JP2005288714A - B-stage resin composition sheet and manufacturing method of copper clad laminate using it - Google Patents
B-stage resin composition sheet and manufacturing method of copper clad laminate using it Download PDFInfo
- Publication number
- JP2005288714A JP2005288714A JP2004102924A JP2004102924A JP2005288714A JP 2005288714 A JP2005288714 A JP 2005288714A JP 2004102924 A JP2004102924 A JP 2004102924A JP 2004102924 A JP2004102924 A JP 2004102924A JP 2005288714 A JP2005288714 A JP 2005288714A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- resin composition
- layer
- copper
- composition sheet
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000011889 copper foil Substances 0.000 claims abstract description 96
- 239000010410 layer Substances 0.000 claims abstract description 49
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 229920006015 heat resistant resin Polymers 0.000 claims description 25
- 238000003475 lamination Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 35
- 239000011347 resin Substances 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 229920000647 polyepoxide Polymers 0.000 description 22
- 239000003822 epoxy resin Substances 0.000 description 20
- 239000000805 composite resin Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004643 cyanate ester Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- -1 4-cyanatophenyl Chemical group 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920001955 polyphenylene ether Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- HMHLDAMOJGEOMQ-UHFFFAOYSA-N (1-cyanato-4-phenylcyclohexa-2,4-dien-1-yl) cyanate Chemical group C1=CC(OC#N)(OC#N)CC=C1C1=CC=CC=C1 HMHLDAMOJGEOMQ-UHFFFAOYSA-N 0.000 description 1
- UFKLQICEQCIWNE-UHFFFAOYSA-N (3,5-dicyanatophenyl) cyanate Chemical compound N#COC1=CC(OC#N)=CC(OC#N)=C1 UFKLQICEQCIWNE-UHFFFAOYSA-N 0.000 description 1
- YDCUTCGACVVRIQ-UHFFFAOYSA-N (3,6-dicyanatonaphthalen-1-yl) cyanate Chemical compound N#COC1=CC(OC#N)=CC2=CC(OC#N)=CC=C21 YDCUTCGACVVRIQ-UHFFFAOYSA-N 0.000 description 1
- GUGZCSAPOLLKNG-UHFFFAOYSA-N (4-cyanatophenyl) cyanate Chemical compound N#COC1=CC=C(OC#N)C=C1 GUGZCSAPOLLKNG-UHFFFAOYSA-N 0.000 description 1
- OFIWROJVVHYHLQ-UHFFFAOYSA-N (7-cyanatonaphthalen-2-yl) cyanate Chemical compound C1=CC(OC#N)=CC2=CC(OC#N)=CC=C21 OFIWROJVVHYHLQ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GXFRMDVUWJDFAI-UHFFFAOYSA-N [2,6-dibromo-4-[2-(3,5-dibromo-4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C(Br)=C(OC#N)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OC#N)C(Br)=C1 GXFRMDVUWJDFAI-UHFFFAOYSA-N 0.000 description 1
- SNYVZKMCGVGTKN-UHFFFAOYSA-N [4-(4-cyanatophenoxy)phenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1OC1=CC=C(OC#N)C=C1 SNYVZKMCGVGTKN-UHFFFAOYSA-N 0.000 description 1
- CNUHQZDDTLOZRY-UHFFFAOYSA-N [4-(4-cyanatophenyl)sulfanylphenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1SC1=CC=C(OC#N)C=C1 CNUHQZDDTLOZRY-UHFFFAOYSA-N 0.000 description 1
- PPZSVSGWDQKBIW-UHFFFAOYSA-N [4-bis(4-cyanatophenoxy)phosphanyloxyphenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1OP(OC=1C=CC(OC#N)=CC=1)OC1=CC=C(OC#N)C=C1 PPZSVSGWDQKBIW-UHFFFAOYSA-N 0.000 description 1
- HYAOCWBXRFEHDV-UHFFFAOYSA-N [4-bis(4-cyanatophenoxy)phosphoryloxyphenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1OP(OC=1C=CC(OC#N)=CC=1)(=O)OC1=CC=C(OC#N)C=C1 HYAOCWBXRFEHDV-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 description 1
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本発明は、プリント配線板用の銅張積層板に使用する積層用のBステージ樹脂組成物シート、並びにこのBステージ樹脂組成物シートを使用して製造される銅張積層板の製造方法に関するものである。本発明のBステージ樹脂組成物シートを、表層に配置して、加熱、硬化して得られる銅張積層板は、銅箔の接着力が良好で、樹脂層と接する銅箔面の表面凹凸が極めて小さいことから、細密回路を作製するのに好適であり、伝送損失が少なく、高周波用途等の高密度プリント配線板として好適に使用される。 The present invention relates to a B-stage resin composition sheet for lamination used in a copper-clad laminate for printed wiring boards, and a method for producing a copper-clad laminate produced using this B-stage resin composition sheet. It is. The copper-clad laminate obtained by placing the B-stage resin composition sheet of the present invention on the surface layer and heating and curing has good adhesion of the copper foil, and the surface roughness of the copper foil surface in contact with the resin layer Since it is extremely small, it is suitable for producing a fine circuit, has little transmission loss, and is suitably used as a high-density printed wiring board for high frequency applications.
近年、小型、薄型、軽量化する電子機器において、プリント配線板の更なる高密度化の要求がますます増加している。従来、プリント配線板に使用する銅張積層板の銅箔としては、銅箔接着力が良好な、銅箔マット面の凹凸が顕著な電解銅箔が使用されている。これらの電解銅箔は、回路形成するためのエッチング工程で、銅箔の足部の一部が、積層板の樹脂表面に残り易く、これを完全に除去するため、エッチング時間を伸ばすと回路がオーバーエッチングされ、細密回路では、接着力が低下する等の問題点があった。また電気信号の伝送回路において、銅箔表面の凹凸の小さい銅箔の方が、伝送損失が少なくなることから、特に高周波用途用に、樹脂層に接する銅箔面を平滑化した積層板が開示(例えば特許文献1参照)されているが、銅箔表面凹凸が 2μm以下になると、幅 40μm以下の回路では接着力が弱く、プリント配線板加工工程中に銅箔が剥離する等の問題点があった。更に、表層銅箔とプリプレグ中のガラス繊維が接触し、耐マイグレーション性等の電気絶縁性が低下するのを防止するため、表層銅箔とプリプレグ間に、ガラス繊維基材を含まない熱硬化性樹脂絶縁層を配置する方法(例えば特許文献2参照)が提案されているが、銅箔のマット面の凹凸が小さい場合、銅箔との接着力が低下し、改善が必要であった。
本発明は、銅箔の接着力が良好で、樹脂層と接する銅箔面の表面凹凸が極めて小さい銅箔付きBステージ樹脂組成物シート、並びに該銅箔付きBステージ樹脂組成物シートを使用する銅張積層板の製造方法の提供を目的とするものである。 The present invention uses a B-stage resin composition sheet with a copper foil and a B-stage resin composition sheet with a copper foil, in which the adhesive strength of the copper foil is good and the surface unevenness of the copper foil surface in contact with the resin layer is extremely small. It aims at providing the manufacturing method of a copper clad laminated board.
本発明は、銅箔の片面に、フィルム形成能を有する高耐熱性樹脂(a)層を形成し、この高耐熱性樹脂(a)層の上にBステージ樹脂組成物(b)層を形成させた銅箔付きBステージ樹脂組成物シートであり、好ましくは、該高耐熱性樹脂(a)層を形成する銅箔面の最大表面凹凸が 2μm以下であり、耐高熱性樹脂(a)層の厚みが 5〜10μmである銅箔付きBステージ樹脂組成物シートであり、この銅箔付きBステージ樹脂組成物シートを少なくとも表層に配置して、積層成形する銅張積層板の製造方法である。 In the present invention, a high heat resistant resin (a) layer having film-forming ability is formed on one surface of a copper foil, and a B stage resin composition (b) layer is formed on the high heat resistant resin (a) layer. B-stage resin composition sheet with copper foil, preferably, the maximum surface irregularity of the copper foil surface forming the high heat resistant resin (a) layer is 2 μm or less, and the high heat resistant resin (a) layer Is a B-stage resin composition sheet with a copper foil having a thickness of 5 to 10 μm, and this is a method for producing a copper-clad laminate in which the B-stage resin composition sheet with a copper foil is disposed at least on the surface layer and laminated. .
本発明の銅箔付きBステージ樹脂組成物シートを使用することにより、銅箔との接着力が良好で、銅箔の樹脂層と接する面の表面凹凸が極めて小さい銅張積層板が得られた。この銅張積層板は、細密回路を作製するのに好適であり、伝送損失が少ないことから、高周波用途等の高密度のプリント配線板に好適であり、工業的な実用性は極めて高いものである。 By using the B-stage resin composition sheet with a copper foil of the present invention, a copper-clad laminate having good adhesion to the copper foil and extremely small surface irregularities on the surface in contact with the resin layer of the copper foil was obtained. . This copper-clad laminate is suitable for producing fine circuits and has low transmission loss. Therefore, this copper-clad laminate is suitable for high-density printed wiring boards for high-frequency applications, and has extremely high industrial practicality. is there.
本発明は、銅箔の片面に、フィルム形成能を有する高耐熱性樹脂(a)層を形成し、この高耐熱性樹脂(a)層の上にBステージ樹脂組成物(b)層を形成させた銅箔付きBステージ樹脂組成物シートであり、これを少なくとも表層に配置して、積層成形する銅張積層板の製造方法である。本発明により得られる銅張積層板は、銅箔との接着力が良好で、樹脂層と接する銅箔面の表面凹凸が極めて小さいことから、細密回路を作製するのに好適であり、且つ伝送損失が少ないことから、高周波用途等の高密度プリント配線板として好適である。 In the present invention, a high heat resistant resin (a) layer having film-forming ability is formed on one surface of a copper foil, and a B stage resin composition (b) layer is formed on the high heat resistant resin (a) layer. This is a B-stage resin composition sheet with a copper foil, which is a method for producing a copper-clad laminate that is laminated and molded at least on the surface layer. The copper-clad laminate obtained by the present invention has good adhesive strength with copper foil, and the surface roughness of the copper foil surface in contact with the resin layer is extremely small. Therefore, the copper-clad laminate is suitable for producing a fine circuit and transmission. Since the loss is small, it is suitable as a high-density printed wiring board for high frequency applications.
本発明で使用する銅箔付きBステージ樹脂組成物シートは、銅箔の片面に、フィルム形成能を有する高耐熱性樹脂(a)を形成して樹脂複合銅箔とし、この高耐熱性樹脂(a)層の上にBステージ樹脂組成物(b)層を形成させた銅箔付きBステージ樹脂組成物シートであれば、特に限定されない。 The B-stage resin composition sheet with copper foil used in the present invention forms a resin composite copper foil by forming a high heat resistant resin (a) having film-forming ability on one surface of the copper foil. It will not specifically limit if it is a B stage resin composition sheet with a copper foil in which the B stage resin composition (b) layer is formed on the a) layer.
本発明で使用する樹脂複合銅箔の高耐熱性樹脂(a)層に使用する高耐熱性樹脂(a)は、フィルム形成能を有する、軟化点250℃以上の高耐熱性樹脂であれば特に限定されない。これらの高耐熱性樹脂(a)としては、具体的には、ポリアミドイミド、熱縮合型ポリイミド、全芳香族ポリアミド、ポリオキシベンザゾール、及びこれらの公知の変性品等が例示される。高耐熱性樹脂(a)の軟化点が250℃未満では、吸湿時に250℃を越えるリフローハンダ処理等の加熱において、膨れを生じる場合があり、軟化点は300℃以上のものが好適である。樹脂複合銅箔の高耐熱性樹脂(a)層の厚さは特に限定はないが、好適には 5〜10μmである。 The high heat-resistant resin (a) used in the high heat-resistant resin (a) layer of the resin composite copper foil used in the present invention is particularly a high heat-resistant resin having a film forming ability and a softening point of 250 ° C. or higher. It is not limited. Specific examples of these high heat resistant resins (a) include polyamideimide, heat condensation type polyimide, wholly aromatic polyamide, polyoxybenzazole, and known modified products thereof. When the softening point of the high heat-resistant resin (a) is less than 250 ° C, swelling may occur in heating such as reflow soldering treatment exceeding 250 ° C when moisture is absorbed, and the softening point is preferably 300 ° C or more. The thickness of the high heat resistant resin (a) layer of the resin composite copper foil is not particularly limited, but is preferably 5 to 10 μm.
銅箔付きBステージ樹脂組成物シートの高耐熱性樹脂(a)層を形成する銅箔は、プリント配線板に使用される公知の銅箔であれば、特に限定されないが、好適には電解銅箔、圧延銅箔、これらの銅合金等が使用される。これらの銅箔に、例えばニッケル、コバルト処理等、公知の表面処理が施されたものも使用可能である。銅箔の厚さは特に限定されないが、好適には35μm以下である。高耐熱性樹脂(a)層を形成する銅箔面の最大表面凹凸は、2μm以下が好適である。 The copper foil for forming the high heat-resistant resin (a) layer of the B-stage resin composition sheet with copper foil is not particularly limited as long as it is a known copper foil used for printed wiring boards, but preferably electrolytic copper. A foil, a rolled copper foil, a copper alloy thereof, or the like is used. These copper foils that have been subjected to a known surface treatment such as nickel or cobalt treatment can also be used. The thickness of the copper foil is not particularly limited, but is preferably 35 μm or less. The maximum surface irregularity of the copper foil surface forming the high heat resistant resin (a) layer is preferably 2 μm or less.
本発明の銅箔と高耐熱性樹脂(a)からなる樹脂複合銅箔を作製する方法は、特に限定はなく、例えば、熱縮合型ポリイミド樹脂溶液をロール等で銅箔上に塗布・乾燥して、溶剤除去後、更に加熱し、架橋させて樹脂複合銅箔とする方法、半硬化状態の熱縮合型ポリイミド樹脂をシート状に形成したものを、銅箔の片面に配置し、真空プレス等で圧着させるとともに加熱し、架橋させて樹脂複合銅箔とする方法等、公知の方法が用いられ得る。 The method for producing the resin composite copper foil comprising the copper foil of the present invention and the high heat-resistant resin (a) is not particularly limited. After removing the solvent, further heating and crosslinking to form a resin composite copper foil, a semi-cured thermally condensed polyimide resin formed into a sheet, placed on one side of the copper foil, vacuum press etc. A known method such as a method in which a resin composite copper foil is formed by pressure bonding and heating and cross-linking may be used.
銅箔付きBステージ樹脂組成物シートのBステージ樹脂組成物(b)層に使用する樹脂組成物(b)としては、プリント配線板に使用される公知の熱硬化性樹脂組成物であれば、特に限定されない。これらの樹脂としては、例えば、エポキシ樹脂、ポリイミド樹脂、シアン酸エステル樹脂、マレイミド樹脂、2重結合付加ポリフェニレンエーテル樹脂、これらの樹脂の臭素やリン含有化合物等の樹脂組成物などが挙げられ、1種或いは2種以上が組み合わせて使用される。耐マイグレーション性等の信頼性、耐熱性等の点から、シアン酸エステル樹脂を必須成分とする樹脂組成物、例えばエポキシ樹脂等との併用が好適である。これら熱硬化性樹脂には、必要に応じて、公知の触媒、硬化剤、硬化促進剤を使用する。 As the resin composition (b) used for the B-stage resin composition (b) layer of the B-stage resin composition sheet with copper foil, if it is a known thermosetting resin composition used for a printed wiring board, There is no particular limitation. Examples of these resins include epoxy resins, polyimide resins, cyanate ester resins, maleimide resins, double bond-added polyphenylene ether resins, and resin compositions such as bromine and phosphorus-containing compounds of these resins. Species or two or more are used in combination. From the viewpoint of reliability such as migration resistance and heat resistance, it is preferable to use a resin composition containing a cyanate ester resin as an essential component, for example, an epoxy resin. For these thermosetting resins, known catalysts, curing agents, and curing accelerators are used as necessary.
Bステージ樹脂組成物(b)層に使用する樹脂組成物(b)に好適に使用されるシアン酸エステル樹脂とは、分子内に2個以上のシアナト基を有する化合物である。具体的に例示すると、1,3-又は1,4-ジシアナトベンゼン、1,3,5-トリシアナトベンゼン、1,3-、1,4-、1,6-、1,8-、2,6-又は2,7-ジシアナトナフタレン、1,3,6-トリシアナトナフタレン、4,4-ジシアナトビフェニル、ビス(4-ジシアナトフェニル)メタン、2,2-ビス(4-シアナトフェニル)プロパン、2,2-ビス(3,5-ジブロモー4-シアナトフェニル)プロパン、ビス(4-シアナトフェニル)エーテル、ビス(4-シアナトフェニル)チオエーテル、ビス(4-シアナトフェニル)スルホン、トリス(4-シアナトフェニル)ホスファイト、トリス(4-シアナトフェニル)ホスフェート、およびノボラックとハロゲン化シアンとの反応により得られるシアネート類等である。 The cyanate ester resin suitably used for the resin composition (b) used in the B-stage resin composition (b) layer is a compound having two or more cyanato groups in the molecule. Specific examples include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2 , 6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, bis (4-dicyanatophenyl) methane, 2,2-bis (4-cyanato Phenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) ) Sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and cyanates obtained by the reaction of novolac and cyanogen halide.
これらのほかに特公昭41-1928、同43-18468、同44-4791、同45-11712、同46-41112、同47-26853及び特開昭51-63149等に記載のフェノールノボラック型シアン酸エステル化合物類等も用い得る。又、ナフタレン型シアン酸エステル化合物類も用いられ得る。更に、これらシアン酸エステル化合物のシアナト基の三量化によって形成されるトリアジン環を有する分子量 400〜6,000 のプレポリマーが使用される。このプレポリマーは、上記のシアン酸エステルモノマーを、例えば鉱酸、ルイス酸等の酸類;ナトリウムアルコラート等、第三級アミン類等の塩基;炭酸ナトリウム等の塩類等を触媒として重合させることにより得られる。この樹脂中には一部未反応のモノマーも含まれており、モノマーとプレポリマーとの混合物の形態をしており、このような原料は本発明の用途に好適に使用される。更にはシアナト化ポリフェニレンエーテル樹脂も使用できる。これらに1官能のシアン酸エステル化合物も特性に大きく影響しない量を添加できる。好適には 1〜10重量%である。これらのシアン酸エステル化合物は上記のものに限定されず、公知のものが使用可能である。これらは1種或いは2種以上が適宜組み合わせて使用される。 In addition to these, phenol novolac type cyanic acid described in JP-B-41-1928, 43-18468, 44-4791, 45-11712, 46-41112, 47-26853 and JP-A-51-63149, etc. Ester compounds and the like can also be used. Naphthalene-type cyanate ester compounds can also be used. Further, a prepolymer having a molecular weight of 400 to 6,000 having a triazine ring formed by trimerization of cyanate groups of these cyanate ester compounds is used. This prepolymer is obtained by polymerizing the above-mentioned cyanate ester monomers using, for example, acids such as mineral acids and Lewis acids; bases such as sodium alcoholates and tertiary amines; salts such as sodium carbonate and the like as catalysts. It is done. This resin also contains a partially unreacted monomer and is in the form of a mixture of a monomer and a prepolymer, and such a raw material is suitably used for the application of the present invention. Furthermore, cyanated polyphenylene ether resin can also be used. A monofunctional cyanate ester compound can also be added to these in an amount that does not significantly affect the properties. 1 to 10% by weight is preferred. These cyanate ester compounds are not limited to those described above, and known compounds can be used. These may be used alone or in combination of two or more.
シアン酸エステル樹脂に好適に併用されるエポキシ樹脂としては、公知のものが使用できる。具体的には、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、レゾルシン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、エポキシ化ポリフェニレンエーテル樹脂;ブタジエン、ペンタジエン、ビニルシクロヘキセン、ジシクロペンチルエーテル等の二重結合をエポキシ化したポリエポキシ化合物類;ポリオール、水酸基含有シリコン樹脂類とエピクロヒドリンとの反応によって得られるポリグリシジル化合物類等が挙げられる。又、これらの公知の臭素付加樹脂、リン含有エポキシ樹脂等が挙げられる。これらは1種或いは2種類以上が適宜組み合わせて使用される。 As an epoxy resin suitably used in combination with a cyanate ester resin, known resins can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcin type epoxy resin, Naphthalene type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, epoxidized polyphenylene ether resin; polyepoxy compounds with epoxidized double bonds such as butadiene, pentadiene, vinylcyclohexene, dicyclopentyl ether; polyol, hydroxyl group Examples thereof include polyglycidyl compounds obtained by the reaction of containing silicon resins with epichlorohydrin. Moreover, these well-known bromine addition resin, phosphorus containing epoxy resin, etc. are mentioned. These may be used alone or in combination of two or more.
Bステージ樹脂組成物(b)層に使用する樹脂組成物(b)には、組成物本来の特性が損なわれない範囲で、所望に応じて種々の添加物を配合することができる。これらの添加物としては、不飽和ポリエステル等の重合性二重結合含有モノマー類及びそのプレポリマー類;ポリブタジエン、マレイン化ブタジエン、ブタジエン-アクリロニトリル共重合体、ポリクロロプレン、ブタジエン-スチレン共重合体、ポリイソプレン、ブチルゴム、フッ素ゴム、天然ゴム等の低分子量液状〜高分子量のelasticなゴム類;ポリエチレン、ポリプロピレン、ポリブテン、ポリ-4-メチルペンテン、ポリスチレン、AS樹脂、ABS樹脂、MBS樹脂、スチレン-イソプレンゴム、アクリルゴム、これらのコアシェルゴム、ポリエチレン-プロピレン共重合体、4-フッ化エチレン-6-フッ化エチレン共重合体類;ポリカーボネート、ポリフェニレンエーテル、ポリスルホン、ポリエステル、ポリフェニレンサルファイド等の高分子量プレポリマー若しくはオリゴマー;ポリウレタン等が例示され、適宜使用される。また、その他、公知の有機、無機の充填剤、染料、顔料、増粘剤、滑剤、消泡剤、分散剤、レベリング剤、光増感剤、難燃剤、光沢剤、重合禁止剤、チキソ性付与剤等の各種添加剤が、所望に応じて適宜組み合わせて用いられる。 In the resin composition (b) used for the B-stage resin composition (b) layer, various additives can be blended as desired as long as the original properties of the composition are not impaired. These additives include unsaturated double bond-containing monomers such as unsaturated polyesters and prepolymers thereof; polybutadiene, maleated butadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, poly Low molecular weight liquid to high molecular weight elastic rubber such as isoprene, butyl rubber, fluoro rubber, natural rubber; polyethylene, polypropylene, polybutene, poly-4-methylpentene, polystyrene, AS resin, ABS resin, MBS resin, styrene-isoprene Rubber, acrylic rubber, these core-shell rubbers, polyethylene-propylene copolymers, 4-fluoroethylene-6-fluoroethylene copolymers; high molecular weight prepolymers such as polycarbonate, polyphenylene ether, polysulfone, polyester, polyphenylene sulfide Properly oligomer; are exemplified polyurethane, etc., it is suitably used. In addition, other known organic and inorganic fillers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, thixotropic properties Various additives such as an imparting agent are used in appropriate combination as desired.
本発明の銅箔付きBステージ樹脂組成物シートに使用するBステージ樹脂組成物(b)層には、全体のプリント配線板の剛性率を向上させることから、基材を使用することが好適である。使用される基材としては、プリント配線板に使用される公知の基材であれば、特に限定されない。具体的には、E、NE、D、S、Tガラス等の一般に公知のガラス繊維の不織布、織布;ポリオキシベンザゾール、全芳香族ポリアミド、液晶ポリエステル等の一般に公知の有機繊維不織布、織布;これらの混抄布;ポリイミドフィルム、全芳香族ポリアミドフィルム、ポリオキシベンザゾールフィルム、液晶ポリエステルフィルム等が挙げられる。これらの基材は、樹脂組成物との密着性を向上させるため、公知の表面処理を施すことが好ましい。 The B-stage resin composition (b) layer used in the B-stage resin composition sheet with a copper foil of the present invention is preferably used as a base material because the rigidity of the entire printed wiring board is improved. is there. As a base material to be used, if it is a well-known base material used for a printed wiring board, it will not specifically limit. Specifically, generally known non-woven fabrics and woven fabrics of glass fibers such as E, NE, D, S, and T glass; generally known non-woven fabrics and woven fabrics such as polyoxybenzazole, wholly aromatic polyamide, and liquid crystalline polyester. Cloth; these mixed papers; polyimide film, wholly aromatic polyamide film, polyoxybenzazole film, liquid crystal polyester film and the like. These base materials are preferably subjected to a known surface treatment in order to improve adhesion with the resin composition.
高耐熱性樹脂(a)層の上にBステージ樹脂組成物(b)層を形成し、銅箔付きBステージ樹脂組成物シートとする方法は特に限定はなく、例えば、熱硬化性樹脂組成物を無溶剤もしくは溶剤に溶解・分散させ、直接高耐熱性樹脂(a)層面に塗布・乾燥するか、或いは離型フィルムに塗布・乾燥してBステージ樹脂組成物シートとし、この樹脂組成物面を、高耐熱性樹脂(a)層面に対向させ、ラミネート等で加熱圧着させ、銅箔付きBステージ樹脂組成物シートとする方法、基材を使用する場合、熱硬化性樹脂組成物ワニスを基材に塗布、乾燥させてプリプレグを作製するか、或いは前記Bステージ樹脂組成物シートを、基材の両面に配置して加熱圧着等で一体化してプリプレグを作製し、高耐熱性樹脂(a)層の上にラミネート等で圧着させる方法等、公知の方法が用いられる。Bステージ樹脂組成物(b)層の厚さは特に限定されないが、好適には 4〜200μmであり、用途によって適宜選択する。Bステージ樹脂組成物(b)の硬化度は、高耐熱性樹脂(a)層上に形成させた時点で、Bステージとする。以上により、本発明の銅箔付きBステージ樹脂組成物シートが得られ、一般の積層用のシートやビルドアップ工法用等として使用できる。 There is no particular limitation on the method of forming the B-stage resin composition (b) layer on the high heat-resistant resin (a) layer to obtain a B-stage resin composition sheet with copper foil. For example, a thermosetting resin composition Is dissolved or dispersed in a solvent-free or solvent and directly applied to the surface of the high heat resistant resin (a) layer or dried, or applied to the release film and dried to form a B-stage resin composition sheet. Facing the high heat-resistant resin (a) layer surface, and heat-pressing with a laminate or the like to make a B-stage resin composition sheet with copper foil, when using a substrate, based on the thermosetting resin composition varnish A prepreg is prepared by applying to a material and drying, or the B-stage resin composition sheet is arranged on both surfaces of a substrate and integrated by thermocompression bonding or the like to produce a prepreg, and a high heat resistant resin (a) Known methods such as laminating on the layer with a laminate Method is used. The thickness of the B-stage resin composition (b) layer is not particularly limited, but is preferably 4 to 200 μm, and is appropriately selected depending on the application. The degree of cure of the B stage resin composition (b) is set to the B stage when it is formed on the high heat resistant resin (a) layer. As described above, the B-stage resin composition sheet with copper foil of the present invention is obtained, and can be used as a general lamination sheet, a build-up method, or the like.
本発明の銅張積層板の製造方法は、上記銅箔付きBステージ樹脂組成物シートを、プリント配線板用の積層材料の少なくとも表層に配置して、積層成形して銅張積層板とするものである。具体的には、銅箔付きBステージ樹脂組成物シートの樹脂層面を、前記樹脂組成物(b)系のプリプレグの少なくとも片面に、対向させて配置し、加熱、加圧、好ましくは真空下で積層成形して銅張積層板とする。プリプレグの代わりに銅箔を張っていない積層板でも良く、多層板を作製する場合は、導体回路を形成した回路基板の両面に銅箔付きBステージ樹脂組成物シートを配置し、加熱、加圧、好ましくは真空下で積層成形して多層銅張積層板とする。 The method for producing a copper-clad laminate of the present invention is such that the B-stage resin composition sheet with a copper foil is placed on at least the surface layer of a laminate material for a printed wiring board and laminated to form a copper-clad laminate. It is. Specifically, the resin layer surface of the B-stage resin composition sheet with copper foil is disposed to face at least one surface of the prepreg of the resin composition (b) system, and is heated and pressurized, preferably under vacuum. Laminate to form a copper clad laminate. Instead of the prepreg, a laminated board without a copper foil may be used. When a multilayer board is produced, a B-stage resin composition sheet with copper foil is placed on both sides of a circuit board on which a conductor circuit is formed, and heated and pressed. Preferably, the multilayer copper clad laminate is formed by lamination under vacuum.
本発明の銅箔付きBステージ樹脂組成物シートに貼り合わせる積層板や回路基板の種類は、特に限定されず、プリント配線板材料用の公知の積層板、金属箔張板、好適には銅張板が使用できる。具体的には、熱硬化性樹脂組成物及び/又は熱可塑性樹脂組成物などを使用した、無機繊維及び/又は有機繊維基材銅張積層板、耐熱性フィルム基材銅張板、更にはこれらの基材の組み合わせた複合基材銅張積層板及びこれらの多層銅張板、アディティブ法等で作製した多層銅張板等、公知のものが使用できる。回路基板の導体厚さは特に限定されないが、好適には 3〜35μmである。この導体回路上は、Bステージ樹脂組成物シートの樹脂との密着性を高める公知の処理、例えば黒色酸化銅処理、薬液処理(例えばメック社のCZ処理)等を施すのが好ましい。 The kind of the laminated board or circuit board to be bonded to the B-stage resin composition sheet with copper foil of the present invention is not particularly limited, and is a known laminated board, metal foil-clad board for printed wiring board materials, preferably copper-clad. A board can be used. Specifically, inorganic fiber and / or organic fiber-based copper-clad laminates, heat-resistant film-based copper-clad plates using thermosetting resin compositions and / or thermoplastic resin compositions, and further these Known materials such as composite base material copper clad laminates obtained by combining these base materials, multilayer copper clad plates, multilayer copper clad plates prepared by the additive method, and the like can be used. The conductor thickness of the circuit board is not particularly limited, but is preferably 3 to 35 μm. On this conductor circuit, it is preferable to perform a known process for enhancing the adhesion of the B-stage resin composition sheet to the resin, for example, black copper oxide treatment, chemical solution treatment (for example, CZ treatment by MEC).
本発明の銅張積層板の積層条件は特に限定されないが、好ましくは、温度 100〜250℃、圧力 5〜40kgf/cm2、真空度 30mmHg以下で 30分〜5時間積層成形する。積層は、最初から最後までこの条件でも良いが、ゲル化までは積層成形し、その後、取り出して加熱炉で後硬化することも可能である。 The lamination conditions of the copper-clad laminate of the present invention are not particularly limited, but are preferably laminated and formed at a temperature of 100 to 250 ° C., a pressure of 5 to 40 kgf / cm 2 , and a degree of vacuum of 30 mmHg or less for 30 minutes to 5 hours. Lamination may be performed under these conditions from the beginning to the end, but it is also possible to laminate and form until gelation, and then take out and post-cure in a heating furnace.
以下に実施例、比較例で本発明を具体的に説明する。尚、『部』は重量部を表す。
<合成例1>
5リットルのフラスコにp-フェニレンジアミン 108部、及びN-メチル-2-ピロリドン(以下NMP)2500部を加えてよく攪拌混合して溶解させた。このフラスコを氷水で冷やして液温を 30℃以下に保持しながら、攪拌下に、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物 294部を徐々に加え、添加終了後に2時間反応させ、ポリアミド酸NMP溶液Aを得た。この溶液Aを加温して粘度 1000ポイズ以下に下げ、これをガラス板の上に置いた厚さ 12μmの電解銅箔(最大表面凹凸:1.1μm、Rz:0.9μm)に塗布し、150℃で30分、200℃で60分加熱乾燥し、更に 300℃で1時間反応させ、その後室温まで冷却し、軟化点300℃以上のポリイミド層(厚さ:9μm)を有する樹脂複合銅箔Bを得た。
The present invention will be specifically described below with reference to examples and comparative examples. “Parts” represents parts by weight.
<Synthesis Example 1>
108 parts of p-phenylenediamine and 2500 parts of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were added to a 5 liter flask, and the mixture was thoroughly stirred and dissolved. While this flask was cooled with ice water and the liquid temperature was kept at 30 ° C. or lower, 294 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was gradually added under stirring, and 2 was added after the addition was completed. Reaction was performed for a time to obtain a polyamic acid NMP solution A. This solution A is heated to reduce the viscosity to 1000 poise or less, and this is applied to a 12 μm thick electrolytic copper foil (maximum surface irregularities: 1.1 μm, Rz: 0.9 μm) placed on a glass plate, and 150 ° C. The resin composite copper foil B having a polyimide layer (thickness: 9 μm) having a softening point of 300 ° C. or higher is then heated and dried at 200 ° C. for 60 minutes, further reacted at 300 ° C. for 1 hour, and then cooled to room temperature. Obtained.
実施例1
2,2-ビス(4-シアナトフェニル)プロパンモノマー 400部を 150℃に溶融させ、撹拌しながら4時間反応させ、モノマーとプレポリマーの混合物を得、これをメチルエチルケトンに溶解し、ワニスCとした。これにビスフェノールA型エポキシ樹脂(エピコート1001、ジャパンエポキシレジン<株>製) 350部、ビフェニル型エポキシ樹脂(NC3000、日本化薬<株>製) 50部、フェノールノボラック型エポキシ樹脂(DEN438、ダウ・ケミカル<株>製) 100部を配合し、アセチルアセトン鉄 0.3部をメチルエチルケトンに溶解混合し、更に焼成タルク(BST200、日本タルク<株>製) 500部を加え、均一に混合してワニスDとした。このワニスDを、厚さ 100μmのガラス織布基材に含浸、乾燥して、厚さ 105μmでゲル化時間(at170℃、以下同じ) 118秒のBステージ樹脂組成物シート(プリプレグ) Eを作製し、この両面に厚さ25μmの離型PETフィルムを当て、80℃、5kgf/cmの線圧でラミネートしてBステージ樹脂組成物シートFとした。次に、合成例1の樹脂複合銅箔Bの樹脂面を、Bステージ樹脂組成物シートFの片面の離型PETフィルムを剥離し、対向して配置して90℃、5kgf/cmの線圧でラミネートして接着させ、銅箔付きBステージ樹脂組成物シートGを作製した。次に、銅箔付きBステージ樹脂組成物シートGの樹脂面の離型PETフィルムを剥離後に、プリプレグEを 8枚を重ねたものの上下面に、プリプレグ面と対向して配置し、190℃、20kgf/cm2、10mmHgの真空下で2時間積層成形して両面銅張積層板Hを作製した。評価結果を表1に示す。
Example 1
400 parts of 2,2-bis (4-cyanatophenyl) propane monomer is melted at 150 ° C. and reacted for 4 hours with stirring to obtain a mixture of monomer and prepolymer, which is dissolved in methyl ethyl ketone, and varnish C did. To this, 350 parts of bisphenol A type epoxy resin (Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts of biphenyl type epoxy resin (NC3000, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type epoxy resin (DEN438, Dow Chemical 100), 100 parts of acetylacetone iron 0.3 parts is dissolved and mixed in methyl ethyl ketone, and 500 parts of baked talc (BST200, Nippon Talc Co., Ltd.) is added and mixed uniformly to make varnish D. . This varnish D is impregnated into a glass woven fabric substrate having a thickness of 100 μm, dried, and a B-stage resin composition sheet (prepreg) E having a thickness of 105 μm and a gel time (at 170 ° C., the same applies hereinafter) of 118 seconds is produced. Then, a release PET film having a thickness of 25 μm was applied to both surfaces and laminated at 80 ° C. with a linear pressure of 5 kgf / cm to obtain a B-stage resin composition sheet F. Next, the release PET film on one side of the B-stage resin composition sheet F is peeled off from the resin surface of the resin composite copper foil B of Synthesis Example 1 and placed facing each other at a linear pressure of 90 ° C. and 5 kgf / cm. Were laminated and bonded to produce a B-stage resin composition sheet G with a copper foil. Next, after peeling off the release PET film on the resin surface of the B-stage resin composition sheet G with copper foil, the prepreg E was placed on the upper and lower surfaces of the 8 sheets, facing the prepreg surface, 190 ° C., A double-sided copper-clad laminate H was prepared by laminate molding for 2 hours under a vacuum of 20 kgf / cm 2 and 10 mmHg. The evaluation results are shown in Table 1.
実施例2
ブロム化ビスフェノールA型エポキシ樹脂(エピコート5045、ジャパンエポキシレジン<株>製) 800部、フェノールノボラック型エポキシ樹脂(DEN431)200部、ジシアンジアミド 35部、2-エチル-4-メチルイミダゾール 1部をメチルエチルケトンとジメチルホルムアミド混合溶剤に溶解混合し、更にタルク(P-3、日本タルク<株>製)700部を添加し、均一に混合してワニスJとした。このワニスJを、厚さ 25μmのPETフィルムの片面に塗布、乾燥して、厚さ 105μmでゲル化時間 155秒の離型フィルム付きBステージ樹脂組成物シートKを作製した。次に、合成例1の樹脂複合銅箔Bの樹脂面を、離型フィルム付きBステージ樹脂組成物シートKの樹脂組成物面と対向して配置し、90℃、5kgf/cmの線圧でラミネートして接着させ、銅付きBステージ樹脂組成物シートLを作製した。一方、厚さ 0.8mmのBTレジン両面銅張(3μm)積層板(CCL-HL832HS、三菱ガス化学<株>製)を使用し、この両面に回路を形成し、黒色酸化銅処理を施して回路基板Mを作製した。次いで、銅付きBステージ樹脂組成物シートLの樹脂組成物面を、回路基板Mの表裏の回路面に、対向して配置し、160℃、20kgf/cm2、10mmHgの真空下で 30分積層成形後にプレス装置から取り出し、加熱炉で 170℃にて5時間硬化させ、4層銅張積層板Nを得た。評価結果を表1に示す。
Example 2
Brominated bisphenol A type epoxy resin (Epicoat 5045, manufactured by Japan Epoxy Resin Co., Ltd.) 800 parts, phenol novolac type epoxy resin (DEN431) 200 parts, dicyandiamide 35 parts, 2-ethyl-4-methylimidazole 1 part with methyl ethyl ketone Dissolved and mixed in a dimethylformamide mixed solvent, 700 parts of talc (P-3, manufactured by Nippon Talc Co., Ltd.) was further added, and mixed uniformly to obtain Varnish J. This varnish J was applied to one side of a PET film having a thickness of 25 μm and dried to prepare a B-stage resin composition sheet K with a release film having a thickness of 105 μm and a gel time of 155 seconds. Next, the resin surface of the resin composite copper foil B of Synthesis Example 1 is placed facing the resin composition surface of the B-stage resin composition sheet K with a release film, and the linear pressure is 90 ° C. and 5 kgf / cm. Lamination and adhesion were performed to prepare a B-stage resin composition sheet L with copper. On the other hand, a BT resin double-sided copper-clad (3μm) laminate (CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 0.8mm is used, a circuit is formed on both sides, and black copper oxide treatment is applied to the circuit. A substrate M was produced. Next, the resin composition surface of the B-stage resin composition sheet L with copper is placed facing the front and back circuit surfaces of the circuit board M, and laminated for 30 minutes under a vacuum of 160 ° C., 20 kgf / cm 2 , 10 mmHg. After forming, the sheet was taken out from the press machine and cured at 170 ° C. for 5 hours in a heating furnace to obtain a four-layer copper-clad laminate N. The evaluation results are shown in Table 1.
比較例1
実施例2において、銅箔付きBステージ樹脂組成物シートLの代わりに離型フィルム付きBステージ樹脂組成物シートKだけを使用し、離型フィルムを剥離して回路基板Tの表裏面に配置し、その両外側に合成例1で使用した銅箔を配置し、実施例2と同様に積層成形して4層銅張積層板Oを作製した。評価結果を表1に示す。
Comparative Example 1
In Example 2, instead of the B-stage resin composition sheet L with copper foil, only the B-stage resin composition sheet K with a release film was used, and the release film was peeled off and placed on the front and back surfaces of the circuit board T. And the copper foil used by the synthesis example 1 was arrange | positioned on the both outer sides, and it laminate-molded similarly to Example 2, and produced the 4-layer copper clad laminated board O. FIG. The evaluation results are shown in Table 1.
比較例2
実施例1において、銅箔付きBステージ樹脂組成物シートGの代わりに、Bステージ樹脂組成物シートFのみを用い、銅箔として厚さ 12μmキャリア銅箔付き 3μm電解銅箔(マット面最大表面凹凸Max.4.1μm、Rz:3.3μm)を使用する以外は、実施例1と同様に積層成形して両面銅張積層板Pを作製した。評価結果を表1に示す。
Comparative Example 2
In Example 1, instead of the B-stage resin composition sheet G with the copper foil, only the B-stage resin composition sheet F was used, and the copper foil had a thickness of 12 μm with the carrier copper foil 3 μm electrolytic copper foil (matt surface maximum surface irregularities) A double-sided copper-clad laminate P was produced by laminate molding in the same manner as in Example 1 except that Max.4.1 μm, Rz: 3.3 μm) was used. The evaluation results are shown in Table 1.
比較例3
樹脂複合銅箔としてポリイミドの代わりにポリフェニレンエーテル樹脂(軟化点240℃)を使用した樹脂複合銅箔Qを作製し、実施例1において、樹脂複合銅箔Bの代わりに樹脂複合銅箔Qを使用する以外は、実施例1と同様に行い、銅箔付きBステージ樹脂組成物シートRを作製し、同様に積層成形して両面銅張板Sを作製した。評価結果を表1に示す。
Comparative Example 3
A resin composite copper foil Q using a polyphenylene ether resin (softening point 240 ° C.) instead of polyimide as a resin composite copper foil is prepared. In Example 1, the resin composite copper foil Q is used instead of the resin composite copper foil B A B-stage resin composition sheet R with a copper foil was produced in the same manner as in Example 1 except that the double-sided copper-clad plate S was produced by laminating in the same manner. The evaluation results are shown in Table 1.
表1 実 施 例 比 較 例
項 目 1 2 1 2 3
銅箔接着力(kgf/cm) 1.60 1.55 0.16 1.51 1.38
最大表面凹凸(μm) 1.2 1.1 1.1 3.6 1.2
吸湿耐熱性 異常なし 異常なし 膨れ発生 異常なし 膨れ発生
孔壁間又は回路間耐マイグレーション性(Ω)
常 態 5×1014 6×1014 6×1014 6×1014 5×1014
300hrs. 3×1011 <108 <108 1×1011 3×1011
500hrs. 5×1011 − 2×1010 3×1010
700hrs. 3×1010 8×109 4×109
1000hrs. 2×1010 5×109 2×109
Z方向耐マイグレーション性(Ω)
常 態 3×1014 3×1014 5×1014 4×1014 5×1014
300hrs. 6×1011 3×1011 <108 7×1010 9×1010
500hrs. 8×1010 4×1010 − 3×1010 2×1010
700hrs. 7×1010 3×1010 2×109 8×109
1000hrs. 7×1010 2×1010 1×108 5×109
弾性率(kgf/mm2) 2410 2159 2105 2451 2377
伝送損失減衰量(dB) 0.08 0.11 0.11 0.41 0.10
Table 1 Example Comparison Example
Item 1 2 1 2 3
Copper foil adhesive strength (kgf / cm) 1.60 1.55 0.16 1.51 1.38
Maximum surface irregularities (μm) 1.2 1.1 1.1 3.6 1.2
Absorption heat resistance No abnormality No abnormality Bulging occurrence No abnormality Bulging occurrence Migration resistance between hole walls or circuits (Ω)
Normal 5 × 10 14 6 × 10 14 6 × 10 14 6 × 10 14 5 × 10 14
300hrs. 3 × 10 11 <10 8 <10 8 1 × 10 11 3 × 10 11
500hrs. 5 × 10 11 − 2 × 10 10 3 × 10 10
700hrs. 3 × 10 10 8 × 10 9 4 × 10 9
1000hrs. 2 × 10 10 5 × 10 9 2 × 10 9
Z-direction migration resistance (Ω)
Normal 3 × 10 14 3 × 10 14 5 × 10 14 4 × 10 14 5 × 10 14
300hrs. 6 × 10 11 3 × 10 11 <10 8 7 × 10 10 9 × 10 10
500hrs. 8 × 10 10 4 × 10 10 −3 × 10 10 2 × 10 10
700hrs. 7 × 10 10 3 × 10 10 2 × 10 9 8 × 10 9
1000hrs. 7 × 10 10 2 × 10 10 1 × 10 8 5 × 10 9
Elastic modulus (kgf / mm 2 ) 2410 2159 2105 2451 2377
Transmission loss attenuation (dB) 0.08 0.11 0.11 0.41 0.10
<測定方法>
1)銅箔接着力:銅箔に銅メッキして厚さ 18μmとしてから JIS C6481に準じて測定した。
2) 最大表面凹凸:銅箔をエッチングした積層板の表面凹凸を表面粗さ計で測定し最大値を示した。
3)吸湿耐熱性:プレッシャクッカー試験機で 121℃/203kPaで3時間処理した後、260℃の半田に 30sec.浸漬し、外観の異常の有無を目視で判定した。
4)孔壁間又は回路間耐マイグレーション性:実施例1、比較例2,3は孔壁間 150μmの貫通孔を有するプリント板を作製し、この孔壁間の絶縁抵抗値を、実施例2、比較例1は内層の回路導体間距離を 40μmとした表層回路のないプリント配線板を作製し、内層の回路間の絶縁抵抗値を、85℃・85%RH、100VDC 印加して測定した。
5)Z方向耐マイグレーション性:表裏に回路を形成したプリント板を作製し、実施例1、比較例2,3は表裏の絶縁抵抗値を、実施例2、比較例1は内層と表面回路間の絶縁抵抗値を、85℃・85%RH、100VDC 印加して測定した。
6)弾性率:回路導体及び孔の形成を行わずに、同様の構成で絶縁体だけの積層板を作製し、JIS C6481のDMA法に準じて弾性率を測定し、25℃の弾性率を示した。
7)伝送損失減衰量:銅張積層板の表層にマイクロストリップライン{ライン幅 250μm、長さ 100mm、銅箔(+銅メッキ)厚さ35μm、絶縁層厚さ 100μm}を作製し、1GHzで測定した。測定器:ネットワークアナライザー(アジデントテクノロジー<株>製、8722ES)
<Measurement method>
1) Copper foil adhesive strength: The copper foil was plated with copper to a thickness of 18 μm and then measured according to JIS C6481.
2) Maximum surface unevenness: The surface unevenness of the laminated plate etched with copper foil was measured with a surface roughness meter, and the maximum value was shown.
3) Moisture absorption heat resistance: Treated with a pressure cooker at 121 ° C / 203kPa for 3 hours, then immersed in 260 ° C solder for 30 seconds, and visually checked for abnormal appearance.
4) Migration resistance between hole walls or between circuits: Example 1 and Comparative Examples 2 and 3 produced printed boards having through-holes of 150 μm between the hole walls. In Comparative Example 1, a printed wiring board without a surface layer circuit having a distance between circuit conductors of the inner layer of 40 μm was prepared, and the insulation resistance value between the circuits of the inner layer was measured by applying 100 VDC at 85 ° C./85% RH.
5) Migration resistance in the Z direction: A printed board having a circuit formed on the front and back sides was prepared. In Example 1, Comparative Examples 2 and 3, the insulation resistance values on the front and back sides were measured. In Example 2 and Comparative Example 1, between the inner layer and the surface circuit The insulation resistance was measured by applying 100 VDC at 85 ° C / 85% RH.
6) Modulus of elasticity: Without the formation of circuit conductors and holes, a laminated board made of only an insulator with the same configuration was measured. The modulus of elasticity was measured according to the DMA method of JIS C6481, and the modulus of elasticity at 25 ° C was measured. Indicated.
7) Transmission loss attenuation: A microstrip line {line width 250μm, length 100mm, copper foil (+ copper plating) thickness 35μm, insulation layer thickness 100μm} on the surface layer of a copper clad laminate was measured at 1GHz. did. Measuring instrument: Network analyzer (manufactured by Agilent Technology Co., Ltd., 8722ES)
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004102924A JP4390056B2 (en) | 2004-03-31 | 2004-03-31 | B-stage resin composition sheet and method for producing copper-clad laminate using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004102924A JP4390056B2 (en) | 2004-03-31 | 2004-03-31 | B-stage resin composition sheet and method for producing copper-clad laminate using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005288714A true JP2005288714A (en) | 2005-10-20 |
JP4390056B2 JP4390056B2 (en) | 2009-12-24 |
Family
ID=35322222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004102924A Expired - Lifetime JP4390056B2 (en) | 2004-03-31 | 2004-03-31 | B-stage resin composition sheet and method for producing copper-clad laminate using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4390056B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012132383A1 (en) * | 2011-03-31 | 2012-10-04 | 住友ベークライト株式会社 | Laminate sheet manufacturing device and method for manufacturing laminate sheet |
KR101308119B1 (en) * | 2006-01-25 | 2013-09-12 | 피아이 알 앤 디 컴파니, 리미티드 | Resin composite copper foil, printed wiring board, and production process thereof |
CN103625037A (en) * | 2012-08-28 | 2014-03-12 | 昆山雅森电子材料科技有限公司 | Combined ultrathin double-side copper foil substrate and making method thereof |
JP2014139012A (en) * | 2005-12-06 | 2014-07-31 | Isola Usa Corp | Laminates for high speed and high frequency printed circuit boards |
CN105984181A (en) * | 2015-02-11 | 2016-10-05 | 昆山雅森电子材料科技有限公司 | Double-sided copper foil substrate for printed circuit board and manufacturing method thereof |
-
2004
- 2004-03-31 JP JP2004102924A patent/JP4390056B2/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014139012A (en) * | 2005-12-06 | 2014-07-31 | Isola Usa Corp | Laminates for high speed and high frequency printed circuit boards |
KR101308119B1 (en) * | 2006-01-25 | 2013-09-12 | 피아이 알 앤 디 컴파니, 리미티드 | Resin composite copper foil, printed wiring board, and production process thereof |
WO2012132383A1 (en) * | 2011-03-31 | 2012-10-04 | 住友ベークライト株式会社 | Laminate sheet manufacturing device and method for manufacturing laminate sheet |
CN103625037A (en) * | 2012-08-28 | 2014-03-12 | 昆山雅森电子材料科技有限公司 | Combined ultrathin double-side copper foil substrate and making method thereof |
CN105984181A (en) * | 2015-02-11 | 2016-10-05 | 昆山雅森电子材料科技有限公司 | Double-sided copper foil substrate for printed circuit board and manufacturing method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP4390056B2 (en) | 2009-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7115681B2 (en) | Resin composition | |
JP5641942B2 (en) | Resin composite copper foil | |
JP2007196471A (en) | Resin composite copper foil, and its manufacturing method | |
JP2003340952A (en) | Method for manufacturing b-stage resin composition sheet containing fibrous cloth base material for additive | |
JP4767517B2 (en) | Resin composite copper foil, copper-clad laminate and printed wiring board using the same | |
JPH08193139A (en) | Prepreg for printed wiring board and metal-clad laminate using the same | |
JP2003313324A (en) | Method for manufacturing base material-filled b-staged resin composition sheet | |
WO2020203469A1 (en) | Resin composition, prepreg, resin-including film, resin-including metal foil, metal-clad laminate plate, and printed wiring board | |
JP4390056B2 (en) | B-stage resin composition sheet and method for producing copper-clad laminate using the same | |
JP2003249751A (en) | Method for producing multilayer printed wiring board using additive method | |
JP4888517B2 (en) | Method for manufacturing printed circuit board for extra fine wire circuit | |
JP2003251757A (en) | B-stage resin composition sheet having heat resistant film base material for lamination | |
JP5253754B2 (en) | Resin composite copper foil | |
JP4390055B2 (en) | Method for producing copper clad laminate | |
JP2003238772A (en) | Curable resin composition and sheet of b-stage resin composition | |
JP2003249764A (en) | Manufacturing method for b-stage resin composition sheet containing base for additive | |
JP2004296601A (en) | Method of manufacturing multilayer board employing b stage resin composition sheet containing heat resistant film | |
JP2003332734A (en) | Method of manufacturing printed wiring board using additive method | |
JP2004319888A (en) | Multilayer printed circuit board | |
JP2003246843A (en) | Curable resin composition | |
JP2005074933A (en) | Copper clad laminated sheet and multilayered board using it | |
JP2005074819A (en) | Copper clad laminateed sheet and multilayered board using it | |
JP2003251739A (en) | Sheet of b-stage resin composition with metal leaf containing base material for additive | |
JP2004165411A (en) | Method of manufacturing extremely thin copper foil-plated board excellent in thickness uniformity of copper foil | |
JPH10337809A (en) | Ultra-thin copper foil with base material reinforced b-stage resin and its manufacture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070208 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090415 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090428 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090619 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090916 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121016 Year of fee payment: 3 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 4390056 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090929 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121016 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121016 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131016 Year of fee payment: 4 |
|
EXPY | Cancellation because of completion of term |