JP2021008044A - Copper-clad laminate - Google Patents
Copper-clad laminate Download PDFInfo
- Publication number
- JP2021008044A JP2021008044A JP2019121607A JP2019121607A JP2021008044A JP 2021008044 A JP2021008044 A JP 2021008044A JP 2019121607 A JP2019121607 A JP 2019121607A JP 2019121607 A JP2019121607 A JP 2019121607A JP 2021008044 A JP2021008044 A JP 2021008044A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- zirconium
- layer
- clad laminate
- based material
- 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 claims abstract description 139
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- 239000010949 copper Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 71
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 59
- 239000011574 phosphorus Substances 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 58
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 56
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 abstract description 33
- 230000003746 surface roughness Effects 0.000 abstract description 7
- 239000011889 copper foil Substances 0.000 description 67
- 239000002585 base Substances 0.000 description 43
- 238000011282 treatment Methods 0.000 description 23
- 229910000881 Cu alloy Inorganic materials 0.000 description 22
- 238000007747 plating Methods 0.000 description 17
- -1 compound salt Chemical class 0.000 description 15
- 239000011888 foil Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000012756 surface treatment agent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910000990 Ni alloy Inorganic materials 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NDZRILJASQYFSY-UHFFFAOYSA-J [Zr+4].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O Chemical compound [Zr+4].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O NDZRILJASQYFSY-UHFFFAOYSA-J 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- CGWDABYOHPEOAD-VIFPVBQESA-N (2r)-2-[(4-fluorophenoxy)methyl]oxirane Chemical compound C1=CC(F)=CC=C1OC[C@@H]1OC1 CGWDABYOHPEOAD-VIFPVBQESA-N 0.000 description 1
- FPFOSIXCIBGKOH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;zirconium(4+) Chemical compound [Zr+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O FPFOSIXCIBGKOH-MTOQALJVSA-J 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- WKCZSFRAGKIIKN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)ethanamine Chemical compound CC(C)(C)C1=CC=C(CCN)C=C1 WKCZSFRAGKIIKN-UHFFFAOYSA-N 0.000 description 1
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 1
- GVHUQXQVSWGYSH-UHFFFAOYSA-N 4-(3-bromophenyl)-2-methyl-1,3-thiazole Chemical compound S1C(C)=NC(C=2C=C(Br)C=CC=2)=C1 GVHUQXQVSWGYSH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- XHVWPOBZBNBEJC-UHFFFAOYSA-K C([O-])([O-])=O.[NH4+].C([O-])([O-])=O.[Zr+3] Chemical compound C([O-])([O-])=O.[NH4+].C([O-])([O-])=O.[Zr+3] XHVWPOBZBNBEJC-UHFFFAOYSA-K 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- ZLSPYXQZLJFBBV-UHFFFAOYSA-H F[Zr](F)(F)(F)(F)F.N Chemical compound F[Zr](F)(F)(F)(F)F.N ZLSPYXQZLJFBBV-UHFFFAOYSA-H 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- UEUMIMKGIUYUGH-UHFFFAOYSA-H [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] UEUMIMKGIUYUGH-UHFFFAOYSA-H 0.000 description 1
- PFYRERIAJQIGKB-UHFFFAOYSA-H [K].F[Zr](F)(F)(F)(F)F Chemical compound [K].F[Zr](F)(F)(F)(F)F PFYRERIAJQIGKB-UHFFFAOYSA-H 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- QZKWFURVKCYMSP-UHFFFAOYSA-N [P].[Fe].[Cu] Chemical compound [P].[Fe].[Cu] QZKWFURVKCYMSP-UHFFFAOYSA-N 0.000 description 1
- XNLPZZOCLLAQIM-UHFFFAOYSA-N acetyl acetate;vanadium Chemical compound [V].CC(=O)OC(C)=O XNLPZZOCLLAQIM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- DTEMQJHXKZCSMQ-UHFFFAOYSA-J phosphonato phosphate;zirconium(4+) Chemical compound [Zr+4].[O-]P([O-])(=O)OP([O-])([O-])=O DTEMQJHXKZCSMQ-UHFFFAOYSA-J 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明は、銅張積層板に関する。 The present invention relates to a copper-clad laminate.
銅張積層板は、樹脂層（ガラス布などの基材と樹脂からなるプリプレグや、樹脂フィルムなど）の片面または両面に、銅系材料層（銅箔または銅合金箔など）が積層されたものであり、プリント配線板の製造などに広く用いられている。 A copper-clad laminate is a copper-based material layer (copper foil, copper alloy foil, etc.) laminated on one or both sides of a resin layer (prepreg made of a base material such as glass cloth and resin, a resin film, etc.). It is widely used in the manufacture of printed wiring boards.
銅張積層板に用いられる銅系材料層は、一般に、必要とされる樹脂層との接着性を確保するため、その表面が粗化処理されている。例えば、特許文献１には、銅表面および銅合金表面の粗面化に有用であり、プリプレグ、ソルダーレジストなどの樹脂との密着性が良好な、深い凹凸が形成された銅表面または銅合金表面が得られる表面処理剤が開示されている。 The surface of the copper-based material layer used for the copper-clad laminate is generally roughened in order to secure the required adhesiveness with the resin layer. For example, Patent Document 1 describes a copper surface or a copper alloy surface having deep irregularities, which is useful for roughening the copper surface and the copper alloy surface and has good adhesion to resins such as prepreg and solder resist. The surface treatment agent for obtaining the above is disclosed.
ところで、近年、通信の高速化に伴い、電気信号の高周波化が進んでおり、これに対応可能なプリント配線板（高周波プリント配線板）が求められている。しかし、高周波域では、銅系材料層の表面粗さが大きいと、表皮効果のために導体損失が大きくなる傾向があり、従来の銅張積層板のように、銅系材料層の表面を粗化処理して、深い凹凸を形成することは望ましくない。そのため、特に銅張積層板を高周波プリント配線板に適用する場合においては、銅系材料層の表面粗さを小さく保ちながら、十分な銅系材料層と樹脂層との接着性を達成することが求められている。 By the way, in recent years, along with the increase in communication speed, the frequency of electric signals has been increasing, and a printed wiring board (high frequency printed wiring board) capable of coping with this has been required. However, in the high frequency region, if the surface roughness of the copper-based material layer is large, the conductor loss tends to be large due to the skin effect, and the surface of the copper-based material layer is roughened like the conventional copper-clad laminate. It is not desirable to perform the chemical treatment to form deep irregularities. Therefore, especially when a copper-clad laminate is applied to a high-frequency printed wiring board, it is possible to achieve sufficient adhesion between the copper-based material layer and the resin layer while keeping the surface roughness of the copper-based material layer small. It has been demanded.
本発明は、銅系材料層の表面粗さが小さく、銅系材料層と樹脂層との接着性に優れ、耐酸性および耐熱性にも優れる銅張積層板を提供することを目的とする。 An object of the present invention is to provide a copper-clad laminate having a small surface roughness of a copper-based material layer, excellent adhesiveness between a copper-based material layer and a resin layer, and excellent acid resistance and heat resistance.
本発明は、以下の各項に関する。
［１］ 銅系材料層と、ジルコニウム（Ａ）とリン（Ｂ）を少なくとも含有する下地皮膜層と、樹脂層とを、この順で含む銅張積層板。
［２］ 前記樹脂層が、フッ素樹脂を含有する、前記［１］に記載の銅張積層板。
［３］ 前記下地皮膜層が、バナジウム（Ｃ１）および／または珪素（Ｃ２）をさらに含有する、前記［１］または［２］に記載の銅張積層板。
The present invention relates to the following items.
[1] A copper-clad laminate containing a copper-based material layer, a base film layer containing at least zirconium (A) and phosphorus (B), and a resin layer in this order.
[2] The copper-clad laminate according to the above [1], wherein the resin layer contains a fluororesin.
[3] The copper-clad laminate according to the above [1] or [2], wherein the undercoat layer further contains vanadium (C1) and / or silicon (C2).
本発明によれば、銅系材料層の表面粗さが小さく、銅系材料層と樹脂層との接着性に優れ、耐酸性および耐熱性にも優れる銅張積層板を提供することができる。 According to the present invention, it is possible to provide a copper-clad laminate having a small surface roughness of a copper-based material layer, excellent adhesion between a copper-based material layer and a resin layer, and excellent acid resistance and heat resistance.
本実施形態に係る銅張積層板は、少なくとも、銅系材料層と、ジルコニウム（Ａ）とリン（Ｂ）を少なくとも含有する下地皮膜層と、樹脂層とを、この順で含むものである。下地皮膜層は、バナジウム（Ｃ１）および／または珪素（Ｃ２）をさらに含有することが好ましい。銅系材料層の表面に、ジルコニウム（Ａ）とリン（Ｂ）とを少なくとも含有する下地皮膜層、好ましくはジルコニウム（Ａ）とリン（Ｂ）とバナジウム（Ｃ１）および／または珪素（Ｃ２）とを少なくとも含有する下地皮膜層を形成することにより、銅系材料層の表面粗さが小さく、その表面が平滑であっても、優れた銅系材料層と樹脂層との接着性を達成することができる。また、プリント配線板の製造は、エッチングやめっき時における酸性液による処理や加熱処理を伴うが、このような下地皮膜層を形成することにより、優れた耐酸性および耐熱性も達成することができる。 The copper-clad laminate according to the present embodiment includes at least a copper-based material layer, a base film layer containing at least zirconium (A) and phosphorus (B), and a resin layer in this order. The undercoat layer preferably further contains vanadium (C1) and / or silicon (C2). On the surface of the copper-based material layer, an undercoat layer containing at least zirconium (A) and phosphorus (B), preferably zirconium (A), phosphorus (B), vanadium (C1) and / or silicon (C2) By forming an undercoat layer containing at least, excellent adhesion between the copper-based material layer and the resin layer can be achieved even if the surface roughness of the copper-based material layer is small and the surface is smooth. Can be done. Further, the production of a printed wiring board involves treatment with an acidic liquid and heat treatment at the time of etching and plating, and by forming such an undercoat layer, excellent acid resistance and heat resistance can also be achieved. ..
本実施形態に係る銅張積層板において、銅系材料層は、樹脂層の片面に積層されていてもよく、樹脂層の両面に積層されていてもよい。また、銅系材料層は、樹脂層の片側または両側の全表面に積層されていても、表面の一部にのみ積層されていてもよい。下地皮膜層は、通常、銅系材料層の全表面に形成・積層されるが、銅系材料層の表面の一部にのみ形成・積層されていてもよい場合もある。なお、銅系材料層が樹脂層の両面に積層されている場合は、片方の銅系材料層が、ジルコニウム（Ａ）とリン（Ｂ）とを少なくとも含有する下地皮膜層を介して、樹脂層に積層されていればよいが、両方の銅系材料層が、ジルコニウム（Ａ）とリン（Ｂ）とを少なくとも含有する下地皮膜層を介して、樹脂層に積層されていることが好ましい。樹脂層の両面に積層された２つの銅系材料層は同一のものであっても、異なるものであってもよく、２つの下地皮膜層も同一のものであっても、異なるものであってもよい。銅系材料層が樹脂層の片面に積層されている場合は、樹脂層の、銅系材料層が積層されている面と反対側の面には、他の層が積層されたものであってもよい。他の層としては、樹脂層を保護するための離型フィルム層が例示されるが、これに限定されるものではない。また、本実施形態に係る銅張積層板は、銅系材料層の、樹脂層が積層されている面と反対側の面に、さらに、他の層が積層されたものであってもよい。この他の層は、本実施形態に係る銅張積層板の下地皮膜層、すなわち、ジルコニウム（Ａ）とリン（Ｂ）とを少なくとも含有する層であってもよい。 In the copper-clad laminate according to the present embodiment, the copper-based material layer may be laminated on one side of the resin layer or on both sides of the resin layer. Further, the copper-based material layer may be laminated on the entire surface of one side or both sides of the resin layer, or may be laminated only on a part of the surface. The undercoat layer is usually formed and laminated on the entire surface of the copper-based material layer, but may be formed and laminated only on a part of the surface of the copper-based material layer. When the copper-based material layer is laminated on both sides of the resin layer, one of the copper-based material layers is a resin layer via an undercoat layer containing at least zirconium (A) and phosphorus (B). However, it is preferable that both copper-based material layers are laminated on the resin layer via an undercoat layer containing at least zirconium (A) and phosphorus (B). The two copper-based material layers laminated on both sides of the resin layer may be the same or different, and the two undercoat layers may be the same or different. May be good. When the copper-based material layer is laminated on one side of the resin layer, the other layer is laminated on the surface of the resin layer opposite to the surface on which the copper-based material layer is laminated. May be good. Examples of the other layer include, but are not limited to, a release film layer for protecting the resin layer. Further, the copper-clad laminate according to the present embodiment may be one in which another layer is further laminated on the surface of the copper-based material layer opposite to the surface on which the resin layer is laminated. The other layer may be a base film layer of the copper-clad laminate according to the present embodiment, that is, a layer containing at least zirconium (A) and phosphorus (B).
＜銅系材料層＞
銅系材料層は、銅、または銅の含有割合が５０質量％以上、より好ましくは６０質量％以上、特に好ましくは７５質量％以上である銅合金から主としてなる層であり、銅合金としては具体的に、ＪＩＳ Ｈ ３１００：２０１２に定められている、銅−亜鉛合金系、銅−鉄−リン合金系、銅−錫合金系、銅−ジルコニウム合金系等が挙げられるが、これらに限定されるものではない。銅系材料層は、プリント配線板に用いられる銅張積層板の銅箔または銅合金箔に一般的に施される表面処理が施されたものであってもよい。表面処理としては、例えば、めっき処理（金属めっき処理、または合金めっき処理）、クロメート処理などが挙げられる。めっき処理としては、従来公知のめっき処理のいずれでもよく、例えば、ニッケル、亜鉛、錫、コバルト、モリブデン、銅、タングステン、リン、砒素、クロム、バナジウム、チタン、アルミニウム、金、銀、白金族元素、鉄、タンタルの群から選ばれる１種以上の元素を含むめっき処理であってよく、前述の元素からなる金属めっきまたは合金めっきであってもよい。より具体的には、亜鉛めっき処理、ニッケルめっき処理、亜鉛−ニッケル合金めっき処理が例示されるが、これらに限定されるものではない。また、銅系材料層は、シランカップリング剤などのカップリング剤による表面処理が施されたものであってもよいが、本発明によれば、通常、銅系材料層に対してカップリング剤による表面処理を行わなくても、優れた銅系材料層と樹脂層との接着性が得られる。なお、このような表面処理は、公知の方法にしたがって行うことができる。
<Copper material layer>
The copper-based material layer is a layer mainly composed of copper or a copper alloy having a copper content of 50% by mass or more, more preferably 60% by mass or more, particularly preferably 75% by mass or more, and is a specific copper alloy. Specific examples thereof include, but are limited to, copper-zinc alloys, copper-iron-phosphorus alloys, copper-tin alloys, copper-zirconium alloys, etc., as defined in JIS H 3100: 2012. It's not a thing. The copper-based material layer may be one that has been subjected to the surface treatment generally applied to the copper foil or the copper alloy foil of the copper-clad laminate used for the printed wiring board. Examples of the surface treatment include plating treatment (metal plating treatment or alloy plating treatment), chromate treatment and the like. The plating treatment may be any of conventionally known plating treatments, for example, nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver and platinum group elements. It may be a plating treatment containing one or more elements selected from the group of iron and tantalum, and may be metal plating or alloy plating composed of the above-mentioned elements. More specifically, zinc plating treatment, nickel plating treatment, and zinc-nickel alloy plating treatment are exemplified, but the present invention is not limited thereto. Further, the copper-based material layer may be surface-treated with a coupling agent such as a silane coupling agent, but according to the present invention, a coupling agent is usually used for the copper-based material layer. Excellent adhesion between the copper-based material layer and the resin layer can be obtained without performing the surface treatment by. In addition, such a surface treatment can be performed according to a known method.
銅系材料層としては、特に限定されないが、例えば、圧延銅板または圧延銅合金板、圧延銅箔または圧延銅合金箔、電解銅箔または電解銅合金箔などの銅板または銅合金板、あるいは銅箔または銅合金箔、および、その表面が上記のような表面処理されたものを好適に用いることができる。また、キャリア付銅箔またはキャリア付銅合金箔、および、これらの銅箔または銅合金箔の表面が上記のような表面処理されたものも好適に用いることができ、この場合、キャリア付銅箔の銅箔またはキャリア付銅合金箔の銅合金箔（いずれも表面処理されていてもよい）が、本実施形態に係る銅張積層板の銅系材料層となる。また、例えば、銅または銅合金めっき材、銅または銅合金クラッド材などの銅系材料層を表面に有する積層体、および、これらの銅系材料層の表面が上記のような表面処理されたものも好適に用いることができ、この場合、積層体に含まれる銅系材料層（表面処理されていてもよい）が、本実施形態に係る銅張積層板の銅系材料層となる。キャリア付銅箔またはキャリア付銅合金箔のキャリアは特に限定されず、電解銅箔などの金属箔や、樹脂フィルムなど、一般的に用いられているものいずれも用いることができる。キャリアの厚さも特に限定されず、適宜選択することができる。キャリア付銅箔、およびキャリア付銅合金箔は、例えば、キャリア付電解銅箔、およびキャリア付電解銅合金箔が一般的であるが、これに限定されるものではない。 The copper-based material layer is not particularly limited, and is, for example, a copper plate or a copper alloy plate such as a rolled copper plate or a rolled copper alloy plate, a rolled copper foil or a rolled copper alloy foil, an electrolytic copper foil or an electrolytic copper alloy foil, or a copper foil. Alternatively, a copper alloy foil and one whose surface has been surface-treated as described above can be preferably used. Further, a copper foil with a carrier or a copper alloy foil with a carrier, and a copper foil or a copper alloy foil with a surface treated as described above can also be preferably used. In this case, the copper foil with a carrier The copper foil or the copper alloy foil of the copper alloy foil with a carrier (both of which may be surface-treated) serves as the copper-based material layer of the copper-clad laminate according to the present embodiment. Further, for example, a laminate having a copper-based material layer such as a copper or copper alloy plating material or a copper or copper alloy clad material on the surface, and a surface-treated surface of these copper-based material layers as described above. In this case, the copper-based material layer (which may be surface-treated) contained in the laminate is the copper-based material layer of the copper-clad laminate according to the present embodiment. The carrier of the copper foil with a carrier or the copper alloy foil with a carrier is not particularly limited, and any of commonly used metal foils such as electrolytic copper foil and resin films can be used. The thickness of the carrier is also not particularly limited and can be appropriately selected. The copper foil with a carrier and the copper alloy foil with a carrier are generally, for example, an electrolytic copper foil with a carrier and an electrolytic copper alloy foil with a carrier, but are not limited thereto.
銅系材料層は、通常、表面が平滑であることが好ましく、具体的には、表面の十点平均粗さ（Ｒｚ）が５μｍ以下であることが好ましく、３μｍ以下であることがより好ましく、１．５μｍ以下であることが特に好ましい。つまり、銅系材料層は、通常、その表面が粗化処理されていないことが好ましい。銅系材料層表面の十点平均粗さ（Ｒｚ）の下限値は、特に限定されず、通常、０μｍに近くなるほど好ましい。なお、十点平均粗さ（Ｒｚ）は、ＪＩＳ Ｃ６５１５：１９９８に準拠して測定することができる。 The surface of the copper-based material layer is usually preferably smooth, and specifically, the ten-point average roughness (Rz) of the surface is preferably 5 μm or less, more preferably 3 μm or less. It is particularly preferably 1.5 μm or less. That is, it is usually preferable that the surface of the copper-based material layer is not roughened. The lower limit of the ten-point average roughness (Rz) of the surface of the copper-based material layer is not particularly limited, and is usually preferably closer to 0 μm. The ten-point average roughness (Rz) can be measured in accordance with JIS C6515: 1998.
銅系材料層の厚さは、特に限定されず、用途などに応じて適宜選択することができるが、通常、好ましくは０．５μｍ〜１０００μｍ、より好ましくは１μｍ〜１００μｍである。 The thickness of the copper-based material layer is not particularly limited and may be appropriately selected depending on the intended use, but is usually preferably 0.5 μm to 1000 μm, and more preferably 1 μm to 100 μm.
＜下地皮膜層＞
下地皮膜層は、ジルコニウム（Ａ）と、リン（Ｂ）とを少なくとも含有する。ここで、ジルコニウム（Ａ）はジルコニウム元素を意味し、リン（Ｂ）はリン元素を意味する。
<Undercoat layer>
The undercoat layer contains at least zirconium (A) and phosphorus (B). Here, zirconium (A) means a zirconium element, and phosphorus (B) means a phosphorus element.
ジルコニウム（Ａ）
ジルコニウム（Ａ）は、単体の形態で存在していてもよく、酸化物、複合酸化物、水酸化物、複合水酸化物、錯体化合物、塩などの化合物の形態で存在していてもよい。
Zirconium (A)
The zirconium (A) may exist in the form of a single substance, or may exist in the form of a compound such as an oxide, a composite oxide, a hydroxide, a composite hydroxide, a complex compound, or a salt.
ジルコニウム（Ａ）の付着量は、ジルコニウム元素換算質量で、１ｍｇ/ｍ２以上であることが好ましく、３ｍｇ/ｍ２以上であることがより好ましく、５ｍｇ/ｍ２以上であることが特に好ましい。また、ジルコニウム（Ａ）の付着量は、ジルコニウム元素換算質量で、２５０ｍｇ/ｍ２以下であることが好ましく、１００ｍｇ/ｍ２以下であることがより好ましく、５０ｍｇ/ｍ２以下であることが特に好ましい。 The amount of zirconium (A) attached is preferably 1 mg / m 2 or more, more preferably 3 mg / m 2 or more, and particularly preferably 5 mg / m 2 or more in terms of zirconium element-equivalent mass. The amount of zirconium (A) adhered is preferably 250 mg / m 2 or less, more preferably 100 mg / m 2 or less, and particularly preferably 50 mg / m 2 or less in terms of zirconium element-equivalent mass. preferable.
リン（Ｂ）
リン（Ｂ）は、単体の形態で存在していてもよく、リン酸類、リン酸エステル、有機ホスホン酸などの化合物、または化合物塩の形態で存在していてもよい。また、リン酸ジルコニウムなどの、リンと本発明の他の構成元素の１種以上を含有する化合物の形態で存在していてもよい。
Rin (B)
Phosphorus (B) may exist in the form of a simple substance, or may exist in the form of a compound such as a phosphoric acid, a phosphoric acid ester, or an organic phosphonic acid, or a compound salt. Further, it may exist in the form of a compound containing phosphorus and one or more of other constituent elements of the present invention, such as zirconium phosphate.
リン（Ｂ）の付着量は、リン元素換算質量で、０．１ｍｇ/ｍ２以上であることが好ましく、０．５ｍｇ/ｍ２以上であることがより好ましく、１ｍｇ/ｍ２以上であることが特に好ましい。また、リン（Ｂ）の付着量は、リン元素換算質量で、１００ｍｇ/ｍ２以下であることが好ましく、５０ｍｇ/ｍ２以下であることがより好ましく、２５ｍｇ/ｍ２以下であることが特に好ましい。 The amount of phosphorus (B) attached is preferably 0.1 mg / m 2 or more, more preferably 0.5 mg / m 2 or more, and 1 mg / m 2 or more in terms of phosphorus element equivalent mass. Is particularly preferable. The amount of phosphorus (B) attached is preferably 100 mg / m 2 or less, more preferably 50 mg / m 2 or less, and particularly preferably 25 mg / m 2 or less in terms of phosphorus element equivalent mass. preferable.
ジルコニウム（Ａ）とリン（Ｂ）の合計の付着量は、各元素換算質量で、１．１ｍｇ/ｍ２以上であることが好ましく、３．５ｍｇ/ｍ２以上であることがより好ましく、６ｍｇ/ｍ２以上であることが特に好ましい。また、ジルコニウム（Ａ）とリン（Ｂ）の合計の付着量は、各元素換算質量で、３５０ｍｇ/ｍ２以下であることが好ましく、１５０ｍｇ/ｍ２以下であることがより好ましく、７５ｍｇ/ｍ２以下であることが特に好ましい。 The total amount of adhesion of zirconium (A) and phosphorus (B) is preferably 1.1 mg / m 2 or more, more preferably 3.5 mg / m 2 or more, and 6 mg in terms of each element-equivalent mass. It is particularly preferable that it is / m 2 or more. The total amount of zirconium (A) and phosphorus (B) adhered is preferably 350 mg / m 2 or less, more preferably 150 mg / m 2 or less, and 75 mg / m in terms of each element-equivalent mass. It is particularly preferably 2 or less.
下地皮膜層は、添加成分（Ｃ）として、バナジウム（Ｃ１）および／または珪素（Ｃ２）を含有することが好ましい。ここで、バナジウム（Ｃ１）はバナジウム元素を意味し、珪素（Ｃ２）は珪素元素を意味する。 The undercoat layer preferably contains vanadium (C1) and / or silicon (C2) as an additive component (C). Here, vanadium (C1) means a vanadium element, and silicon (C2) means a silicon element.
バナジウム（Ｃ１）
バナジウム（Ｃ１）は、単体の形態で存在していてもよく、酸化物、複合酸化物、水酸化物、複合水酸化物、錯体化合物、化合物塩などの化合物の形態で存在していてもよい。
Vanadium (C1)
Vanadium (C1) may exist in the form of a single substance, or may exist in the form of a compound such as an oxide, a composite oxide, a hydroxide, a composite hydroxide, a complex compound, or a compound salt. ..
バナジウム（Ｃ１）の付着量は、バナジウム元素換算質量で、０．５ｍｇ/ｍ２以上であることが好ましく、１ｍｇ/ｍ２以上であることがより好ましく、２ｍｇ/ｍ２以上であることが特に好ましい。また、バナジウム（Ｃ１）の付着量は、バナジウム元素換算質量で、１００ｍｇ/ｍ２以下であることが好ましく、５０ｍｇ/ｍ２以下であることがより好ましく、２５ｍｇ/ｍ２以下であることが特に好ましい。 Adhesion amount of vanadium (C1) is a vanadium element reduced mass, is preferably 0.5 mg / m 2 or more, more preferably 1 mg / m 2 or more, in particular not less 2 mg / m 2 or more preferable. The amount of vanadium (C1) adhered is preferably 100 mg / m 2 or less, more preferably 50 mg / m 2 or less, and particularly preferably 25 mg / m 2 or less in terms of vanadium element equivalent mass. preferable.
珪素（Ｃ２）
珪素（Ｃ２）は、酸化物、すなわちシリカの形態で存在することが好ましく、例えば、結晶質シリカ、または非晶質シリカの形態で存在していてもよい。また、珪素を含有する複合酸化物などの形態で存在していてもよい。
Silicon (C2)
Silicon (C2) preferably exists in the form of an oxide, i.e. silica, and may, for example, exist in the form of crystalline silica or amorphous silica. Further, it may exist in the form of a composite oxide containing silicon.
珪素（Ｃ２）の付着量は、珪素元素換算質量で、０．５ｍｇ/ｍ２以上であることが好ましく、１ｍｇ/ｍ２以上であることがより好ましく、２．５ｍｇ/ｍ２以上であることが特に好ましい。また、珪素（Ｃ２）の付着量は、珪素元素換算質量で、１２０ｍｇ/ｍ２以下であることが好ましく、５０ｍｇ/ｍ２以下であることがより好ましく、２５ｍｇ/ｍ２以下であることが特に好ましい。 The amount of silicon (C2) adhered is preferably 0.5 mg / m 2 or more, more preferably 1 mg / m 2 or more, and 2.5 mg / m 2 or more in terms of silicon element-equivalent mass. Is particularly preferable. The amount of silicon (C2) adhered is preferably 120 mg / m 2 or less, more preferably 50 mg / m 2 or less, and particularly preferably 25 mg / m 2 or less in terms of silicon element-equivalent mass. preferable.
バナジウム（Ｃ１）と珪素（Ｃ２）を併用する場合、バナジウム（Ｃ１）と珪素（Ｃ２）の合計の付着量は、各元素換算質量で、１ｍｇ/ｍ２以上であることが好ましく、２ｍｇ/ｍ２以上であることがより好ましく、４．５ｍｇ/ｍ２以上であることが特に好ましい。また、バナジウム（Ｃ１）と珪素（Ｃ２）の合計の付着量は、各元素換算質量で、２２０ｍｇ/ｍ２以下であることが好ましく、１００ｍｇ/ｍ２以下であることがより好ましく、５０ｍｇ/ｍ２以下であることが特に好ましい。 When vanadium (C1) and silicon (C2) are used in combination, the total adhesion amount of vanadium (C1) and silicon (C2) is preferably 1 mg / m 2 or more in terms of each element-equivalent mass, and is 2 mg / m. more preferably 2 or more, particularly preferably 4.5 mg / m 2 or more. The total amount of adhesion of vanadium (C1) and silicon (C2) is preferably 220 mg / m 2 or less, more preferably 100 mg / m 2 or less, and 50 mg / m in terms of each element equivalent mass. It is particularly preferably 2 or less.
なお、上記の各成分の付着量は、いずれも、片面（１層）当たりの付着量である。また、各成分の付着量は、例えば、蛍光Ｘ線分析法により測定することができる。具体的には、所定面積の銅系材料層の表面に形成された下地皮膜を蛍光Ｘ線分析装置で分析し、検出された元素の強度から元素換算質量を算出し、単位面積当たりの付着量を求めることができる。 The amount of adhesion of each of the above components is the amount of adhesion per one side (one layer). Further, the amount of adhesion of each component can be measured by, for example, a fluorescent X-ray analysis method. Specifically, the base film formed on the surface of the copper-based material layer having a predetermined area is analyzed by a fluorescent X-ray analyzer, the elemental reduced mass is calculated from the detected element intensity, and the amount of adhesion per unit area is calculated. Can be sought.
下地皮膜層の厚さは、特に限定されず、各成分の付着量が上記の範囲内になるように適宜選択することができるが、通常、好ましくは１〜１０００ｎｍ、より好ましくは５〜５００ｎｍである。 The thickness of the undercoat layer is not particularly limited and can be appropriately selected so that the amount of adhesion of each component is within the above range, but it is usually preferably 1 to 1000 nm, more preferably 5 to 500 nm. is there.
＜樹脂層＞
樹脂層は、樹脂を含有する層であればよく、樹脂から主としてなる層であっても、ガラス繊維布（織布または不織布）などの基材と樹脂とを含む層、例えば、基材に樹脂または樹脂組成物が含浸された層であってもよい。樹脂層に含まれる樹脂は、１種であっても、２種以上の樹脂の混合物であってもよい。また、樹脂層は、必要に応じて、無機粒子（フィラー）や無機繊維、その他の各種添加剤などを含有することができる。なお、銅張積層板の樹脂層の基材は、特に限定されず、上記以外のものも用いることができる。
<Resin layer>
The resin layer may be a layer containing resin, and even if it is a layer mainly made of resin, a layer containing a base material such as a glass fiber cloth (woven cloth or non-woven fabric) and a resin, for example, a resin on the base material. Alternatively, the layer may be impregnated with the resin composition. The resin contained in the resin layer may be one kind or a mixture of two or more kinds of resins. In addition, the resin layer can contain inorganic particles (fillers), inorganic fibers, and various other additives, if necessary. The base material of the resin layer of the copper-clad laminate is not particularly limited, and other than the above can be used.
樹脂層に含まれる樹脂としては、特に限定されず、用途などに応じて適宜選択することができる。 The resin contained in the resin layer is not particularly limited, and can be appropriately selected depending on the intended use and the like.
樹脂として、具体的には、ポリテトラフルオロエチレン（ＰＴＦＥ）、パーフルオロアルコキシフッ素樹脂（ＰＦＡ）、四フッ化エチレン・六フッ化プロピレン共重合体（ＦＥＰ）、エチレン・四フッ化エチレン共重合体（ＥＴＦＥ）、エチレン・クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体などのフッ素樹脂、液晶ポリマー（ＬＣＰ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリフェニレンエーテル（ＰＰＥ）、エポキシ樹脂、ビスマレイミドトリアジン樹脂、シクロオレフィンポリマー、ポリイミドなどが挙げられる。中でも、フッ素樹脂が好ましく、ポリテトラフルオロエチレン（ＰＴＦＥ）が特に好ましい。 Specific examples of the resin include polytetrafluoroethylene (PTFE), perfluoroalkoxyfluororesin (PFA), ethylene tetrafluoride / propylene hexafluoride copolymer (FEP), and ethylene / ethylene tetrafluoride copolymer. (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), fluororesin such as tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, liquid crystal polymer (LCP), polyether ether ketone (PEEK), polyphenylene ether ( PPE), epoxy resin, bismaleimide triazine resin, cycloolefin polymer, polyimide and the like. Of these, fluororesin is preferable, and polytetrafluoroethylene (PTFE) is particularly preferable.
樹脂層としては、プリント配線板の樹脂基材として市販されている樹脂フィルムまたはプリプレグを用いることもできる。 As the resin layer, a commercially available resin film or prepreg as a resin base material for a printed wiring board can also be used.
樹脂層の厚さは、特に限定されず、用途などに応じて適宜選択することができるが、通常、好ましくは１０〜１０００μｍ、より好ましくは２０〜５００μｍである。 The thickness of the resin layer is not particularly limited and may be appropriately selected depending on the intended use, but is usually preferably 10 to 1000 μm, more preferably 20 to 500 μm.
＜銅張積層板の製造方法＞
本実施形態に係る銅張積層板は、例えば、次のようにして製造することができる。ただし、銅張積層板の製造方法は、以下の方法に限定されるものではない。
<Manufacturing method of copper-clad laminate>
The copper-clad laminate according to the present embodiment can be manufactured, for example, as follows. However, the method for manufacturing the copper-clad laminate is not limited to the following methods.
まず、銅系材料層となる銅箔または銅板、あるいは銅合金箔または銅合金板（上記のような表面処理が施されたものであってもよい）の上に、または、銅系材料層を表面に有する積層体を用いる場合は、その銅系材料層（表面処理されていてもよい）の上に、下地皮膜層を形成・積層する。 First, a copper-based material layer is placed on a copper foil or a copper plate to be a copper-based material layer, or a copper alloy foil or a copper alloy plate (which may be surface-treated as described above). When a laminate having a surface is used, an undercoat layer is formed and laminated on the copper-based material layer (which may be surface-treated).
下地皮膜層は、例えば、ジルコニウム化合物と、リン化合物と、必要に応じて、バナジウム化合物、珪素化合物などを溶剤に溶解または分散させて、下地皮膜層形成用の表面処理剤を調製し、これを、銅系材料層に塗布した後、乾燥させることで、形成することができる。 For the undercoat layer, for example, a zirconium compound, a phosphorus compound, and, if necessary, a vanadium compound, a silicon compound, etc. are dissolved or dispersed in a solvent to prepare a surface treatment agent for forming the undercoat layer. , Can be formed by applying to a copper-based material layer and then drying.
ジルコニウム化合物としては、ジルコニウムを含有していれば特に限定されないが、例えば、テトラキス（アセチルアセトナト）ジルコニウム（IV）、塩化酸化ジルコニウム（IV）、塩化ジルコニウム（IV）、ケイ酸ジルコニウム、酢酸酸化ジルコニウム（IV）、酸化ジルコニウム（IV）、硝酸酸化ジルコニウム（IV）、メタジルコニウム酸セシウム、メタジルコニウム酸リチウム、メタジルコニウム酸亜鉛（II）、メタジルコニウム酸アルミニウム（III）、メタジルコニウム酸カルシウム、メタジルコニウム酸コバルト（II）、メタジルコニウム酸ストロンチウム、メタジルコニウム酸銅（II）、メタジルコニウム酸ナトリウム、メタジルコニウム酸ニッケル（II）、メタジルコニウム酸バリウム、メタジルコニウム酸ビスマス（III）、メタジルコニウム酸マグネシウム、オキシ炭酸ジルコニウム、ヘキサフルオロジルコニウム（IV）酸アンモニウム、ヘキサフルオロジルコニウム（IV）酸カリウム、ヨウ化ジルコニウム、リン酸二水素酸化ジルコニウム（IV）、塩基性炭酸ジルコニウム、炭酸ジルコニウムアンモニウム、炭酸ジルコニルアンモニウム、硝酸ジルコニウム、硝酸ジルコニル、硫酸ジルコニウム（IV）、硫酸ジルコニル、ヘキサフルオロジルコニウム酸、オキシリン酸ジルコニウム、ピロリン酸ジルコニウム、リン酸二水素ジルコニル、オキシ塩化ジルコニウム、フッ化ジルコニウム、酢酸ジルコニル、酸化ジルコニウム、水酸化ジルコニウムなどを好適に用いることができる。ジルコニウム化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The zirconium compound is not particularly limited as long as it contains zirconium, and for example, tetrakis (acetylacetonato) zirconium (IV), zirconium chloride (IV), zirconium chloride (IV), zirconium silicate, zirconium acetate. (IV), zirconium oxide (IV), zirconium nitrate (IV), cesium metazirconium, lithium metazirconium, zinc metazirconium (II), aluminum metazirconium (III), calcium metazirconium, metazirconium Cobalt acid (II), strontium metazirconium, copper (II) metazirconium, sodium metazirconate, nickel metazirconate (II), barium metazirconium, bismuth metazirconium (III), magnesium metazirconium, Zirconium oxycarbonate, ammonium hexafluorozirconium (IV), potassium hexafluorozirconium (IV), zirconium iodide, zirconium dihydrogen phosphate (IV), basic zirconium carbonate, ammonium zirconium carbonate, zirconium ammonium carbonate, nitrate Zirconium, zirconium nitrate, zirconium sulfate (IV), zirconium sulfate, hexafluorozirconium acid, zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen phosphate, zirconium oxychloride, zirconium fluoride, zirconium acetate, zirconium oxide, zirconium hydroxide Etc. can be preferably used. One type of zirconium compound may be used alone, or two or more types may be used in combination.
リン化合物としては、リンを含有していれば特に限定されないが、例えば、リン酸類、リン酸エステル、有機ホスホン酸等を挙げることができる。リン酸類としては、具体的には、リン酸（オルトリン酸）、メタリン酸、ポリリン酸を包含する縮合リン酸、及びその塩（アンモニウム塩、ナトリウム塩、カルシウム塩、マグネシウム塩、リチウム塩等）を挙げることができる。なお、メタリン酸は、トリメタリン酸、テトラメタリン酸、ヘキサメタリン酸等を包含する。また、ポリリン酸は、鎖状のリン酸縮合物であって、ピロリン酸、トリポリリン酸、テトラポリリン酸等を包含する。リン酸エステルとしては、具体的には、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、モノメチルホスフェート、ジメチルホスフェート、エチルホスフェート、ジエチルホスフェート、モノブチルホスフェート、ジブチルホスフェート、フィチン酸、及びその塩（アンモニウム塩、ナトリウム塩、カルシウム塩、マグネシウム塩、リチウム塩等）、リボフラビンりん酸エステル等を挙げることができる。有機ホスホン酸としては、具体的には、ニトリロトリスメチレンホスホン酸、１−ヒドロキシエチリデン１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸などを好適に用いることができる。リン化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The phosphorus compound is not particularly limited as long as it contains phosphorus, and examples thereof include phosphoric acids, phosphoric acid esters, and organic phosphonic acids. Specific examples of the phosphoric acids include phosphoric acid (orthophosphoric acid), metaphosphoric acid, condensed phosphoric acid including polyphosphoric acid, and salts thereof (ammonium salt, sodium salt, calcium salt, magnesium salt, lithium salt, etc.). Can be mentioned. The metaphosphate includes trimetaphosphate, tetramethaphosphate, hexametaphosphate and the like. Further, the polyphosphoric acid is a chain-shaped phosphoric acid condensate, and includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid and the like. Specific examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, phytic acid, and salts thereof (ammonium salt, sodium). Salts, calcium salts, magnesium salts, lithium salts, etc.), riboflavin phosphates, etc. can be mentioned. As the organic phosphonic acid, specifically, nitrilotrismethylenephosphonic acid, 1-hydroxyethylidene 1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and the like can be preferably used. One type of phosphorus compound may be used alone, or two or more types may be used in combination.
バナジウム化合物としては、バナジウムを含有していれば特に限定されないが、例えば、オキシ二塩化バナジウム、オキシ三塩化バナジウム、三塩化バナジウム、酸化バナジウム、四バナジン酸鉄（III）、臭化バナジウム（III）、オキシ蓚酸バナジウム、ヨウ化バナジウム（II）、五酸化バナジウム、メタバナジン酸、ピロバナジン酸ナトリウム、バナジン酸ナトリウム、メタバナジン酸アンモニウム、メタバナジン酸ナトリウム、メタバナジン酸カリウム、オキシ三塩化バナジウム、三酸化バナジウム、二酸化バナジウム、オキシ硫酸バナジウム、バナジウムオキシアセチルアセテート、バナジウムアセチルアセテート、リンバナドモリブデン酸等のバナジウム塩等又はバナジン酸塩などを好適に用いることができる。バナジウム化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The vanadium compound is not particularly limited as long as it contains vanadium, and for example, vanadium oxydichloride, vanadium oxytrichloride, vanadium trichloride, vanadium oxide, iron tetravanadate (III), vanadium bromide (III). , Vanadium oxyphosphate, vanadium iodide (II), vanadium pentoxide, metavanadic acid, sodium pyrovanadate, sodium vanadate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide , Vanadium oxysulfate, vanadium oxyacetyl acetate, vanadium acetyl acetate, vanadium salts such as limvanado molybdic acid, vanadate and the like can be preferably used. One type of vanadium compound may be used alone, or two or more types may be used in combination.
珪素化合物としては、珪素を含有していれば特に限定されないが、例えば、コロイダルシリカや、アルカリケイ酸塩や、有機シラン化合物などのシリカに転化する化合物を好適に用いることができる。
コロイダルシリカとしては、ＳｉＯ２を水に分散した湿式シリカゾルや、乾式シリカゾルであることが好適である。
アルカリケイ酸塩としては、ＳｉＯ2・ｎＭｂ2Ｏ（ここで、ｎは１〜５であり、Ｍｂはアルカリ金属である）で示される無機珪素化合物であることが好適である。
有機シラン化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、テトラ-t-ブトキシシラン、およびこれらの部分縮合物である事が好適である。
珪素化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The silicon compound is not particularly limited as long as it contains silicon, but for example, a compound that converts to silica such as colloidal silica, an alkali silicate, and an organic silane compound can be preferably used.
The colloidal silica is preferably a wet silica sol in which SiO 2 is dispersed in water or a dry silica sol.
The alkali silicate is preferably an inorganic silicon compound represented by SiO 2 · nMb 2 O (where n is 1 to 5 and Mb is an alkali metal).
As the organic silane compound, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetra-t-butoxysilane, and a partial condensate thereof are preferable.
One type of silicon compound may be used alone, or two or more types may be used in combination.
表面処理剤中の各化合物の含有量は、特に限定されず、適宜選択することができる。 The content of each compound in the surface treatment agent is not particularly limited and can be appropriately selected.
表面処理剤に用いる溶剤は特に限定されず、一般的に用いられているものから適宜選択して用いることができ、有機溶剤も用いることができるが、通常、水が好ましい。溶剤は、２種以上を組み合わせて用いてもよい。 The solvent used for the surface treatment agent is not particularly limited, and can be appropriately selected from commonly used solvents, and an organic solvent can also be used, but water is usually preferable. Two or more kinds of solvents may be used in combination.
表面処理剤には、必要に応じて、一般的に用いられている各種添加剤、例えば、無機化合物や、樹脂などの有機化合物、界面活性剤、消泡剤、レベリング剤、防菌防ばい剤などを添加してもよい。 The surface treatment agent includes various commonly used additives such as inorganic compounds, organic compounds such as resins, surfactants, defoamers, leveling agents, and antibacterial antibacterial agents, if necessary. Etc. may be added.
表面処理剤の塗布は、特に限定されず、公知の方法で行うことができ、例えば、バーコート法、スプレー法、スピンコート法、ロールコート法、カーテンコート法、浸漬法などで行うことができる。 The application of the surface treatment agent is not particularly limited and can be carried out by a known method, for example, a bar coating method, a spray method, a spin coating method, a roll coating method, a curtain coating method, a dipping method or the like. ..
表面処理剤塗布後の乾燥条件も、特に限定されず、適宜選択することができるが、通常、銅系材料層の最高到達温度（ＰＭＴ）が６０〜３００℃の温度になるように加熱乾燥して溶剤を除去することが好ましい。乾燥温度は、銅系材料層の表面を乾燥できれば特に制限されるものではないが、銅系材料層の最高到達温度（ＰＭＴ）が６０〜２５０℃の範囲内がより好ましく、６０〜２００℃の範囲内が特に好ましい。 The drying conditions after applying the surface treatment agent are also not particularly limited and can be appropriately selected, but usually, the copper-based material layer is heated and dried so that the maximum temperature reached (PMT) is 60 to 300 ° C. It is preferable to remove the solvent. The drying temperature is not particularly limited as long as the surface of the copper-based material layer can be dried, but the maximum temperature reached (PMT) of the copper-based material layer is more preferably in the range of 60 to 250 ° C., and 60 to 200 ° C. Within the range is particularly preferred.
なお、下地皮膜層を形成する前に、必要に応じて、銅系材料層に対して酸脱脂、アルカリ脱脂、酸洗浄、アルカリ洗浄、水洗などの洗浄化処理、および処理後の乾燥などを行ってもよい。このような洗浄化処理および乾燥は、公知の方法にしたがって行うことができる。 Before forming the undercoat layer, if necessary, the copper-based material layer is subjected to cleaning treatment such as acid degreasing, alkali degreasing, acid washing, alkali washing, and water washing, and drying after the treatment. You may. Such cleaning treatment and drying can be performed according to a known method.
次いで、このようにして銅系材料層の表面に形成した下地皮膜層の上に、樹脂層となる樹脂フィルムまたはプリプレグなどを重ね合わせ、加熱・加圧し、接合することによって、本実施形態に係る銅張積層板を製造することができる。銅系材料層が樹脂層の両面に積層されている銅張積層板を製造する場合は、下地皮膜層を介して、銅系材料層を、樹脂フィルムまたはプリプレグなどの両面に同時に接合してもよいし、片面ずつ順に接合してもよい。 Next, according to the present embodiment, a resin film or prepreg to be a resin layer is superposed on the base film layer formed on the surface of the copper-based material layer in this manner, heated and pressurized, and joined. A copper-clad laminate can be manufactured. When manufacturing a copper-clad laminate in which a copper-based material layer is laminated on both sides of a resin layer, the copper-based material layer may be simultaneously bonded to both sides of a resin film or prepreg via a base film layer. Alternatively, one side may be joined in order.
下地皮膜層を表面に形成した銅系材料層と、樹脂フィルムまたはプリプレグなどとの積層は、特に限定されず、公知の加熱・加圧装置を用いて行うことができる。加圧条件および加熱条件も、特に限定されず、用いる材料、樹脂の種類などに応じて適宜選択することができる。 The lamination of the copper-based material layer having the base film layer formed on the surface thereof and the resin film, prepreg, or the like is not particularly limited, and can be performed using a known heating / pressurizing device. The pressurizing condition and the heating condition are also not particularly limited, and can be appropriately selected depending on the material to be used, the type of resin, and the like.
本実施形態に係る銅張積層板は、銅系材料層と樹脂層との接着性に優れ、プリント配線板に加工する際に必要とされる耐酸性および耐熱性にも優れている。本実施形態に係る銅張積層板は、プリント配線板、特に高周波プリント配線板に好適に用いることができる。 The copper-clad laminate according to the present embodiment has excellent adhesiveness between the copper-based material layer and the resin layer, and is also excellent in acid resistance and heat resistance required for processing into a printed wiring board. The copper-clad laminate according to the present embodiment can be suitably used for a printed wiring board, particularly a high-frequency printed wiring board.
以下、実施例および比較例により本発明をさらに詳しく説明する。なお、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
実施例および比較例において、銅箔、および下地皮膜層を表面に形成した銅箔（以下、「下地皮膜層形成銅箔」と言う。）、銅張積層板の評価は次の方法で行った。 In the examples and comparative examples, the copper foil, the copper foil having the undercoat layer formed on the surface (hereinafter referred to as "undercoat layer formed copper foil"), and the copper-clad laminate were evaluated by the following methods. ..
＜銅箔表面の十点平均粗さ（Ｒｚ）＞
銅箔表面の十点平均粗さ（Ｒｚ）は、ＪＩＳ Ｃ６５１５：１９９８に準拠して測定した。
<10-point average roughness (Rz) of copper foil surface>
The ten-point average roughness (Rz) of the copper foil surface was measured according to JIS C6515: 1998.
＜下地皮膜層形成銅箔の下地皮膜層の各成分の付着量＞
下地皮膜層を形成した後の下地皮膜層形成銅箔を所定の形状（３ｃｍ幅×３ｃｍ長さ）に切断して測定サンプルとし、蛍光Ｘ線分析装置（（株）リガク製、ＺＳＸ ＰｒｉｍｕｓＩＩ）で分析して、検出された元素の強度から元素換算質量を算出し、下地皮膜層の単位面積当たりのジルコニウム、リン、バナジウム、珪素の付着量を求めた。
<Amount of each component of the undercoat layer of the copper foil forming the undercoat layer>
After the undercoat layer is formed, the undercoat layer-forming copper foil is cut into a predetermined shape (3 cm width x 3 cm length) to prepare a measurement sample, and a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., ZSX PrimusII) is used. The analysis was performed to calculate the elemental reduced mass from the detected element intensity, and the amount of zirconium, phosphorus, vanadium, and silicon adhered per unit area of the undercoat layer was determined.
＜接着性＞
作製した銅張積層板を１ｃｍ幅×７ｃｍ長さに切断し、ＪＩＳ Ｃ５０１２：１９９３に準拠して、導体の引き剥がし強さ（剥離強度）を測定し、以下の評価基準に従って評価した。なお、本評価においては、評点２点以下のものを接着性に劣るものとして評価した。
※評価基準：剥離強度
１点：０Ｎ／ｃｍ以上１Ｎ／ｃｍ未満
２点：１Ｎ／ｃｍ以上３Ｎ／ｃｍ未満
３点：３Ｎ／ｃｍ以上５Ｎ／ｃｍ未満
４点：５Ｎ／ｃｍ以上
<Adhesiveness>
The prepared copper-clad laminate was cut into a width of 1 cm and a length of 7 cm, and the peeling strength (peeling strength) of the conductor was measured in accordance with JIS C5012: 1993, and evaluated according to the following evaluation criteria. In this evaluation, those with a score of 2 points or less were evaluated as being inferior in adhesiveness.
* Evaluation criteria: Peeling strength 1 point: 0 N / cm or more and less than 1 N / cm 2 points: 1 N / cm or more and less than 3 N / cm 3 points: 3 N / cm or more and less than 5 N / cm 4 points: 5 N / cm or more
＜耐酸性＞
作製した銅張積層板を１ｃｍ幅×７ｃｍ長さに切断し、１ｍｏｌ／Ｌの塩酸水溶液中に２５℃で１時間浸漬した。その後、樹脂含有層を下地皮膜層から剥離し、下記式で定義される、剥離後の銅箔表面における下地皮膜の残存率を目視評価により求め、以下の評価基準に従って評価した。なお、本評価においては、評点２点以下のものを耐酸性に劣るものとして評価した。
下地皮膜の残存率（％）＝（銅箔表面における下地皮膜が存在する部分の面積）／（銅箔表面における下地皮膜が存在する部分と下地皮膜が存在しない部分との合計面積）×１００
※評価基準：下地皮膜の残存率
１点：５０％未満
２点：５０％以上８０％未満
３点：８０％以上１００％未満
４点：１００％
<Acid resistance>
The prepared copper-clad laminate was cut into 1 cm width × 7 cm length and immersed in a 1 mol / L hydrochloric acid aqueous solution at 25 ° C. for 1 hour. Then, the resin-containing layer was peeled from the base film layer, and the residual rate of the base film on the surface of the copper foil after peeling defined by the following formula was determined by visual evaluation and evaluated according to the following evaluation criteria. In this evaluation, those with a score of 2 points or less were evaluated as being inferior in acid resistance.
Residual rate of the base film (%) = (Area of the part where the base film exists on the copper foil surface) / (Total area of the part where the base film exists and the part where the base film does not exist on the copper foil surface) × 100
* Evaluation criteria: Residual rate of base film 1 point: less than 50% 2 points: 50% or more and less than 80% 3 points: 80% or more and less than 100% 4 points: 100%
＜耐熱性＞
作製した銅張積層板を加熱炉内で２７５℃で２分間加熱処理し、その後、１ｃｍ幅×７ｃｍ長さに切断し、接着性の評価と同様に、ＪＩＳ Ｃ５０１２：１９９３に準拠して、導体の引き剥がし強さ（剥離強度）を測定した。そして、接着性の評価で求めた初期の剥離強度を基準にして、下記式で定義される、加熱処理後の剥離強度維持率を算出し、以下の評価基準に従って評価した。なお、本評価においては、評点２点以下のものを耐熱性に劣るものとして評価した。
加熱処理後の剥離強度維持率（％）＝（加熱処理後の剥離強度）／（加熱処理前の初期の剥離強度）×１００
※評価基準：加熱処理後の剥離強度維持率
１点：０％以上２５％未満
２点：２５％以上５０％未満
３点：５０％以上７５％未満
４点：７５％以上
<Heat resistance>
The prepared copper-clad laminate was heat-treated at 275 ° C. for 2 minutes in a heating furnace, and then cut into 1 cm width × 7 cm length, and the conductor was subjected to JIS C5012: 1993 as in the evaluation of adhesiveness. The peeling strength (peeling strength) of the material was measured. Then, the peel strength maintenance rate after the heat treatment defined by the following formula was calculated based on the initial peel strength obtained in the evaluation of the adhesiveness, and evaluated according to the following evaluation criteria. In this evaluation, those with a score of 2 points or less were evaluated as being inferior in heat resistance.
Peeling strength retention rate after heat treatment (%) = (Peeling strength after heat treatment) / (Initial peeling strength before heat treatment) x 100
* Evaluation criteria: Peeling strength maintenance rate after heat treatment 1 point: 0% or more and less than 25% 2 points: 25% or more and less than 50% 3 points: 50% or more and less than 75% 4 points: 75% or more
［実施例１］
電解銅箔（純度９９．８質量％以上、厚さ１８μｍ、Ｒｚ１．５μｍ）を用意し、これを、アルカリ脱脂剤（日本パーカライジング株式会社製、商品名「ファインクリーナーＥ６４００」）の２質量％水溶液中に６５℃で１分間浸漬脱脂した後、イオン交換水に浸漬して洗浄した。さらに、１０質量％硫酸水溶液中に２５℃で１分間浸漬酸洗した後、イオン交換水に浸漬して洗浄した。続いて、循環式熱風乾燥炉内で銅箔を８０℃で１分間乾燥した。
[Example 1]
Prepare an electrolytic copper foil (purity 99.8% by mass or more, thickness 18 μm, Rz 1.5 μm), and use this as a 2% by mass aqueous solution of an alkaline degreasing agent (manufactured by Nippon Parkering Co., Ltd., trade name “Fine Cleaner E6400”). It was immersed in ion-exchanged water for 1 minute for degreasing and then immersed in ion-exchanged water for washing. Further, it was pickled in a 10 mass% sulfuric acid aqueous solution at 25 ° C. for 1 minute, and then immersed in ion-exchanged water for washing. Subsequently, the copper foil was dried at 80 ° C. for 1 minute in a circulating hot air drying furnace.
乾燥後、銅箔の表面に、ジルコニウム（Ａ）源として、炭酸ジルコニウムアンモニウム、リン（Ｂ）源として、ニトリロトリスメチレンホスホン酸を含有し、溶剤として水を含有する下地皮膜層形成用表面処理剤を、＃３ＳＵＳマイヤーバーを用いてバーコート法で塗布し、熱風循環式乾燥炉内で１００℃で１分間乾燥させて、銅箔表面に下地皮膜層を形成した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リンの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２であった。 After drying, a surface treatment agent for forming an undercoat layer containing zirconium (A) as a source of zirconium (A), nitrilotrismethylenephosphonic acid as a source of phosphorus (B), and water as a solvent on the surface of the copper foil. Was applied by a bar coating method using a # 3 SUS Meyer bar and dried in a hot air circulation type drying furnace at 100 ° C. for 1 minute to form an undercoat layer on the copper foil surface. When the amount of zirconium and phosphorus adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and the amount of phosphorus adhered was , Phosphorus element equivalent mass was 1.5 mg / m 2 .
得られた下地皮膜層形成銅箔の下地皮膜層を形成した面に、ＰＴＦＥ系プリプレグ（ロジャースコーポレーション製、商品名「ＲＯ３００３ＴＭＢｏｎｄｐｌｙ」、０．１ｍｍ厚み）を張り合わせ、プレス温度（加熱温度）３７０℃、プレス圧力３０ｋｇｆ／ｃｍ２、プレス時間４５分間の条件でプレス接着して、下地皮膜層形成銅箔の下地皮膜層上にフッ素樹脂含有層を有する銅張積層板を得た。 Forming a base film layer of the obtained base film layer A PTFE-based prepreg (manufactured by Rogers Corporation, trade name "RO3003 TM Bondply", 0.1 mm thickness) is bonded to the surface on which the base film layer of the copper foil is formed, and the press temperature (heating temperature) is 370. Press-bonding was performed under the conditions of ° C., press pressure of 30 kgf / cm 2 , and press time of 45 minutes to obtain a copper-clad laminate having a fluororesin-containing layer on the undercoat layer of the copper foil forming the undercoat layer.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例２］
（Ａ）ジルコニウム源として、炭酸ジルコニウムアンモニウム、（Ｂ）リン源として、ニトリロトリスメチレンホスホン酸、（Ｃ１）バナジウム源として、メタバナジン酸アンモニウムを含有し、溶剤として水を含有する下地皮膜層形成用表面処理剤を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リン、バナジウムの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２、バナジウムの付着量は、バナジウム元素換算質量で、４．０ｍｇ／ｍ２であった。
[Example 2]
Surface for forming an undercoat layer containing (A) zirconium carbonate as a zirconium source, (B) nitrilotrismethylenephosphonic acid as a phosphorus source, (C1) ammonium metavanadate as a vanadium source, and water as a solvent. An undercoat layer-forming copper foil was produced in the same manner as in Example 1 except that a treatment agent was used. When the amount of zirconium, phosphorus, and vanadium adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and phosphorus adhered. The amount was 1.5 mg / m 2 in terms of phosphorus element equivalent, and the amount of vanadium attached was 4.0 mg / m 2 in terms of vanadium element equivalent.
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例３］
（Ａ）ジルコニウム源として、炭酸ジルコニウムアンモニウム、（Ｂ）リン源として、ニトリロトリスメチレンホスホン酸、（Ｃ２）珪素源として、日産化学株式会社製、商品名「スノーテックスＯＬ」を含有し、溶剤として水を含有する下地皮膜層形成用表面処理剤を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リン、珪素の付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２、珪素の付着量は、珪素元素換算質量で、８．５ｍｇ／ｍ２であった。
[Example 3]
Contains (A) zirconium carbonate ammonium carbonate as a zirconium source, (B) nitrilotrismethylenephosphonic acid as a phosphorus source, and (C2) silicon source manufactured by Nissan Chemical Co., Ltd. under the trade name "Snowtex OL" as a solvent. A copper foil for forming an undercoat layer was produced in the same manner as in Example 1 except that a surface treatment agent for forming an undercoat layer containing water was used. When the adhesion amounts of zirconium, phosphorus, and silicon were measured for the undercoat film layer of the obtained undercoat layer-forming copper foil, the adhesion amount of zirconium was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and phosphorus adhered. the amount is, in terms of phosphorus mass, 1.5 mg / m 2, the adhesion amount of silicon in elemental silicon reduced mass, it was 8.5 mg / m 2.
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例４］
（Ａ）ジルコニウム源として、炭酸ジルコニウムアンモニウム、（Ｂ）リン源として、ニトリロトリスメチレンホスホン酸、（Ｃ１）バナジウム源として、メタバナジン酸アンモニウム、（Ｃ２）珪素源として、日産化学株式会社製、商品名「スノーテックスＯＬ」を含有し、溶剤として水を含有する下地皮膜層形成用表面処理剤を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リン、バナジウム、珪素の付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２、バナジウムの付着量は、バナジウム元素換算質量で、４．０ｍｇ／ｍ２、珪素の付着量は、珪素元素換算質量で、８．５ｍｇ／ｍ２であった。
[Example 4]
(A) Zirconium carbonate as a zirconium source, (B) Nitrilotrismethylenephosphonic acid as a phosphorus source, (C1) Ammonium metavanadate as a vanadium source, (C2) Silicon source, manufactured by Nissan Chemical Co., Ltd. An undercoat layer-forming copper foil was produced in the same manner as in Example 1 except that a surface treatment agent for forming an undercoat layer containing "Snowtex OL" and water as a solvent was used. When the adhesion amounts of zirconium, phosphorus, vanadium, and silicon were measured for the undercoat film layer of the obtained undercoat layer-forming copper foil, the adhesion amount of zirconium was 9.2 mg / m 2 in reduced mass in terms of zirconium element, and phosphorus. The amount of adhesion is 1.5 mg / m 2 in terms of phosphorus element, the amount of vanadium is 4.0 mg / m 2 in terms of vanadium element, and the amount of silicon attached is 8 in terms of silicon element. It was .5 mg / m 2 .
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例５］
電解銅箔に代えて、圧延銅箔（純度９９．９質量％以上、厚さ１８μｍ、Ｒｚ１．０μｍ）を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リンの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２であった。
[Example 5]
An undercoat layer-forming copper foil was produced in the same manner as in Example 1 except that a rolled copper foil (purity 99.9% by mass or more, thickness 18 μm, Rz 1.0 μm) was used instead of the electrolytic copper foil. When the amount of zirconium and phosphorus adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and the amount of phosphorus adhered was , Phosphorus element equivalent mass was 1.5 mg / m 2 .
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例６］
亜鉛−ニッケル合金めっきによる耐熱処理と、電解クロメートによる防錆処理を施した電解銅箔（厚さ１８μｍ、Ｒｚ１．５μｍ）を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リンの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２であった。
[Example 6]
Undercoat layer-forming copper foil in the same manner as in Example 1 except that an electrolytic copper foil (thickness 18 μm, Rz 1.5 μm) subjected to heat-resistant treatment by zinc-nickel alloy plating and rust prevention treatment by electrolytic chromate was used. Was produced. When the amount of zirconium and phosphorus adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and the amount of phosphorus adhered was , Phosphorus element equivalent mass was 1.5 mg / m 2 .
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例７］
亜鉛−ニッケル合金めっきによる耐熱処理を施した電解銅箔（厚さ１８μｍ、Ｒｚ１．５μｍ）を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リンの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２であった。
[Example 7]
An undercoat layer-forming copper foil was produced in the same manner as in Example 1 except that an electrolytic copper foil (thickness 18 μm, Rz 1.5 μm) subjected to heat resistance treatment by zinc-nickel alloy plating was used. When the amount of zirconium and phosphorus adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and the amount of phosphorus adhered was , Phosphorus element equivalent mass was 1.5 mg / m 2 .
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［実施例８］
電解クロメートによる防錆処理を施した電解銅箔（厚さ１８μｍ、Ｒｚ１．５μｍ）を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウム、リンの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２であった。
[Example 8]
An undercoat layer-forming copper foil was produced in the same manner as in Example 1 except that an electrolytic copper foil (thickness 18 μm, Rz 1.5 μm) subjected to rust prevention treatment by electrolytic chromate was used. When the amount of zirconium and phosphorus adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of reduced mass of zirconium element, and the amount of phosphorus adhered was , Phosphorus element equivalent mass was 1.5 mg / m 2 .
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［比較例１］
（Ａ）ジルコニウム源として、炭酸ジルコニウムアンモニウムを含有し、リン（Ｂ）源を含まず、溶剤として水を含有する下地皮膜層形成用表面処理剤を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、ジルコニウムの付着量を測定したところ、ジルコニウムの付着量は、ジルコニウム元素換算質量で、９．２ｍｇ／ｍ２であった。
[Comparative Example 1]
(A) The same as in Example 1 except that a surface treatment agent for forming an undercoat layer, which contains ammonium carbonate as a zirconium source, does not contain a phosphorus (B) source, and contains water as a solvent, is used. An undercoat layer-forming copper foil was prepared. When the amount of zirconium adhered to the obtained undercoat layer of the obtained undercoat layer-forming copper foil was measured, the amount of zirconium adhered was 9.2 mg / m 2 in terms of zirconium element equivalent mass.
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［比較例２］
（Ｂ）リン源として、ニトリロトリスメチレンホスホン酸を含有し、ジルコニウム（Ａ）源を含まず、溶剤として水を含有する下地皮膜層形成用表面処理剤を用いた以外は、実施例１と同様にして下地皮膜層形成銅箔を作製した。得られた下地皮膜層形成銅箔の下地皮膜層について、リンの付着量を測定したところ、リンの付着量は、リン元素換算質量で、１．５ｍｇ／ｍ２であった。
[Comparative Example 2]
(B) Same as in Example 1 except that a surface treatment agent for forming an undercoat layer containing nitrilotrismethylenephosphonic acid as a phosphorus source, no zirconium (A) source, and water as a solvent was used. To prepare a copper foil for forming an undercoat layer. When the amount of phosphorus adhered to the base film layer of the obtained base film layer-forming copper foil was measured, the amount of phosphorus adhered was 1.5 mg / m 2 in terms of phosphorus element equivalent mass.
次いで、この下地皮膜層形成銅箔を用いた以外は実施例１と同様にして銅張積層板を作製した。 Next, a copper-clad laminate was produced in the same manner as in Example 1 except that the copper foil for forming the base film layer was used.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［比較例３］
電解銅箔上に下地皮膜層を形成しなかった以外は、実施例１と同様にして銅張積層板を作製した。
[Comparative Example 3]
A copper-clad laminate was produced in the same manner as in Example 1 except that the undercoat layer was not formed on the electrolytic copper foil.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［比較例４］
亜鉛−ニッケル合金めっきによる耐熱処理と、電解クロメートによる防錆処理を施した電解銅箔上に下地皮膜層を形成しなかった以外は、実施例６と同様にして銅張積層板を作製した。
[Comparative Example 4]
A copper-clad laminate was produced in the same manner as in Example 6 except that the undercoat layer was not formed on the electrolytic copper foil subjected to the heat-resistant treatment by zinc-nickel alloy plating and the rust prevention treatment by electrolytic chromate.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［比較例５］
亜鉛−ニッケル合金めっきによる耐熱処理を施した電解銅箔上に下地皮膜層を形成しなかった以外は、実施例７と同様にして銅張積層板を作製した。
[Comparative Example 5]
A copper-clad laminate was produced in the same manner as in Example 7 except that the undercoat layer was not formed on the electrolytic copper foil that had been heat-resistant by zinc-nickel alloy plating.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
［比較例６］
電解クロメートによる防錆処理を施した電解銅箔上に下地皮膜層を形成しなかった以外は、実施例８と同様にして銅張積層板を作製した。
[Comparative Example 6]
A copper-clad laminate was produced in the same manner as in Example 8 except that the undercoat layer was not formed on the electrolytic copper foil that had been subjected to the rust prevention treatment by electrolytic chromate.
作製した銅張積層板の接着性、耐酸性、耐熱性を評価した。その結果を表１に示す。 The adhesiveness, acid resistance, and heat resistance of the prepared copper-clad laminate were evaluated. The results are shown in Table 1.
本発明によれば、銅系材料層の表面粗さが小さく、銅系材料層と樹脂層との接着性に優れ、耐酸性および耐熱性にも優れる銅張積層板を提供することができる。この銅張積層板は、プリント配線板、特に高周波プリント配線板等に特に好適に用いることができる。 According to the present invention, it is possible to provide a copper-clad laminate having a small surface roughness of a copper-based material layer, excellent adhesion between a copper-based material layer and a resin layer, and excellent acid resistance and heat resistance. This copper-clad laminate can be particularly preferably used for a printed wiring board, particularly a high-frequency printed wiring board or the like.
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| JP2004183015A (en) * | 2002-11-29 | 2004-07-02 | Nippon Parkerizing Co Ltd | Metal surface treating agent, metal surface treating method and surface treated metallic material |
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| WO2017138230A1 (en) * | 2016-02-08 | 2017-08-17 | 東洋鋼鈑株式会社 | Organic resin-coated steel sheet, method for producing same, and can and can lid each using said organic resin-coated steel sheet |
| JP2018188720A (en) * | 2017-05-11 | 2018-11-29 | 日本パーカライジング株式会社 | Aqueous metal surface treatment agent, metal material having surface treatment layer and manufacturing method of the same |
| JP2019104171A (en) * | 2017-12-12 | 2019-06-27 | 住友電気工業株式会社 | Metal-resin laminate |
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| JP2004183015A (en) * | 2002-11-29 | 2004-07-02 | Nippon Parkerizing Co Ltd | Metal surface treating agent, metal surface treating method and surface treated metallic material |
| JP2013023705A (en) * | 2011-07-15 | 2013-02-04 | Nippon Parkerizing Co Ltd | Agent of treating metal surface, and metallic material treated with the same |
| JP2015134957A (en) * | 2013-12-18 | 2015-07-27 | 日本パーカライジング株式会社 | Aqueous metal surface treatment agent, metal surface treatment film and metal material having metal surface treatment film |
| WO2017138230A1 (en) * | 2016-02-08 | 2017-08-17 | 東洋鋼鈑株式会社 | Organic resin-coated steel sheet, method for producing same, and can and can lid each using said organic resin-coated steel sheet |
| JP2018188720A (en) * | 2017-05-11 | 2018-11-29 | 日本パーカライジング株式会社 | Aqueous metal surface treatment agent, metal material having surface treatment layer and manufacturing method of the same |
| JP2019104171A (en) * | 2017-12-12 | 2019-06-27 | 住友電気工業株式会社 | Metal-resin laminate |
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| WO2023053948A1 (en) * | 2021-09-29 | 2023-04-06 | 信越ポリマー株式会社 | Metal-clad laminated plate |
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