure is that to have a resin of siloxane structure then better.
Again, the resin with imide structure also can be the resin with following general formula (1) structure.
[changing 1]
And then, if it is then better to have a resin polyamide-imide resin of imide structure.
More particularly, if have that the resin of imide structure contains that the mixture of following imide dicarboxylic acid and diisocyanate cpd react polyamide-imide resin, then preferable, described what contain the imide dicarboxylic acid is to make to contain siloxane diamine and following general formula (2a) or (2b) mixture of represented diamines and trimellitic acid 1,2-anhydride react and get.
[changing 2]
[formula (2a) or (2b) in, X
21The represented divalent base or the represented divalent base of following general formula (3b) of aliphatic alkyl, the halogenation aliphatic alkyl of carbon number 1～3, alkylsulfonyl, ether, carbonyl, singly-bound, following general formula (3a) of expression carbon number 1～3, X
22Aliphatic alkyl, halogenation aliphatic alkyl, alkylsulfonyl, ether or the carbonyl of carbon number 1～3, the R of expression carbon number 1～3
21, R
22And R
23Independent separately or identical, expression hydrogen atom, hydroxyl, methoxyl group, methyl or halogenation methyl.
[changing 3]
Wherein, in the formula (3a), X
31The aliphatic alkyl of expression carbon number 1～3, halogenation aliphatic alkyl, alkylsulfonyl, ether, carbonyl or the singly-bound of carbon number 1～3).
In addition, resin with imide structure also can be, contain the mixture of following imide dicarboxylic acid and the polyamide-imide resin that diisocyanate cpd reacts gained, described imide dicarboxylic acid is to make to contain the represented diamines of following general formula (4), siloxane diamine and following general formula (5a) or (5b) mixture of represented diamines, react with trimellitic acid 1,2-anhydride and.
[changing 4]
[changing 5]
(formula (5a) or (5b) in, X
51The represented divalent base or the represented divalent base of following general formula (6b) of aliphatic alkyl, the halogenation aliphatic alkyl of carbon number 1～3, alkylsulfonyl, ether, carbonyl, singly-bound, following general formula (6a) of expression carbon number 1～3, X
52Aliphatic alkyl, halogenation aliphatic alkyl, alkylsulfonyl, ether or the carbonyl of carbon number 1～3, the R of expression carbon number 1～3
51, R
52And R
53Independent separately or identical, expression hydrogen atom, hydroxyl, methoxyl group, methyl or halogenation methyl.
[changing 6]
But, in the formula (6a), X
61The aliphatic alkyl of expression carbon number 1～3, halogenation aliphatic alkyl, alkylsulfonyl, ether, carbonyl or the singly-bound of carbon number 1～3).
Again, the resin with above-mentioned imide structure also can be, and has the polyimide resin of the represented structure of following general formula (7) or has the represented structure of following general formula (7) and the polyimide resin of the structure that following general formula (8) is represented.
[changing 7]
[changing 8]
(in formula (7) or (8), Ar
1Represent 4 valency aromatic series bases, Ar
2Expression divalent aromatic series base, R
71And R
72Independent separately or identical, expression divalent alkyl; R
73, R
74, R
75And R
76Independent separately or identical, the alkyl of expression carbon number 1～6; N represents 1～50 integer).
In addition, the resin with imide structure also can be, and has the polyamide-imide resin of the represented structure of following general formula (9).Such polyamide-imide resin will become the resin that contains the represented structure of above-mentioned general formula (1) in molecule.
[changing 9]
(in the formula (9), R
91, R
92, R
93And R
94The ring texture of the polyamide-imide resin of expression formation respectively or a part of carbon atom of chain-like structure).
In prepreg of the present invention, the thermosetting resin preferred epoxy that resin combination is contained.Wherein, then better if having the Resins, epoxy of the epoxypropyl more than 2.
In addition, above-mentioned resin combination preferably further contains the resin combination of P contained compound, in such resin combination, for the resin that 100 weight parts have imide structure, better as if the phosphorus that contains 0.1～5 weight % in thermosetting resin that contains 1～140 weight part and the resin solid composition.
Again, resin combination is if further contain hindered phenol system (Hindered Phenols) or sulphur organic compound system antioxidant, and is then better.
As such antioxidant, be preferably and be selected from by butylation hydroxyl methoxy benzene, 2,6-two-tertiary butyl-4-ethylphenol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, four-(methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl propionic ester) methane, Tyox B, in the distearyl thiodipropionate form a group at least a kind.
In addition, prepreg of the present invention has been when having solidify to form base material, in the VTM of its UL-94 test below the preferred 100mm of burning extent.
In addition, the invention provides the subsides tinsel plywood that uses the invention described above prepreg gained.Also promptly, subsides tinsel plywood of the present invention is with the overlapping given number of the invention described above prepreg, and disposes tinsel at it on the one-sided or both sides, carries out heating and pressurizing and gets.
In addition, the invention provides the printed circuit board (PCB) of the subsides tinsel plywood gained that uses the invention described above.Also promptly, printed circuit board (PCB) of the present invention is that the described tinsel in the subsides tinsel plywood of the invention described above is carried out circuit fabrication and got.
By the subsides tinsel plywood and the printed circuit board (PCB) of prepreg gained of the present invention, can be at random crooked, have good dimensional stability, thermotolerance and anti-PCT.In addition, because of flexible when making printed circuit board (PCB), so can be contained in the basket of e-machine with high-density.
Description of drawings
Fig. 1 is the part stereographic map of an example of expression prepreg.
Fig. 2 is the partial cross section figure that an example of tinsel plywood is pasted in expression.
Fig. 3 is the partial cross section view of an example of expression printed circuit board (PCB).
Among the figure:
3: the reinforcing fiber resin layer
10: tinsel
30: substrate
60: metal plating
70: communicating pores
100: prepreg
200: paste the tinsel plywood
300: printed circuit board (PCB)
Embodiment
Below, as required on one side with reference to accompanying drawing, on one side best mode for carrying out the invention is described in detail.
(prepreg)
At first, prepreg is illustrated.The prepreg of this example is that the resin combination that will contain resin with imide structure and thermosetting resin soaks to be contained in the fiber base material that thickness is 5～50 μ m and forms.Below, at first each contained in resin combination composition is illustrated.
(resin) with imide structure
Resin with imide structure is meant the compound that has an imide structure at intramolecularly at least, for example preferred polyamide imide resin, polyimide resin or the maleic anhydride imide resin that contracts.
At first, polyamide-imide resin is illustrated.Polyamide-imide resin is meant the resin that contains imide and amide group repeating unit.As such polyamide-imide resin, be the most suitable with the silicone-modified polyamide-imide resin that in repeating unit, has siloxane structure.
As polyamide-imide resin with such siloxane structure, preferably make the mixture that contains following imide dicarboxylic acid, react the resin of gained with aromatic diisocyanate compounds, described imide dicarboxylic acid, be make contain siloxane diamine and above-mentioned general formula (2a) or (2b) the represented diamines with 2 above aromatic rings (aromatic diamine) mixture, react with trimellitic acid 1,2-anhydride and get.
With regard to silicone-modified polyamide-imide resin with siloxane structure synthetic, have the diamines a of 2 above aromatic rings and the mixture ratio of siloxane diamine b, be preferable with a/b=99.9/0.1～0/100 (mol ratio), a/b=95/5～30/70 is better, a/b=90/10～40/60 the best.If the mixture ratio of siloxane diamine b is too high, Tg will be reduced.If low excessively, then when making prepreg, remain in soaking in the resin to contain the solvent quantitative change many making.
As aromatic diamine, for example can enumerate 2, two (4-(4-amino-benzene oxygen) phenyl) propane (BAPP) of 2-, two (4-(3-amino-benzene oxygen) phenyl) sulfone, two (4-(4-amino-benzene oxygen) phenyl) sulfone, 2, two (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of 2-, two (4-(4-amino-benzene oxygen) phenyl) methane, 4, two (4-amino-benzene oxygen) biphenyl of 4-, two (4-(4-amino-benzene oxygen) phenyl) ether, two (4-(4-amino-benzene oxygen) phenyl) ketone, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 2,2 '-dimethyl diphenyl-4,4 '-diamines, 2,2 '-two (trifluoromethyl) biphenyl-4,4 '-diamines, 2,6,2 ', 6 '-tetramethyl--4,4 '-diamines, 5,5 '-dimethyl-2,2 '-sulphonyl-biphenyl-4,4 '-diamines, 3,3 '-dihydroxybiphenyl-4,4 '-diamines, (4,4 '-diamino) diphenyl ether, (4,4 '-diamino) sulfobenzide, (4,4 '-diamino) benzophenone, (3,3 '-diamino) benzophenone, (4,4 '-diamino) ditan, (4,4 '-diamino) diphenyl ether, (3,3 '-diamino) diphenyl ether etc.
As siloxane diamine, can enumerate the compound shown in the following note general formula (10a)～(10b) again.
[changing 10]
As the siloxane diamine shown in the last note general formula (10a), can enumerate as X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500) (more than, Shin-Etsu Chemial Co., Ltd system trade(brand)name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) (above ， East レ ダ ウ ユ one or two Application グ シ リ ユ one Application Co., Ltd. system trade(brand)name) etc.As the siloxane diamine shown in the last note general formula (10d), can enumerate as X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (more than, Shin-Etsu Chemial Co., Ltd system trade(brand)name) etc.
As making the employed diisocyanate cpd of polyamide-imide resin, can enumerate the compound shown in the following note general formula (11).
[changing 11]
OCN-D-NCO …(11)
In the formula (11), D is meant the organic radical with at least 1 aromatic nucleus or the aliphatic alkyl of divalent, wherein preferably from by-C
6H
4-CH
2-C
6H
4-shown in base, tolylene, naphthylidene, hexa-methylene, 2,2, at least a kind of group selecting in one group that 4-tri-methyl hexamethylene and isophorone base are formed.
As the diisocyanate cpd shown in the last note general formula (11), though can use aliphatic diisocyanate or aromatic diisocyanate, to use the aromatic series diisocyanate preferable, best is that both also use.
As aromatic diisocyanate, for example can enumerate 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthylene-1,2,4-tolylene dipolymers etc. are wherein to use MDI the best.By using MDI, can improve the bendability of the polyamide-imide resin of gained as aromatic diisocyanate.
As aliphatic diisocyanate, can enumerate for example hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, isophorone group diisocyanate etc.
Also using under the situation of aromatic diisocyanate and aliphatic diisocyanate, with respect to aromatic diisocyanate, the aliphatic diisocyanate that adds about 5～10 moles of % is preferable.By and usefulness, can further improve the thermotolerance of the polyamide-imide resin of gained.
As the polyamide-imide resin that is contained in the resin combination, it is also preferable to have a polyamide-imide resin that contains the structure of aliphatics ring shown in note general formula (1).Wherein, especially with have above-mentioned shown in siloxane structure and both polyamide-imide resin the bests of fatty family ring structure.Such polyamide-imide resin forms the resin that contains structure shown in the note general formula (9).
Have siloxane structure and fatty family both polyamide-imide resins of ring structure as such, preferably contain the mixture of following imide dicarboxylic acid and the polyamide-imide resin that diisocyanate cpd reacts gained, described imide dicarboxylic acid is to make the alicyclic diamine, siloxane diamine and the above-mentioned general formula (5a) that comprise the represented fatty family ring of above-mentioned general formula (4) or (5b) mixture of the represented diamines with 2 above aromatic rings (aromatic diamine), react with trimellitic acid 1,2-anhydride and.
Alicyclic diamine shown in the above-mentioned general formula (4) is meant 4, and 4 '-diamino-dicyclohexyl methane, and compound that easily obtain relevant with it have for example ワ Application ダ ミ Application (New Japan Chem Co., Ltd's system trade(brand)name).As above-mentioned reaction used siloxane diamine and aromatic diamine, can enumerate compound same as described above again.With regard to having such siloxane structure and fatty family both polyamide-imide resins of ring structure synthetic, diamines a (mole) shown in the above-mentioned general formula (4), blending ratio with the total b (mole) of diamines with 2 above aromatic rings and siloxane diamine, be preferable with a/b=0.1/99.9～99.9/0.1 (mol ratio), a/b=10/90～50/50 is better, a/b=20/80～40/60 the best.
In the manufacturing that contains the polyamide-imide resin of structure shown in above-mentioned siloxane structure and/or the general formula (1), except that adding siloxane diamine, aromatic diamine, alicyclic diamine etc., also can use the aliphatie diamine class.As such aliphatie diamine, can enumerate compound shown in the following note general formula (12).
[changing 12]
In the formula (12), X
121Expression methylene radical, alkylsulfonyl, ether, carbonyl or singly-bound, R
121And R
12Represent hydrogen atom, alkyl, phenyl or substituted-phenyl respectively, p represents 1～50 integer.
As R
121And R
122Concrete example, be preferable with alkyl, phenyl or the substituted-phenyl of hydrogen atom, carbon number 1～3, as the substituting group that can be incorporated into phenyl, can enumerate alkyl, halogen atom of carbon number 1～3 etc.From satisfying the viewpoint of low elastic modulus and high Tg simultaneously, aliphatie diamine is with X in the above-mentioned general formula (12)
121For the aliphatie diamine of ether is preferable.
As such aliphatie diamine, can enumerate as ジ エ Off ア one ミ Application D-400 (amine equivalent 400), ジ エ Off ア one ミ Application D-2000 (amine equivalent 1000, chemical (Sun-technolchemical) Co., Ltd. of above sun science and technology system trade(brand)name) etc.
As above-mentioned polyamide-imide resin, preferably contain the above polyamide-imide resin that in a molecule, contains the polyamidoimide molecule of 10 above amide group of 70 moles of %.Its scope can be by the color atlas of GPC (gel permeation chromatography) gained of polyamide-imide resin, and the mole number (A) of the amide group in the other unit weight of trying to achieve obtains.For example based on the mole number (A) of amide group contained among polyamide-imide resin (a) g, with 10 * a/A as the molecular weight (C) that contains the polyamidoimide of 10 amide group in the molecule, then the color atlas mean average molecular weight by the GPC gained is that zone more than the C reaches the situation more than 70%, is equivalent to contain the above polyamidoimide molecule that contains 10 above amide group in a molecule of 70 moles of %.The quantivative approach of amide group can be utilized NMR, IR, hydroxamic acid-iron color reaction method, N-bromamide method etc.
Then, polyimide resin is illustrated.Polyimide resin is meant the resin that contains imide structure in the repeating unit.And as polyimide resin, preferably in repeating unit, further has siloxane structure, wherein more preferably have the polyimide resin of structure shown in the above-mentioned general formula (7), or have the structure shown in structure shown in the above-mentioned general formula (7) and the following general formula (8).Such polyimide resin can obtain by diamine compound and tetracarboxylic dianhydride's reaction.
As the diamine compound that is used for obtaining to have the polyimide resin of structure shown in the above-mentioned general formula (7), can enumerate siloxane diamine.As such siloxane diamine, can enumerate the compound identical compound used with making above-mentioned polyamide-imide resin.
In addition, as the diamine compound that is used for obtaining to have simultaneously the polyimide resin of structure shown in structure shown in the above-mentioned general formula (7) and the above-mentioned general formula (8), can enumerate the composition of siloxane diamine and aromatic diamine.As siloxane diamine, can enumerate the compound identical compound used with making above-mentioned polyamide-imide resin.In addition, as aromatic diamine, can enumerate as-phenylenediamine, right-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, p-diaminodiphenyl, 4,4 '-diamino-diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino-right-terphenyl, 2, two (4-(4-amino-benzene oxygen) phenyl) propane (BAPP) of 2-, two (4-(3-amino-benzene oxygen) phenyl) sulfone, two (4-(4-amino-benzene oxygen) phenyl) sulfone, 2, two (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of 2-, two (4-(4-amino-benzene oxygen) phenyl) methane, 4, two (4-amino-benzene oxygen) biphenyl of 4-, two (4-(4-amino-benzene oxygen) phenyl) ether, two (4-(4-amino-benzene oxygen) phenyl) ketone, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 2,2 '-dimethyl diphenyl-4,4 '-diamines, 2,2 '-two (trifluoromethyl) biphenyl-4,4 '-diamines, 2,6,2 ', 6 '-tetramethyl--4,4 '-diamines, 5,5 ' dimethyl-2,2 '-sulphonyl-biphenyl-4,4 '-diamines, 3,3 '-dihydroxybiphenyl-4,4 '-diamines, (4,4 '-diamino) diphenyl ether, (4,4 '-diamino) sulfobenzide, (4,4 '-diamino) benzophenone, (3,3 '-diamino) benzophenone, (4,4 '-diamino) ditan, (4,4 '-diamino) diphenyl ether, (3,3 '-diamino) diphenyl ether etc.
Make up in this wise under the situation that siloxane diamine and aromatic diamine use, the blending ratio of aromatic diamine a and siloxane diamine b, be preferable with a/b=99.9/0.1～0/100 (mol ratio), a/b=95/5～30/70 is better, a/b=90/10～50/50 the best.If the blending ratio of siloxane diamine b is too high, Tg will be reduced.If low excessively, then when making prepreg, remain in soaking in the resin to contain the solvent quantitative change many making.
As the tetracarboxylic dianhydride, can enumerate as 3,3 ' again,, 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,4,5,6-naphthalene tetracarboxylic acid dianhydride, 3,4,9, the 10-perylenetetracarboxylic dianhydride, 3,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7, the luxuriant and rich with fragrance tetracarboxylic dianhydride of 8-, 4,4 '-(hexafluoro isopropylidene) O-phthalic acid dianhydride etc.
Secondly, the maleic anhydride imide resin that contracts is illustrated.As the maleic anhydride imide resin that contracts, can enumerate as diamine compound and maleic anhydride are reacted with 1: 2 mol ratio and form span and come acid anhydrides to contract behind the imines, again the resin that mixes with triazines or other thermosetting resin.As diamine compound, can enumerate and above-mentioned same compound.
(thermosetting resin)
As thermosetting resin used among the present invention, can enumerate as Resins, epoxy, polyimide resin, unsaturated polyester resin, urethane resin, span and come contract imide resin, triazine-span of acid anhydrides to come acid anhydrides contract imide resin, resol etc.For example, preferable with respect to the polyamide-imide resin of 100 weight parts under the situation of using polyamide-imide resin as resin with the thermosetting resin that uses 1～200 weight part with imide structure, use 1～140 weight part better.
As thermosetting resin, preferably has the resin of the organic group that can react with the amide group of polyamide-imide resin.Particularly as polyamide-imide resin, as mentioned above, preferred silicone-modified polyamide-imide resin at this moment, as thermosetting resin, preferably has the resin of the organic group that can react with the amide group in the silicone-modified polyamide-imide resin.More particularly, the Resins, epoxy that preferably has epoxypropyl.With respect to the polyamide-imide resin of 100 weight parts, the amount of thermosetting resin if be lower than 1 weight part, then will make the solvent resistance deterioration.On the other hand, if surpass 200 weight parts, then because of unreacted thermosetting resin will reduce Tg, or it is insufficient that thermotolerance is become, or reduce that it is flexible, so not good.Therefore, the amount of thermosetting resin, with respect to the polyamide-imide resin of 100 weight parts, preferred 3～100 weight parts, more preferably 10～60 weight parts.
As Resins, epoxy, can enumerate as dihydroxyphenyl propane, varnish with novolac type phenol resin, ortho-cresol varnish with multivalence phenol or 1 such as novolac type phenol resin, the pure and mild epoxy chloropropane of multivalence such as 4-butyleneglycol react and poly-glycidyl ethers, react with the polyprotonic acid of phthalic acid, hexahydro-phthalic acid etc. and epoxy chloropropane and poly-epoxypropyl ester, N-epoxypropyl derivative with compound of amine, acid amides or heterocyclic nitrogenous bases, alicyclic epoxy resin etc.
By using Resins, epoxy as thermosetting resin, prepreg can solidify under the temperature below the 180C.Again, as Resins, epoxy, for by with the reaction of the amide group of silicone-modified polyamide-imide resin, improve heat, machinery, electric characteristic, preferably use the combination that has Resins, epoxy and its solidifying agent of 2 above epoxypropyl, Resins, epoxy and its curing catalyst or have Resins, epoxy and its solidifying agent and the curing catalyst of 2 above epoxypropyl with 2 above epoxypropyl.Epoxypropyl is The more the better, if better more than 3.According to the quantity of epoxypropyl, the use level difference of thermosetting resin, epoxypropyl is many more, even use level also can less.
Curing agent for epoxy resin, curing catalyst so long as with the material of Resins, epoxy reaction or promote that solidified material gets final product, be not limited to them, for example can use amine, imidazoles, multifunctional phenols, anhydrides etc.As amine, can use dicyano diamide, diaminodiphenyl-methane, amidino groups urea etc.As multifunctional phenols, can use the halogenated compound of Resorcinol, Resorcinol, dihydroxyphenyl propane and these materials, and can use conduct and the varnish novolac type phenol resin of the condenses of formaldehyde, solvable novolac type phenol resin etc.As anhydrides, can use Tetra hydro Phthalic anhydride, benzophenone tetracarboxylic dianhydride, nadic acid methyl esters etc.As curing catalyst, can use alkyl substituted imidazole as imidazoles, benzoglyoxaline etc.
About the requirement of these solidifying agent or curing catalyst, under the situation of Ammonia, preferably make the equivalent of activation hydrogen of ammonia and the epoxy equivalent (weight) amount about equally of Resins, epoxy.At curing catalyst is under the situation of imidazoles, is not the equivalence ratio of considering simply with activation hydrogen, with respect to 100 parts by weight of epoxy resin, and preferred 0.001～10 weight part of its content.Under the situation of multifunctional phenols or anhydrides,, must use 0.6～1.2 normal phenol hydroxyl or carboxyl with respect to 1 normal Resins, epoxy.If the amount of these solidifying agent or curing catalyst very little then with residual uncured Resins, epoxy, reduces Tg (glass tansition temperature); If with the solidifying agent and the curing catalyst of remained unreacted, reduce insulativity excessively at most.About the epoxy equivalent (weight) of Resins, epoxy, because of also can reacting therefore preferred this factor of consideration with the amide group of silicone-modified polyamide-imide resin.
(other composition)
In resin combination, have the resin of imide structure and also can contain other composition below the thermosetting resin except above-mentioned.As other such composition, at first can enumerate P contained compound.
P contained compound is the composition that can improve the flame retardant resistance of prepreg, and is particularly, preferable with phosphorus flame retardant (phosphorous filler).As phosphorus flame retardant, can enumerate as OP930 (Network ラ リ ア Application ト corporate system trade(brand)name, phosphorus content 23.5 weight %), HCA-HQ (Sanko Co., Ltd.'s system trade(brand)name, phosphorus content 9.6 weight %), the above Misao Kusano of Tripyrophosphoric acid trimeric cyanamide PMP-100 (phosphorus content 13.8 weight %) PMP-200 (phosphorus content 9.3 weight %) PMP-300 (phosphorus content 9.8 weight %) system trade(brand)name etc.
As the addition of the phosphorus flame retardant of P contained compound, though if how can further improve flame retardant resistance, yet if cross at most or reduce the flexible of base material, or the thermotolerance of reduction when making printed circuit board (PCB).The amount of addible phosphorus flame retardant, though difference is arranged with material of soaking the fiber base material that has contained resin combination or thickness, for example as employed fiber base material in the aftermentioned prepreg, at the fiber base material of used thickness 5～50 μ m (for example, cloth) under the situation, the amount of phosphorus flame retardant preferably is adjusted to, and the plywood that utilizes this prepreg manufacturing can obtain burning extent and be the flame retardant resistance below the 100mm in the VTM of UL-94 test.Such plywood has enough performances aspect flexible, and also has enough performances aspect the thermotolerances such as thermal shock test.
As above-mentioned, resin combination contains under the situation of polyamide-imide resin and thermosetting resin, and amide group or imide in this polyamide-imide resin become nitrogenous source, help flame retardant resistance.At this moment, about being matched with the amount of the P contained compounds such as phosphorus flame retardant in the resin combination, in the resin solid state component gross weight of resin combination, the amount of phosphorus is preferable with 0.1～5 weight %, and 2～4 weight % are better.Therefore, the content of phosphorus flame retardant can consider that the phosphorus content that is contained in wherein decides.
In resin combination, also can contain hindered phenol and be the more than one antioxidant in antioxidant and the sulphur organic compound system antioxidant again.For example, be antioxidant if use hindered phenol, then not only can not reduce other characteristic of boring (drill) processibility etc., also can improve electrical insulation characteristics.
As hindered phenol is antioxidant, butylation hydroxyl methoxy benzene is arranged, 2, single phenol such as 6-two-tertiary butyl-4-ethylphenol system, be 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 4, bis-phenols such as 4 '-butylidene-bis(3-methyl-6-t-butyl phenol) system, and 1,1,3-three (2-methyl-4-hydroxyl-5-butyl phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, four-(polymer phenol such as methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl propionic ester) methane system.As sulphur organic compound system antioxidant, Tyox B, distearyl thiodipropionate etc. are arranged again.Antioxidant is preferably selected a kind at least from above-mentioned antioxidant group, also can merge multiple the use in addition.Again, with respect to the thermosetting resin of 100 weight parts, preferred 0.1～20 weight part of the use level of antioxidant.Particularly, with respect to 100 parts by weight of epoxy resin, the use level of antioxidant is 0.1～20 weight part more preferably.The use level of antioxidant is lower than 0.1 weight part, can't improve insulativity; If surpass 20 weight parts, will reduce insulativity on the contrary.
As mentioned above, the prepreg of this example is the resin combination that contains resin, thermosetting resin and other composition with imide structure to be soaked be contained in the fiber base material that thickness is 5～50 μ m to form.Fig. 1 is the part stereographic map of the example of expression prepreg.Prepreg 100 shown in Figure 1 is with fiber base material and soaks the laminar prepreg that resin combination was constituted that is contained in wherein.
Such prepreg can be by mixing prepreg, dissolve, be scattered in the organic solvent with resin combination, and then the varnish of gained soaked be contained in the fiber base material, drying obtains.As such organic solvent, so long as have the solvability of relative resin combination or dispersed getting final product, there is no restriction especially, can enumerate for example N,N-DIMETHYLACETAMIDE, dimethyl formamide, methyl-sulphoxide, N-N-methyl-2-2-pyrrolidone N-, γ-Ding lactones, tetramethylene sulfone, pimelinketone etc.
Though prepreg is above-mentioned resin combination with resin combination, the resin combination that wherein is preferably as follows, the resin combination that promptly contains resin (silicone-modified polyamide-imide resin, polyamide-imide resin or polyimide resin) that 100 weight parts have imide structure and 1～200 weight part (preferred 1～140 weight part) thermosetting resin with the structure shown in the last note formula (1).Thus, the evaporation rate of varnish solvent accelerates in the resin combination, even under the low temperature below 150 ℃ of the curing reaction that can't promote thermosetting resin, also may make the residual solvent composition below 5 weight %.Again, such resin combination, and have good adherence between fiber base material or Copper Foil.Particularly for silicone-modified polyamide-imide resin, silicone-modified because of the high polyamide-imide resin of thermotolerance is carried out, so can obtain good effect.Thus, reduce because of making the residual solvent composition, thus with the stacked operation of Copper Foil in, prepreg also has good scolding tin thermotolerance except that making the foaming that produces because of solvent evaporates tails off.
More particularly, prepreg can soak by the varnish that makes resin combination and be contained in the fiber base material, and drying is made under 80～180 ℃ scope.As fiber base material, get final product so long as can be used in the base material that make to paste tinsel plywood and multilayer printed circuit board, there is no especially and limit, can enumerate and for example weave cotton cloth or fiber base material such as non-woven fabrics.Material as fiber base material, can enumerate as inorganic fibres such as glass, aluminum oxide, asbestos, boron, silicon oxidation lead glass, silex glass, チ ラ ノ, silicon carbide, silicon nitride, zirconium whites, or the blended ratio of organic fibres such as aromatic poly, polyether-ether-ketone, polyetherimide, polyethersulfone, graphite, Mierocrystalline cellulose etc. and these materials, wherein to use the glass fibre the best of weaving cotton cloth.
Wherein, as the fiber base material that is used in prepreg, be the suitableeest with woven fiber glass with 5～50 μ m thickness.By the woven fiber glass of used thickness 5～50 μ m, can obtain can be arbitrarily crooked printed circuit board (PCB), and follow temperature in the manufacturing process, moisture absorption etc., its dimensional change is reduced.
Though creating conditions of such prepreg etc. be there is no restriction especially, yet preferably is made as the condition of the above degree of employed solvent evaporates 80 weight % in the varnish.Also without particular limitation to manufacture method or drying conditions etc., the temperature in the time of for example can be with drying is made as 80～180 ℃, and the time also can be taken into account the varnish gelation time and adjust.Again, the dipping lacquer amount of fiber base material preferably is set as, with respect to the total amount of varnish solid composition and fiber base material, varnish solid composition is 30～80 weight %.
Described prepreg is a flame retardant resistance below the 100mm making this prepreg preferably have burning extent in the VTM of UL-94 test under solidifying as the situation of base material.Particularly contain under the situation of above-mentioned P contained compound, if it is then better to satisfy such condition at resin combination.
The evaluation of flame retardant resistance can be tested by the VTM of UL-94 and carry out.The material of test usefulness for example can be made by the following method, promptly, etching is removed after the copper that uses on the attached copper plywood in two sides that above-mentioned prepreg is made into, cut length 200mm, width 50mm, again it is twisted in the axle of diameter 12.7mm, and fixing with adhesive tape from the position of an end 125mm, make it become tubular, extract axle thereafter.
Measure as follows then, that is, make this sample vertical, after its upper end is fixed with the spring sealing, 3 seconds of 20mm blue flame that end in contact is produced by the methane gas burner, and measure residual fire time and burning extent.In this measures,, be considered as the sufficient prepregs of thermotolerance such as having fully flexible or thermal shock test if the demonstration burning extent is the following flame retardant resistance of 100mm.
(pasting the tinsel plywood)
By using above-mentioned prepreg, can obtain insulcrete, plywood, subsides tinsel plywood.In other words, for example, can by with above-mentioned prepreg separately or with its many stacked duplexers of making, overlapped metal paper tinsel on its single face or two sides as required, 150～280 ℃, preferably under the scope of 180～250 ℃ of temperature, and 0.5～20MPa, preferably heating and pressurizing is shaped under the scope of 1～8MPa pressure, makes insulcrete, duplexer, subsides tinsel plywood.Can obtain to paste the tinsel plywood when particularly using tinsel.
As tinsel, can use Copper Foil or aluminium foil, can use the tinsel of 5～200 μ m.Again, as tinsel, also can use as the middle layer with nickel, nickel-phosphorus, nickel-tin alloy, nickel-ferro alloy, lead, Lead-tin alloy etc., and on its two sides, be provided with the copper layer of the copper layer of 0.5～15 μ m and 10～300 μ m and 3 layers of structure composite foil forming, and with aluminium and the compound formed 2 layers of structure composite foil of Copper Foil.
Fig. 2 is the partial cross section figure that an example of tinsel plywood is pasted in expression.Subsides tinsel plywood 200 is that the duplexer of the prepreg 100 of heating, the given number that pressurizes (is 3 at this) forms with the Copper Foil 10 that is disposed at its both sides, and it is made of with 2 tinsels 10 of adherence in these substrate 30 two sides the laminar substrate 30 that the duplexer with reinforcing fiber resin layer 3 constitutes.
(printed circuit board (PCB))
More the person can obtain printed circuit board (PCB) by using above-mentioned subsides tinsel plywood.In other words, by carry out form (circuit fabrication) of circuit by the tinsel of pasting the tinsel plywood, can obtain printed circuit board (PCB).Such circuit fabrication can be undertaken by elimination method known methods such as (subtractive).
Fig. 3 is the partial cross section view of an example of expression printed circuit board (PCB).Printed circuit board (PCB) 300 shown in Figure 3 is made of substrate same as described above 30 and 2 tinsels 10 being engaged in substrate 30 two sides, and its some is removed and forms Wiring pattern on tinsel.And, on printed circuit board (PCB) 300, be formed with a plurality of communicating poress 70 that connect these circuit card 300 interareas with the direction of roughly keeping straight on.The metal plating 60 of given thickness is formed on the hole wall of this communicating pores 70.In addition, on printed circuit board (PCB) 300, be packaged with given circuit block (not shown) usually.
Embodiment
Below, though illustrate in greater detail the present invention by embodiment, the present invention is not limited only to these embodiment.
(synthesis example 1A)
Add 3,3 ', 4 of 31.0g (0.10 mole) in the detachable flask of 1L, the m-xylene of the NMP of 4 '-diphenyl ether tetracarboxylic dianhydride, 200g (N-N-methyl-2-2-pyrrolidone N-), 200g stirs down in room temperature (25 ℃).Then, use dropping funnel to splash into the reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd system trade(brand)name, amine equivalent 430) of 34.4g (0.04 mole) as siloxane diamine.In stirring ice-cold this reaction soln down, add the BAPP (2,2-two (4-(4-amino-benzene oxygen) phenyl) propane) of 24.6g (0.06 mole), and under room temperature, stirred 2 hours as aromatic diamine, obtain polyamic acid.This polyamic acid solution is warming up to 190 ℃, and heated and stirred 20 hours is removed its water and two benzene azeotropics of following the imines cyclisation to be generated.After reaction finishes, can obtain the nmp solution of polyimide resin.
(synthesis example 2A)
Add 3,3 ', 4 of 29.4g (0.10 mole) in the detachable flask of 1L, the m-xylene of the NMP of 4 '-benzophenone tetracarboxylic dianhydride, 200g (N-N-methyl-2-2-pyrrolidone N-), 200g stirs under room temperature.Then, use dropping funnel to splash into the reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd system trade(brand)name, amine equivalent 430) of 34.4g (0.04 mole) as siloxane diamine.In stirring ice-cold this reaction soln down, add the BAPP (2,2-two (4-(4-amino-benzene oxygen) phenyl) propane) of 24.6g (0.06 mole) again, and stirred 2 hours down in room temperature (25 ℃) as aromatic diamine, obtain polyamic acid.This polyamic acid solution is warming up to 190 ℃, and heated and stirred 20 hours is removed water and the m-xylene azeotropic of following the imines cyclisation to be generated.After reaction finishes, can obtain the nmp solution of polyimide resin.
(embodiment 1A)
After the nmp solution of the polyimide resin of 265.0g (resin solid composition 30.2 weight %) synthesis example 1A, 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of NC3000 (Nippon Kayaku K. K's system trade(brand)name), the 0.2g of Resins, epoxy, till stir about became evenly to resin in 1 hour., for deaeration, in room temperature (25 ℃) under leave standstill 24 hour, promptly can be used as resin combination varnish thereafter.
(embodiment 2A)
After the nmp solution of the polyimide resin of 216.8g (resin solid composition 36.9 weight %) synthesis example 2A, 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of NC3000 (Nippon Kayaku K. K's system trade(brand)name), the 0.2g of Resins, epoxy, till stir about became evenly to resin in 1 hour., for deaeration, in room temperature (25 ℃) under leave standstill 24 hour, promptly can be used as resin combination varnish thereafter.
(embodiment 3A)
After the nmp solution of the polyimide resin of 248.3g (resin solid composition 30.2 weight %) synthesis example 1A, 50.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of DER331L (big Japanese ink Co., Ltd. system trade(brand)name), the 0.25g of Resins, epoxy, till stir about became evenly to resin in 1 hour., for deaeration, in room temperature (25 ℃) under leave standstill 24 hour, promptly can be used as resin combination varnish thereafter.
(prepreg and the making of pasting the tinsel plywood)
After the resin combination varnish of made among embodiment 1A～3A soaked the woven fiber glass (rising sun シ ユ エ one ベ Le Co., Ltd. system, trade(brand)name 1037) that is contained in thickness 0.028mm, heating 15 minutes, drying under 150 ℃, obtaining the resin composition is the prepreg of 70 weight %.Its junction surface and prepreg are harmonious the electrolytic copper foil (Furukawa Co., Ltd. system, trade(brand)name F2-WS-12) of thickness 12 μ m in the both sides of this prepreg and overlapping, under 200 ℃, 90 minutes, the pressing conditions of 4.0MPa, make two sides copper-surfaced plywood.
(comparative example 1A)
After soaking the resin combination varnish of embodiment 1A in the woven fiber glass (Nitto Boseiki Co., Ltd.'s system, trade(brand)name 7010) that is contained in thickness 0.10mm (100 μ m), in 150 ℃ of heating 25 minutes and drying down, the prepreg of acquisition resin composition 70 weight %.Its junction surface and prepreg are harmonious the electrolytic copper foil (Furukawa Co., Ltd. system, trade(brand)name F2-WS-12) of thickness 12 μ m in the both sides of this prepreg and overlapping, under 200 ℃, 90 minutes, the pressing conditions of 4.0MPa, make two sides copper-surfaced plywood.
Use the two sides copper-surfaced plywood of gained to carry out evaluation shown below.
(assessment item)
(1) the Copper Foil stripping strength (Copper Foil peels off intensity, peel strength) of the two sides copper-surfaced plywood of mensuration gained.
(2) impregnated in the solder bath of 260 ℃, 288 ℃ and 300 ℃ 5 minutes, observe unusual phenomenon such as whether expansion is arranged, peel off.The benchmark of estimating is as follows.Zero: no abnormal; *: have unusual.
(3) will remove plywood bending after the Copper Foil by corrosion, estimate that it is flexible.The benchmark of estimating is as follows.Zero: non-cracking; *: fracture is arranged.
(4) two sides copper-surfaced plywood is carried out circuit fabrication, make the test film of daisy chain pattern.To each test film carry out 1000 times with-65 ℃/30 minutes, 125 ℃/30 minutes as 1 round-robin thermal shock test, measure its resistance change.The benchmark of estimating is as follows.Zero: in the resistance change 10%; *: resistance change surpasses 10%.Gained the results are shown in table 1.
Table 1
| Project | Unit | Embodiment 1A | Embodiment 2A | Embodiment 3A | Comparative example 1A |
| Polyimide resin | - | Synthesis example 1A | Synthesis example 2A | Synthesis example 1A | Synthesis example 1A |
| Resins, epoxy | - | NC3000 | NC3000 | DER331L | NC3000 |
| Polyimide/epoxy | Weight part | 80/20 | 80/20 | 75/25 | 80/20 |
| Flexible | - | ○ | ○ | ○ | × |
| The scolding tin thermotolerance | - | ○ | ○ | ○ | ○ |
| Thermal shock test | - | ○ | ○ | ○ | ○ |
| The Copper Foil stripping strength | kN/m | 1.2 | 0.9 | 1.0 | 1.1 |
All prepregs of embodiment 1A～3A all demonstrate up to 0.9～1.2kN/m Copper Foil stripping strength, so good.Again, no matter scolding tin thermotolerance (260 ℃ of scolding tin, 288 ℃ of scolding tin, 300 ℃ of scolding tin) is carrying out under which temperature more than 5 minutes, and so unusual phenomenon such as all do not have the expansion observed, peel off is good.Again, in thermal shock test, even carry out 1000 circulations, all in 10%, connection reliability is good for resistance change.In addition, be rich in flexible, can be at random crooked.
With respect to this, the two sides copper-surfaced plywood of comparative example 1A does not have flexible, when trying bending, has produced crackle in the part of woven fiber glass and resin.And warpage has taken place.
(synthesis example 1B)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 14.9g (0.06 mole) as DDS (diamino diphenyl sulfone) with diamines of 2 above aromatic rings, 43.0g (0.05 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 430), 72.0g (0.36 mole) is as ジ エ Off ア one ミ Application D-2000 (sun science and technology chemistry (Sun-technolchemical) Co., Ltd. system trade(brand)name of aliphatie diamine, amine equivalent 1000), 11.3g (0.054 mole) is as the ワ Application ダ ミ Application (New Japan Chem Co., Ltd's system trade(brand)name) of the diamines shown in the general formula (4), (80.7g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 589g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 55.1g (0.22 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of polyamide-imide resin.
(synthesis example 2B)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 14.9g (0.06 mole) as DDS (diamino diphenyl sulfone) with diamines of 2 above aromatic rings, 51.6g (0.06 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 430), 52.0g (0.26 mole) is as ジ エ Off ア one ミ Application D-2000 (sun science and technology chemistry (Sun-technolchemical) Co., Ltd. system trade(brand)name of aliphatie diamine, amine equivalent 1000), 11.3g (0.054 mole) is as the ワ Application ダ ミ Application (New Japan Chem Co., Ltd's system trade(brand)name) of the diamines shown in the general formula (4), (80.7g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 575g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 55.1g (0.22 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of polyamide-imide resin.
(synthesis example 3B)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 14.9g (0.06 mole) as DDS (diamino diphenyl sulfone) with diamines of 2 above aromatic rings, 43.0g (0.05 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 430), 72.0g (0.36 mole) is as ジ エ Off ア one ミ Application D-2000 (sun science and technology chemistry (Sun-technolchemical) Co., Ltd. system trade(brand)name of aliphatie diamine, amine equivalent 1000), 11.3g (0.054 mole) is as the ワ Application ダ ミ Application (New Japan Chem Co., Ltd's system trade(brand)name) of the diamines shown in the general formula (4), (80.7g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 599g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 60.1g (0.24 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of polyamide-imide resin.
(embodiment 1B)
After the nmp solution of the polyamide-imide resin (PAI) of 250.0g (resin solid composition 32 weight %) synthesis example 1B and 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of NC3000 (Nippon Kayaku K. K's system trade(brand)name), the 0.2g of Resins, epoxy (Ep), after stir about became evenly to resin in 1 hour, for deaeration, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as resin combination varnish.
(embodiment 2B)
Except that the nmp solution of the polyamide-imide resin (PAI) that uses synthesis example 2B replaces the polyamide-imide resin (PAI) of synthesis example 1B, all the other all make resin combination varnish with the method that is same as embodiment 1B.
(embodiment 3B)
Except that the nmp solution of the polyamide-imide resin (PAI) that uses synthesis example 3B replaces the polyamide-imide resin (PAI) of synthesis example 1B, all the other all make resin combination varnish with the method that is same as embodiment 1B.
(reference example 1B)
Remove KS6600 (Hitachi Chemical Co., Ltd.'s system of using as the polyamide-imide resin (PAI) that does not have general formula (1) structure, trade(brand)name) nmp solution replaces outside the polyamide-imide resin (PAI) of synthesis example 1B, and all the other all make resin combination varnish with the method that is same as embodiment 1B.
(prepreg and the making of pasting the tinsel plywood)
After the resin combination varnish of made among embodiment 1B～3B and the reference example 1B soaked the woven fiber glass (rising sun シ ユ エ one ベ Le Co., Ltd. system, trade(brand)name 1037) that is contained in thickness 0.028mm, in 15 ℃ of heating 15 minutes and dry down, obtaining the resin composition is the prepreg of 70 weight %.
Its junction surface and prepreg are harmonious the electrolytic copper foil (Furukawa Co., Ltd. system, trade(brand)name F2-WS-12) of thickness 12 μ m in the both sides of this prepreg and overlapping, under 230 ℃, 90 minutes, the pressing conditions of 4.0MPa, make two sides copper-surfaced plywood.Use the two sides copper-surfaced plywood of gained to carry out evaluation shown below.
(assessment item)
(1) the Copper Foil stripping strength (Copper Foil peels off intensity, peel strength) of the two sides copper-surfaced plywood of mensuration gained.
(2) impregnated in 260 ℃, 288 ℃ the solder bath, be measured to the time that expands, peel off etc. till the unusual phenomenon.
(3) will remove plywood bending after the Copper Foil by corrosion, estimate that it is flexible.The benchmark of estimating is as follows.Zero: non-cracking; *: fracture is arranged.
(4) will remove plywood behind the Copper Foil by corrosion, and impose 121 ℃, the moisture absorption of 2 atmospheric PCT saturation conditionss and handle after 1 hour, impregnated in 260 ℃ the solder bath 20 seconds again, the unusual phenomenon (anti-PCT) of observing plywood whether expansion is arranged, peeling off etc.The benchmark of estimating is as follows.Zero: no abnormal; *: have unusual.
Gained the results are shown in table 2.
Table 2
| Project | Unit | Embodiment 1B | Embodiment 2B | Embodiment 3B | Reference example 1B |
| PAI | - | Synthesis example 1B | Synthesis example 2B | Synthesis example 3B | KS6600 |
| PAI/Ep | Weight part | 80/20 | 80/20 | 80/20 | 80/20 |
| Flexible | - | ○ | ○ | ○ | × |
| 260 ℃ of scolding tin | Second | ＞300 | ＞300 | ＞300 | 150 |
| 288 ℃ of scolding tin | Second | ＞300 | ＞300 | ＞300 | 60 |
| Anti-PCT | - | ○ | ○ | ○ | × |
| The Copper Foil stripping strength | kN/m | 1.0 | 0.8 | 0.9 | 0.6 |
Contain have general formula all prepregs of embodiment 1B～3B of polyamide-imide resin of structure of (1), all demonstrate Copper Foil stripping strength (Copper Foil peels off intensity), so good up to 0.8～1.0kN/m.Again, no matter scolding tin thermotolerance (260 ℃ of scolding tin, 288 ℃ of scolding tin) is carrying out under which temperature more than 5 minutes, and so the unusual phenomenon of all do not have the expansion observed, peeling off etc. is good.And be rich in flexible, buckled layer lamination at random.Handle even carry out 121 ℃, the moisture absorption of 2 atmospheric PCT saturation conditionss in addition, impregnated in 260 ℃ the solder bath 20 seconds again, do not observe yet expand or peel off wait unusually.
With respect to this, the prepreg of reference example 1B or subsides tinsel plywood have lower Copper Foil stripping strength 0.6kN/m.And lack flexiblely, when the buckled layer lamination, produced fracture.In addition, also poor on relevant its scolding tin thermotolerance and the anti-PCT, can be observed expand or peel off wait unusually.
(synthesis example 1C)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 29.8g (0.12 mole) as DDS (diamino diphenyl sulfone) with diamines of 2 above aromatic rings, 34.4g (0.04 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 430), (80.0g 0.04 mole) ジ エ Off ア one ミ Application D-2000 (sun science and technology KCC system trade(brand)name, amine equivalent 1000), (80.7g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 605g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 60.1g (0.24 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of silicone-modified polyamide-imide resin.
(synthesis example 2C)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 41.1g (0.10 mole) as BAPP (2 with diamines of 2 above aromatic rings, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-), 43.0g (0.05 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 430), (100.0g 0.05 mole) ジ エ Off ア one ミ Application D-2000 (sun science and technology KCC system trade(brand)name, amine equivalent 1000), (80.7g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 603g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 60.1g (0.24 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of silicone-modified polyamide-imide resin.
(embodiment 1C)
After the nmp solution of the silicone-modified polyamide-imide resin (PAI) of 250.0g (resin solid composition 32 weight %) synthesis example 1C and 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of NC3000 (Nippon Kayaku K. K's system trade(brand)name), the 0.2g of Resins, epoxy (Ep), till stir about became evenly to resin in 1 hour.Then, will add with the slurry form of methyl ethyl ketone as the 20g OP930 (Network ラ リ ア Application ト society system trade(brand)name) of P contained compound (phosphorus flame retardant), and stirred 1 hour.At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as the resin combination varnish of phosphorus content 3.92 weight % for deaeration.
(embodiment 2C)
After the nmp solution of the silicone-modified polyamide-imide resin (PAI) of 228.6g (resin solid composition 35 weight %) synthesis example 2C and 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of NC3000 (Nippon Kayaku K. K's system trade(brand)name), the 0.2g of Resins, epoxy (Ep), till stir about became evenly to resin in 1 hour.Then, will add with the slurry form of methyl ethyl ketone, further stirred 1 hour as the 20g OP930 (Network ラ リ ア Application ト society system trade(brand)name) of P contained compound (phosphorus flame retardant).At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as the resin combination varnish of phosphorus content 3.92 weight % for deaeration.
(embodiment 3C)
After the nmp solution of the silicone-modified polyamide-imide resin (PAI) of 250.0g (resin solid composition 32 weight %) synthesis example 1C and 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of DER331L (ダ ウ KCC system trade(brand)name), the 0.2g of Resins, epoxy (Ep), till stir about became evenly to resin in 1 hour.Then, will add with the slurry form of methyl ethyl ketone, further stirred 1 hour as the 20g OP930 (Network ラ リ ア Application ト society system trade(brand)name) of P contained compound (phosphorus flame retardant).At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as the resin combination varnish of phosphorus content 3.92 weight % for deaeration.
(embodiment 4C)
After the nmp solution of the silicone-modified polyamide-imide resin (PAI) of 250.0g (resin solid composition 32 weight %) synthesis example 1C and 40.0g (dimethylacetamide solutions of resin solid composition 50 weight %) cooperated as the 2-ethyl-4-methylimidazole of DER331L (ダ ウ KCC system trade(brand)name), the 0.2g of Resins, epoxy (Ep), till stir about became evenly to resin in 1 hour.Then, will add with the slurry form of methyl ethyl ketone, further stirred 1 hour as the 30g OP930 (Network ラ リ ア Application ト society system trade(brand)name) and the HCA-HQ (three photochemistry Co., Ltd. trade(brand)names) of 10.0g of P contained compound (phosphorus flame retardant).At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as the resin combination varnish of phosphorus content 5.72 weight % for deaeration.
(reference example 1C)
As P contained compound, (trade(brand)name: レ オ Off オ ス 110 (Ajincomoto Co., Inc's systems)), all the other all carry out with the method that is same as embodiment 1C, can make the resin combination varnish of phosphorus content 0.06 weight % except that using aqueous phosphorus compound.
(reference example 2C)
Except that the nmp solution and the NC3000 (Nippon Kayaku K. K system trade(brand)name) of 120.0g (dimethylacetamide solutions of resin solid composition 50 weight %) of the silicone-modified polyamide-imide resin (PAI) that uses 114.3g (resin solid composition 32 weight %) synthesis example 1C as Resins, epoxy (Ep), all the other all carry out with the method that is same as embodiment 1C, can make the resin combination of phosphorus content 3.92 weight %.
(prepreg and the making of pasting the tinsel plywood)
After the resin combination varnish of made among embodiment 1C～4C and reference example 1C, the 2C soaked the woven fiber glass (rising sun シ ユ エ one ベ Le Co., Ltd. system, trade(brand)name 1037) that is contained in thickness 0.028mm, heating 15 minutes, drying can obtain the prepreg that the resin composition is 70 weight % under 150 ℃.
Its junction surface and prepreg are harmonious the electrolytic copper foil (Furukawa Co., Ltd. system, trade(brand)name F2-WS-12) of thickness 12 μ m in the both sides of this prepreg and overlapping, under 230 ℃, 90 minutes, the pressing conditions of 4.OMPa, make two sides copper-surfaced plywood.Use the two sides copper-surfaced plywood of gained to carry out evaluation shown below.
(assessment item)
(1) the Copper Foil stripping strength (Copper Foil peels off intensity, peel strength) of the two sides copper-surfaced plywood of mensuration gained.
(2) impregnated in 260 ℃, 288 ℃ the solder bath, be measured to the time that expands, peel off etc. till the unusual phenomenon.
(3) will remove plywood bending after the Copper Foil by corrosion, estimate that it is flexible.The benchmark of estimating is as follows.Zero: non-cracking; △: have a little fracture *: fracture is arranged.
(4) VTM of the evaluation of flame retardant resistance by UL-94 tests and carries out.That is, at first etching is removed after the copper on the attached copper plywood in two sides, cuts length 200mm, width 50mm, it is twisted on the axle of diameter 12.7mm again, and fixing with adhesive tape from the position of an end 125mm, make it become tubular, extract axle thereafter, made sample.Make this sample vertical then, after its upper end is fixed with the spring sealing, 3 seconds of 20mm blue flame that end in contact is produced by the methane gas burner, and measure residual fire time and burning extent.
(5) two sides copper-surfaced plywood is carried out circuit fabrication, make the test film of daisy chain pattern.To each test film carry out 1000 times with-65 ℃/30 minutes, 125 ℃/30 minutes as 1 round-robin thermal shock test, measure its resistance change.The benchmark of estimating is as follows.Zero: in the resistance change 10%; *: resistance change surpasses 10%.Each evaluation result is shown in table 3.
Table 3
| Project | Unit | Embodiment 1C | Embodiment 2C | Embodiment 3C | Embodiment 4C | Reference example 1C | Reference example 2C |
| PAI | - | Synthesis example 1C | Synthesis example 2C | Synthesis example 1C | Synthesis example 1C | Synthesis example 1C | Synthesis example 1C |
| PAI/Ep | Weight part | 80/20 | 80/20 | 80/20 | 80/20 | 80/20 | 37/60 |
| Contain P-compound | - | OP930 | OP930 | OP930 | OP930 HCA-HQ | レオフオス 110 | OP930 |
| P content | Weight % | 3.92 | 3.92 | 3.92 | 5.72 | 0.06 | 3.92 |
| Flexible | - | ○ | ○ | ○ | ○ | △ | × |
| Flame retardant resistance | - | VTM-0 | VTM-0 | VTM-0 | VTM-0 | HB | - |
| Burning extent * | mm | 80 | 80 | 80 | 80 | 125 | - |
| 260 ℃ of scolding tin | Second | ＞300 | ＞300 | ＞300 | ＞300 | 40 | 50 |
| 288 ℃ of scolding tin | Second | ＞300 | ＞300 | ＞300 | ＞300 | 10 | 20 |
| Thermal shock test | - | ○ | ○ | ○ | ○ | × | × |
| The Copper Foil stripping strength | kN/m | 1.0 | 1.0 | 0.9 | 0.8 | 0.6 | 0.5 |
*: the VTM test of UL-94
All prepregs of embodiment 1C～4C all demonstrate the Copper Foil stripping strength (Copper Foil peels off intensity) up to 0.8～1.0kN/m, so good.Again, no matter scolding tin thermotolerance (260 ℃ of scolding tin, 288 ℃ of scolding tin) is carrying out under which temperature more than 5 minutes, and so the unusual phenomenon of all do not have the expansion observed, peeling off etc. is good.Again, be (80mm) below the 100mm according to the burning extent of the diameter 12.7mm test film of the VTM test determination of UL94, the flame retardant resistance of all experimental examples is all VTM-0.In addition, on thermal shock test, even carry out 1000 circulations, all in 10%, it is good to connect reliability for resistance change.
With respect to this, the prepreg of the reference example 1C of phosphorus content 0.06 weight % has lower Copper Foil stripping strength 0.6kN/m, and flame retardant resistance is HB, and burning extent is 125mm.Again, with respect to 100 weight parts of polyamide imide resins, thermosetting resin (Resins, epoxy) is the reference example 2C of 162 weight parts, lacks flexiblely, has produced fracture when the buckled layer lamination.Therefore, can't make the test portion of the evaluation usefulness of flame retardant resistance, so can't measure burning extent.Again, reference example 1C, 2C are all poor on relevant its scolding tin thermotolerance, can be observed expand or peel off wait unusually, and in thermal shock test, resistance change is big.In addition, in thermal shock test, in reference example 1C and 2C, carry out separately 200 times and 100 circulations, its opposing value changes all above 10%.
(synthesis example 1D)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 12.4g (0.05 mole) as DDS (diamino diphenyl sulfone) with diamines of 2 above aromatic rings, 51.6g (0.06 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 430), (72.0g 0.036 mole) ジ エ Off ア one ミ Application D-2000 (sun science and technology KCC system trade(brand)name, amine equivalent 1000), (11.34g 0.054 mole) ワ Application ダ ミ Application (New Japan Chem Co., Ltd's system trade(brand)name), (80.68g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 612g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 60.1g (0.24 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of silicone-modified polyamide-imide resin.
(synthesis example 2D)
Having the 25ml water and basis weight susceptor of the band cock that has connected reflux exchanger, thermometer, in the detachable flask of the 1L of agitator, add 24.63g (0.06 mole) as BAPP (2 with diamines of 2 above aromatic rings, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-), 124.6g (0.14 mole) is as reactive silicone oil KF-8010 (Shin-Etsu Chemial Co., Ltd's system trade(brand)name of siloxane diamine, amine equivalent 445), (80.68g 0.42 mole) TMA (trimellitic acid 1,2-anhydride), and add the NMP (N-N-methyl-2-2-pyrrolidone N-) of 539g as non-proton property polar solvent, stirred 30 minutes down in 80 ℃.
Then, drop into as can with the toluene 150ml of water azeotropic aromatic hydrocarbons after, improve temperature, it was refluxed 2 hours.Affirmation ponding in the water and basis weight susceptor Yi Bian remove the distillate that lodges in the water and basis weight susceptor, Yi Bian temperature is increased to about 190 ℃, is removed toluene with this to 7.2ml, when not observing the distillating of water., room temperature (25 ℃) fallen back in solution temperature, drop into the MDI (4,4 '-diphenylmethanediisocyanate) of 60.07g (0.24 mole), reacted 2 hours down in 190 ℃ as aromatic diisocyanate thereafter.After reaction finishes, obtained the nmp solution of silicone-modified polyamide-imide resin.
(embodiment 1D)
With the nmp solution of the silicone-modified polyamide-imide resin of 218.75g (resin solid composition 32 weight %) synthesis example 1D, 60.0g (dimethylacetamide solutions of resin solid composition 50 weight %) NC3000 (Resins, epoxy as heat reactive resin, Nippon Kayaku K. K's system trade(brand)name), 2-ethyl-4-methylimidazole and the 0.5g of 0.3g are 4 of antioxidant as hindered phenol, after 4 '-butylidene two (3-methyl-6-tert butyl phenol) cooperates, till stir about became evenly to resin in 1 hour.Then, 20g is added as pulp as the OP930 (Network ラ リ ア Application ト society system trade(brand)name) of phosphorous filler, further stirred 1 hour with the methyl ethyl ketone of 40g.At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as resin combination varnish for deaeration.
(embodiment 2D)
With the nmp solution of the silicone-modified polyamide-imide resin of 218.75g (resin solid composition 32 weight %) synthesis example 1D, 60.0g (dimethylacetamide solutions of resin solid composition 50 weight %) DER331L (Resins, epoxy as thermosetting resin, ダ ウ KCC system trade(brand)name), 2-ethyl-4-methylimidazole and the 0.5g of 0.3g are 1 of antioxidant as hindered phenol, 1, after 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane cooperates, till stir about became evenly to resin in 1 hour.Then, 15g is added as pulp as the OP930 (Network ラ リ ア Application ト society system trade(brand)name) of phosphorous filler, further stirred 1 hour with the methyl ethyl ketone of 30g.At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as resin combination varnish for deaeration.
(embodiment 3D)
With the nmp solution of the silicone-modified polyamide-imide resin of 218.75g (resin solid composition 32 weight %) synthesis example 1D, 60.0g (dimethylacetamide solutions of resin solid composition 50 weight %) ZX-1548-2 (Resins, epoxy as thermosetting resin, Toto Kasei KK system trade(brand)name), after the 2-ethyl-4-methylimidazole of 0.3g and 0.5g cooperate as the dilauryl thiopropionate of sulphur organic compound system antioxidant, till stir about became evenly to resin in 1 hour.Then, 20g is added as pulp as the OP930 (Network ラ リ ア Application ト society system trade(brand)name) of phosphorous filler, further stirred 1 hour with the methyl ethyl ketone of 40g.At last,, under room temperature (25 ℃), left standstill 24 hours, promptly can be used as resin combination varnish for deaeration.
(embodiment 4D)
Except that the nmp solution of the silicone-modified polyamide-imide resin that uses 200.0g (resin solid composition 35 weight %) synthesis example 2D replaces the silicone-modified polyamide-imide resin of synthesis example 1D, all the other all make resin combination varnish with the method that is same as embodiment 1D.
(embodiment 5D)
Except that the nmp solution of the silicone-modified polyamide-imide resin that uses 200.0g (resin solid composition 35 weight %) synthesis example 2D replaces the silicone-modified polyamide-imide resin of synthesis example 1D, all the other all make resin combination varnish with the method that is same as embodiment 2D.
(reference example 1D)
Except that mismatching as hindered phenol is 4 of antioxidant, and outside 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), all the other all make resin combination varnish with the method that is same as embodiment 1D.
(reference example 2D)
Except that mismatching as hindered phenol is 1,1 of antioxidant, and outside 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, all the other all make resin combination varnish with the method that is same as embodiment 2D.
(reference example 3D)
Except that the dilauryl thiopropionate of mismatching as sulphur organic compound system antioxidant, all the other all make resin combination varnish with the method that is same as embodiment 3D.
(reference example 4D)
Removing and mismatching hindered phenol is 4 of antioxidant, and outside 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), all the other all make resin combination varnish with the method that is same as embodiment 4D.
(reference example 5D)
Except that mismatching as hindered phenol is 1,1 of antioxidant, and outside 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, all the other all make resin combination varnish with the method that is same as embodiment 5D.
(prepreg and the making of pasting two sides copper plywood)
After the resin combination varnish of made among embodiment 1D～5D and the reference example 1D～5D soaked the woven fiber glass (rising sun シ ユ エ one ベ Le Co., Ltd. system, trade(brand)name 1037) that is contained in thickness 0.028mm, heating 15 minutes, drying can obtain the prepreg that the resin composition is 70 weight % under 150 ℃.Its junction surface and prepreg are harmonious the electrolytic copper foil (Furukawa Co., Ltd. system, trade(brand)name F2-WS-12) of thickness 12 μ m in the both sides of 1 this prepreg and overlapping, under 230 ℃, 90 minutes, the pressing conditions of 4.OMPa, make two sides copper-surfaced plywood.In addition, with overlapping 8 of this prepreg, its junction surface and prepreg are harmonious the electrolytic copper foil (Furukawa Co., Ltd. system, trade(brand)name F2-WS-12) of thickness 12 μ m in its both sides and overlapping, under 230 ℃, 90 minutes, the pressing conditions of 4.OMPa, make two sides copper-surfaced plywood.In addition, use is carried out the evaluation of following (1)～(4) with 1 made two sides copper-surfaced plywood of prepreg.Use again with 8 made two sides copper-surfaced plywoods of prepreg and carry out the evaluation of following (5), (6).
(assessment item)
(1) the Copper Foil stripping strength (Copper Foil peels off intensity, peel strength) of the two sides copper-surfaced plywood of mensuration gained.
(2) impregnated in 260 ℃, 300 ℃ the solder bath, be measured to the time that expands, peel off etc. till the unusual phenomenon.
(3) will remove plywood bending after the Copper Foil by corrosion, estimate that it is flexible.The benchmark of estimating is as follows.Zero: non-cracking; △: have a little fracture *: fracture is arranged.
(4) VTM of the evaluation of flame retardant resistance by UL-94 tests and carries out.That is, at first etching is removed after the copper on the attached copper plywood in two sides, cuts length 200mm, width 50mm, it is twisted on the axle of diameter 12.7mm again, and fixing with adhesive tape from the position of an end 125mm, make it become tubular, extract axle thereafter, made sample.Make this sample vertical then, after its upper end is fixed with the spring sealing, 3 seconds of 20mm blue flame that end in contact is produced by the methane gas burner, and measure residual fire time and burning extent.With burning extent is to be decided to be flame retardant resistance VTM-0 below the 100mm.
(5) two sides copper-surfaced plywood is carried out circuit fabrication, make the test film of daisy chain pattern.To each test film carry out 1000 times with-65 ℃/30 minutes, 125 ℃/30 minutes as 1 round-robin thermal shock test, measure its resistance change.The benchmark of estimating is as follows.OK: in the resistance change 10%; NG: resistance change surpasses 10%.
(6) two sides copper-surfaced plywood is carried out circuit fabrication, carried out moving (migration) test.Through hole (through hole) manufacturing in hole is to use the drill bit of 0.9mm diameter, with the 60000rpm revolution, carries out under the condition of drill speed 1.800mm/min.Hole wall is made as 350 μ m at interval, to each test portion, measured the insulation resistance in 400 holes (through hole and through hole between be separated with 200 places) in time.In 85 ℃/90%RH atmosphere, under the experiment condition of 100V impressed voltage, be determined at the required fate that opens circuit between through hole and the through hole.And the mensuration of insulation resistance is to carry out with 100V/1 minute, and opens circuit becoming less than 10 8 power Ω to be judged to be when following.Each evaluation result is shown in table 4.
Table 4
| Project | Unit | Embodiment 1D | Embodiment 2D | Embodiment 3D | Embodiment 4D | Embodiment 5D | Reference example 1D | Reference example 2D | Reference example 3D | Reference example 4D | Reference example 5D |
| Required fate opens circuit | My god | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | 30 | 7 | 10 | 35 | 11 |
| The Copper Foil stripping strength | kN/m | 1.1 | 0.9 | 1.0 | 0.8 | 0.9 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| 260 ℃ of scolding tin thermotolerances | Second | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 |
| 300 ℃ of scolding tin thermotolerances | Second | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 | ＞300 |
| Thermal shock test | - | OK | OK | OK | OK | OK | OK | OK | OK | OK | OK |
| Flexible | - | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Flame retardant resistance | - | VTM-0 | VTM-0 | VTM-0 | VTM-0 | VTM-0 | VTM-0 | VTM-0 | VTM-0 | VTM-0 | VTM-0 |
The two sides copper-surfaced plywood of embodiment 1D～5D all demonstrates the Copper Foil stripping strength (Copper Foil peels off intensity) up to 0.8～1.1kN/m, so good.Again, no matter scolding tin thermotolerance (260 ℃ of scolding tin, 300 ℃ of scolding tin) is carrying out under which temperature more than 5 minutes, and so the unusual phenomenon of all do not have the expansion observed, peeling off etc. is good.Again, be below the 100mm according to the burning extent of the test film of the diameter 12.7mm of the VTM test determination of UL94, the flame retardant resistance of all embodiment is all VTM-0.Again, in thermal shock test, even carry out 1000 circulations, all in 10%, connection reliability is good for resistance change.And be rich in flexible, buckled layer lamination at random.Again, in cooperating the embodiment 1D～5D of (c) oxidation inhibitor, even also do not have the generation of opening circuit through 60 days, 1D～5D compares with reference example, shows high insulation characterisitic.In addition, after through 60 days, insulation resistance is more than 10 the 11 power Ω in embodiment 1D～5D.
Claims (16)
1. a prepreg is characterized in that, is to make the resin combination that contains resin with imide structure and thermosetting resin soak to be contained in the fiber base material that thickness is 5～50 μ m to form.
2. prepreg according to claim 1, wherein said resin with imide structure has siloxane structure.
3. prepreg according to claim 1 and 2, wherein said resin with imide structure has the structure of following general formula (1).
[changing 1]
4. according to any described prepreg in the claim 1～3, wherein said resin with imide structure is a polyamide-imide resin.
5. according to any described prepreg in the claim 1～4, wherein said resin with imide structure is that the mixture and the diisocyanate cpd that contain following imide dicarboxylic acid react the polyamide-imide resin that gets, and described imide dicarboxylic acid is to make to contain siloxane diamine and following general formula (2a) or (2b) mixture of represented diamines and trimellitic acid 1,2-anhydride react and get;
[changing 2]
(formula (2a) or (2b) in, X
21The represented divalent base or the represented divalent base of following general formula (3b) of aliphatic alkyl, the halogenation aliphatic alkyl of carbon number 1～3, alkylsulfonyl, ether, carbonyl, singly-bound, following general formula (3a) of expression carbon number 1～3; X
22The aliphatic alkyl of expression carbon number 1～3, halogenation aliphatic alkyl, alkylsulfonyl, ether or the carbonyl of carbon number 1～3; R
21, R
22And R
23Independent separately or identical, expression hydrogen atom, hydroxyl, methoxyl group, methyl or halogenation methyl;
[changing 3]
Wherein, in the formula (3a), X
31The aliphatic alkyl of expression carbon number 1～3, halogenation aliphatic alkyl, alkylsulfonyl, ether, carbonyl or the singly-bound of carbon number 1～3).
6. according to any described prepreg in the claim 1～4, wherein said resin with imide structure is to contain the mixture of following imide dicarboxylic acid and the polyamide-imide resin that diisocyanate cpd reacts gained, described imide dicarboxylic acid is to make to contain the represented diamines of following general formula (4), siloxane diamine and following general formula (5a) or (5b) mixture of represented diamines, react with trimellitic acid 1,2-anhydride and;
[changing 4]
[changing 5]
(formula (5a) or (5b) in, X
51The represented divalent base or the represented divalent base of following general formula (6b) of aliphatic alkyl, the halogenation aliphatic alkyl of carbon number 1～3, alkylsulfonyl, ether, carbonyl, singly-bound, following general formula (6a) of expression carbon number 1～3; X
52The aliphatic alkyl of expression carbon number 1～3, halogenation aliphatic alkyl, alkylsulfonyl, ether or the carbonyl of carbon number 1～3; R
51, R
52And R
53Independent separately or identical, expression hydrogen atom, hydroxyl, methoxyl group, methyl or halogenation methyl;
[changing 6]
Wherein, in the formula (6a), X
61The aliphatic alkyl of expression carbon number 1～3, halogenation aliphatic alkyl, alkylsulfonyl, ether, carbonyl or the singly-bound of carbon number 1～3).
7. prepreg according to claim 1 and 2, wherein said have the resin of imide structure for to have the polyimide resin of the represented structure of following general formula (7) or to have the represented structure of following general formula (7) and the polyimide resin of the structure that following general formula (8) is represented;
[changing 7]
[changing 8]
(in formula (7) or (8), Ar
1Represent 4 valency aromatic series bases, Ar
2Expression divalent aromatic series base, R
71And R
72Independent separately or identical, expression divalent alkyl, R
73, R
74, R
75And R
76Independent separately or identical, the alkyl of expression carbon number 1～6, n represents 1～50 integer).
8. according to any described prepreg in the claim 1～4, wherein said resin with imide structure is the polyamide-imide resin with the represented structure of following general formula (9);
[changing 9]
(in the formula (9), R
91, R
92, R
93And R
94The ring texture of the polyamide-imide resin of expression formation respectively or a part of carbon atom of chain-like structure).
9. according to any described prepreg in the claim 1～8, wherein said thermosetting resin is a Resins, epoxy.
10. according to any described prepreg in the claim 1～9, wherein said heat reactive resin is the Resins, epoxy with the epoxypropyl more than 2.
11. according to any described prepreg in the claim 1～10, wherein said resin combination also contains P contained compound, with respect to the described resin of 100 weight parts, contain the described thermosetting resin of 1～140 weight part in this resin combination with imide structure; And phosphorus accounts for 0.1～5 weight % in the gross weight of resin solid composition.
12. according to any described prepreg in the claim 1～11, wherein said resin combination also contains hindered phenol system or sulphur organic compound system antioxidant.
13. prepreg according to claim 12, wherein said antioxidant is, be selected from by butylation hydroxyl methoxy benzene, 2,6-two-tertiary butyl-4-ethylphenol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, four-(methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl propionic ester) methane, Tyox B, in the distearyl thiodipropionate form a group at least a kind.
14. according to any described prepreg in the claim 1～13, wherein when having solidify to form base material, the burning extent in the VTM of the UL-94 test is below the 100mm.
15. one kind is pasted the tinsel plywood, it is characterized in that, with the overlapping given number of the prepreg of any record in the claim 1～14, and disposes tinsel at it on the one-sided or both sides, carries out heating and pressurizing and gets.
16. a printed circuit board (PCB) is characterized in that, the described tinsel in the subsides tinsel plywood of record in the claim 15 is carried out circuit fabrication and got.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP060582/2004 | 2004-03-04 | ||
| JP2004060582 | 2004-03-04 | ||
| JP2004060581 | 2004-03-04 | ||
| JP060581/2004 | 2004-03-04 | ||
| JP062186/2004 | 2004-03-05 | ||
| JP2004062186 | 2004-03-05 | ||
| JP2004086630 | 2004-03-24 | ||
| JP086630/2004 | 2004-03-24 | ||
| PCT/JP2005/003753 WO2005085335A1 (en) | 2004-03-04 | 2005-03-04 | Prepreg, metal-clad laminate and printed circuit board using same |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101454256A Division CN101348575A (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
| CNA2008101454260A Division CN101348576A (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1930219A true CN1930219A (en) | 2007-03-14 |
| CN1930219B CN1930219B (en) | 2010-06-02 |
Family
ID=37859518
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800069472A Expired - Fee Related CN1930219B (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
| CNA2008101454260A Pending CN101348576A (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
| CNA2008101454256A Pending CN101348575A (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101454260A Pending CN101348576A (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
| CNA2008101454256A Pending CN101348575A (en) | 2004-03-04 | 2005-03-04 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN1930219B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812805B (en) * | 2012-11-28 | 2017-06-30 | 日立化成株式会社 | Silicone compounds, modified imide resin, compositions of thermosetting resin, prepregs, the film with resin, plywood, multilayer printed-wiring board and semiconductor package part |
| US10323126B2 (en) | 2012-11-28 | 2019-06-18 | Hitachi Chemical Company, Ltd. | Siloxane compound, modified imide resin, thermosetting resin composition, prepreg, film with resin, laminated plate, multilayer printed wiring board, and semiconductor package |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI614285B (en) * | 2016-11-11 | 2018-02-11 | 財團法人工業技術研究院 | Polymers and resin composition employing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4455806B2 (en) * | 2001-05-24 | 2010-04-21 | 日立化成工業株式会社 | Prepreg and laminate |
| JP4136509B2 (en) * | 2001-12-18 | 2008-08-20 | 三井金属鉱業株式会社 | Manufacturing method of prepreg, manufacturing apparatus of prepreg, and manufacturing method of copper foil with insulating layer |
-
2005
- 2005-03-04 CN CN2005800069472A patent/CN1930219B/en not_active Expired - Fee Related
- 2005-03-04 CN CNA2008101454260A patent/CN101348576A/en active Pending
- 2005-03-04 CN CNA2008101454256A patent/CN101348575A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812805B (en) * | 2012-11-28 | 2017-06-30 | 日立化成株式会社 | Silicone compounds, modified imide resin, compositions of thermosetting resin, prepregs, the film with resin, plywood, multilayer printed-wiring board and semiconductor package part |
| US10323126B2 (en) | 2012-11-28 | 2019-06-18 | Hitachi Chemical Company, Ltd. | Siloxane compound, modified imide resin, thermosetting resin composition, prepreg, film with resin, laminated plate, multilayer printed wiring board, and semiconductor package |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101348576A (en) | 2009-01-21 |
| CN1930219B (en) | 2010-06-02 |
| CN101348575A (en) | 2009-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1200976C (en) | Heat resistant compsns. | |
| CN1293147C (en) | Thermosetting resin composition and prepreg and laminated sheet using the same | |
| CN1208418C (en) | Adhesive composition, process for producing the same, adhesive film made with the same, substrate for semiconductor mounting, and semiconductor device | |
| CN100341938C (en) | Halogen-free nonflammable epoxy resin composition, halogen-free nonfammable epoxy resin composition for build-up type multi-layer board | |
| CN1169878C (en) | Flame-retardant epoxy resin composition and liminate made with same | |
| CN1324085C (en) | Flame-retardant heat-resistant resin composition and adhesive film comprising the same | |
| CN1225502C (en) | Laminate for printed circuit board and resin composition for producing same | |
| CN1130427C (en) | Epoxy resin composition and semi-solidified sheet and multilayer printed circuit board produced therewith | |
| CN1066474C (en) | Heat resistant resin composition, heat resistant film adhesive and process for producing the same | |
| CN1206279C (en) | Thermosetting polyphenylene ether resin composition, cured resin composition obtained therefrom, and lamiated structure | |
| CN1914246A (en) | Thermosetting resin composition and use thereof | |
| CN1821337A (en) | Binder composition for semiconductor device and binder sheet for semiconductor device | |
| CN1795238A (en) | Epoxy resin composition | |
| CN100335534C (en) | Polyimide film and method for production thereof, and polyimide/metal laminate using polyimide | |
| CN1865382A (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN1159151C (en) | Soft substrate plate | |
| CN1662120A (en) | Adhesion assisting agent-bearing metal foil, printed wiring board, and production method of printed wiring board | |
| CN1309786C (en) | Thermosetting resin composition and laminates and circuit board substrates made by using same | |
| CN1643071A (en) | Resin composition | |
| CN1933967A (en) | Adhesion-enhanced polyimide film, process for its production, and laminated body | |
| CN1617651A (en) | Formation method of metal layer on resin layer, printed wiring board, and production method thereof | |
| CN1608100A (en) | Resin composition, prepreg, laminate, and semiconductor package | |
| CN1891778A (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN1304460C (en) | Polyamideimide resin, method for producing polyamideimide resin, polyamideimide resin composition containing the same, film-forming material and adhesive for electronic parts made thereof | |
| CN1208054A (en) | Phenol resin composition and method of producing phenol resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CI01 | Publication of corrected invention patent application |
Correction item: Inventor Correct: Yamaguchi Masaki False: Yamada Masaki Number: 22 Volume: 26 |
|
| CI02 | Correction of invention patent application |
Correction item: Inventor Correct: Yamaguchi Masaki False: Yamada Masaki Number: 22 Page: Description Volume: 26 |
|
| ERR | Gazette correction |
Free format text: CORRECT: INVENTOR; FROM: MASAKI YAMADA TO: MASAKI YAMAGUCHI |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100602 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |