TWI627876B - Metal foil with carrier - Google Patents
Metal foil with carrier Download PDFInfo
- Publication number
- TWI627876B TWI627876B TW102127743A TW102127743A TWI627876B TW I627876 B TWI627876 B TW I627876B TW 102127743 A TW102127743 A TW 102127743A TW 102127743 A TW102127743 A TW 102127743A TW I627876 B TWI627876 B TW I627876B
- Authority
- TW
- Taiwan
- Prior art keywords
- metal foil
- carrier
- less
- resin
- plate
- Prior art date
Links
- 239000011888 foil Substances 0.000 title claims abstract description 337
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 332
- 239000002184 metal Substances 0.000 title claims abstract description 331
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims description 91
- 229920005989 resin Polymers 0.000 claims description 91
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 76
- 239000011889 copper foil Substances 0.000 claims description 61
- 239000000758 substrate Substances 0.000 claims description 61
- 238000004519 manufacturing process Methods 0.000 claims description 58
- 150000003839 salts Chemical class 0.000 claims description 44
- 238000007747 plating Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 13
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 13
- 238000010030 laminating Methods 0.000 claims description 12
- 150000004662 dithiols Chemical class 0.000 claims description 10
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 claims description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 4
- 125000002118 cyano ester group Chemical group 0.000 claims 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 2
- 150000001916 cyano esters Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 50
- 239000010949 copper Substances 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 15
- 238000007772 electroless plating Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 thiol compound Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 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
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- IDXOZZNUOVLNGO-UHFFFAOYSA-N 12-sulfanyldodecan-3-ol Chemical compound OC(CCCCCCCCCS)CC IDXOZZNUOVLNGO-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- AMNLXDDJGGTIPL-UHFFFAOYSA-N 2,4-dimethylbenzenethiol Chemical compound CC1=CC=C(S)C(C)=C1 AMNLXDDJGGTIPL-UHFFFAOYSA-N 0.000 description 1
- GFCRSKBAFJBQQS-UHFFFAOYSA-N 2-ethyl-11-sulfanylundecanoic acid Chemical compound C(=O)(O)C(CCCCCCCCCS)CC GFCRSKBAFJBQQS-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017868 Cu—Ni—Co Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910001199 N alloy Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- YLWCNZQVNYRELK-UHFFFAOYSA-N dodecane-1-thiol;sodium Chemical compound [Na].CCCCCCCCCCCCS YLWCNZQVNYRELK-UHFFFAOYSA-N 0.000 description 1
- 238000000454 electroless metal deposition Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- AWIJRPNMLHPLNC-UHFFFAOYSA-N thiocarboxylic acid group Chemical group C(=S)O AWIJRPNMLHPLNC-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
- H05K3/0061—Laminating printed circuit boards onto other substrates, e.g. metallic substrates onto a metallic substrate, e.g. a heat sink
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
本發明提供一種樹脂製之板狀載體與金屬箔之剝離強度經調節之附有載體之金屬箔。 The present invention provides a metal foil with a carrier having a peeling strength adjusted by a resin-made plate-shaped carrier and a metal foil.
本發明之附有載體之金屬箔係由樹脂製之板狀載體、與可剝離地密接於該載體之至少一面之金屬箔所構成者，係使用於分子內具有2個以下之巰基之化合物貼合板狀載體與金屬箔而成。 The metal foil with a carrier of the present invention is composed of a resin-made plate-shaped carrier and a metal foil which is detachably adhered to at least one side of the carrier, and is used for a compound having two or less sulfhydryl groups in the molecule. The plate-shaped carrier is formed of a metal foil.
Description
本發明係關於一種附有載體之金屬箔。更詳細而言，係關於一種於印刷配線板所使用之單面或者2層以上之多層積層板或極薄之無芯基板之製造中使用之附有載體之金屬箔。 The present invention relates to a metal foil with a carrier. More specifically, it relates to a metal foil with a carrier used for the manufacture of a single-sided or two-layer multilayer laminated board or an extremely thin coreless substrate used for a printed wiring board.
通常，印刷配線板以使合成樹脂含漬於合成樹脂板、玻璃板、玻璃不織布、紙等基材而獲得之稱為「預浸體(Prepreg)」之介電材為基本之構成材料。又，於與預浸體相對之側接合有具有導電性之銅或銅合金箔等片材。通常將如此組裝之積層物稱為CCL(Copper Clad Laminate，敷銅層板)材。通常將銅箔之與預浸體接觸之面設為無光澤面，以提高接合強度。亦有使用鋁、鎳、鋅等箔，代替銅或銅合金箔之情況。該等之厚度為5~200μm左右。將該通常使用之CCL(Copper Clad Laminate)材示於圖1。 In general, a printed wiring board is a basic constituent material called a "prepreg" obtained by coating a synthetic resin with a substrate such as a synthetic resin sheet, a glass plate, a glass nonwoven fabric, or paper. Further, a sheet such as copper or a copper alloy foil having conductivity is bonded to the side opposite to the prepreg. The laminate thus assembled is generally referred to as a CCL (Copper Clad Laminate) material. The surface of the copper foil that is in contact with the prepreg is usually set to a matte side to improve the bonding strength. There are also cases where foils such as aluminum, nickel, and zinc are used instead of copper or copper alloy foils. These thicknesses are about 5 to 200 μm. The commonly used CCL (Copper Clad Laminate) material is shown in Fig. 1.
於專利文獻1中提出有一種附有載體之金屬箔，其由合成樹脂製之板狀載體、與可機械剝離地密接於該載體之至少一面之金屬箔構成，記載有該附有載體之金屬箔可供於印刷配線板之組裝之意旨。並且，表示板狀載體與金屬箔之剝離強度較理想為1gf/cm~1kgf/cm。根據該附有載體之金屬箔，由於利用合成樹脂而整個面地支持銅箔，故而可防止於積層中於銅箔產生皺褶。又，由於該附有載體之金屬箔係金屬箔與合成樹脂 無間隙地密接，故而於對金屬箔表面進行鍍金或蝕刻時，可將其投入至鍍金或蝕刻用之藥液中。進而，由於合成樹脂之線膨脹係數處於與作為基板之構成材料之銅箔及聚合後之預浸體同等之水平，故而無引起電路之位置偏移之情況，因此具有不良品產生變少，可提高良率之優異之效果。 Patent Document 1 proposes a metal foil with a carrier made of a synthetic resin-made plate-shaped carrier and a metal foil which is mechanically peelably adhered to at least one side of the carrier, and the metal with the carrier is described. The foil is intended for assembly of printed wiring boards. Further, the peel strength of the plate-shaped carrier and the metal foil is preferably from 1 gf/cm to 1 kgf/cm. According to the metal foil with a carrier, since the copper foil is supported over the entire surface by the synthetic resin, it is possible to prevent wrinkles from occurring in the copper foil in the laminate. Moreover, the metal foil-based metal foil with the carrier and the synthetic resin When the surface of the metal foil is plated or etched, it can be put into a liquid for gold plating or etching. Further, since the linear expansion coefficient of the synthetic resin is at the same level as the copper foil as the constituent material of the substrate and the prepreg after the polymerization, the positional deviation of the circuit is not caused, and thus the number of defective products is reduced. Improve the excellent results of yield.
[專利文獻1]日本特開2009-272589號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-272589
[專利文獻2]日本特開2000-196207號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-196207
專利文獻1中記載之附有載體之金屬箔係藉由簡化印刷電路板之製造步驟及提高良率而對削減製造成本貢獻較大之劃時代之發明，但針對板狀載體與金屬箔之剝離強度之最佳化及其手段尚留有研究之餘地。尤其是，作為對於本發明者而言較明顯之問題，可列舉板狀載體與金屬箔之剝離強度因板狀載體之材質變得過高之方面，較理想為提供一種可簡便地調節該剝離強度之手段。因此，本發明之課題在於提供一種樹脂製之板狀載體與金屬箔之剝離強度經調節之附有載體之金屬箔。 The metal foil with a carrier described in Patent Document 1 is an epoch-making invention that contributes to a reduction in manufacturing cost by simplifying the manufacturing steps of the printed circuit board and improving the yield, but the peel strength of the plate-shaped carrier and the metal foil There is still room for research on the optimization and its means. In particular, as a problem that is obvious to the inventors, the peeling strength of the plate-shaped carrier and the metal foil is excessively high because the material of the plate-shaped carrier is too high, and it is preferable to provide a simple adjustment of the peeling. The means of strength. Accordingly, an object of the present invention is to provide a metal foil with a carrier having a peel strength of a resin-made plate-shaped carrier and a metal foil adjusted.
本發明者等人對樹脂板與金屬箔之間之剝離強度之調節方法進行努力研究，結果發現如下可能性：於樹脂板與金屬箔之貼合之前，利用具有特定之結構之巰基之化合物對至少一表面進行被覆處理，藉此可實現適應所需之用途之剝離強度，從而完成本發明。 The inventors of the present invention have conducted an effort to adjust the peel strength between the resin sheet and the metal foil, and as a result, have found that it is possible to use a compound pair having a specific structure of a mercapto group before the resin sheet is bonded to the metal foil. At least one surface is subjected to a coating treatment, whereby the peel strength for the desired use can be achieved, thereby completing the present invention.
即，本發明如以下所述。 That is, the present invention is as follows.
(1)一種附有載體之金屬箔，其係由樹脂製之板狀載體、與可剝離地密接於該載體之至少一面之金屬箔所構成者，且係使用於分子內具有2個 以下之巰基之化合物貼合板狀載體與金屬箔而成。 (1) A metal foil with a carrier which is composed of a resin-made plate-shaped carrier and a metal foil which is peelably adhered to at least one side of the carrier, and is used in the molecule. The following thiol-based compound is formed by laminating a plate-shaped carrier and a metal foil.
(2)如(1)記載之附有載體之金屬箔，其中上述於分子內具有2個以下之巰基之化合物係選自由硫醇、二硫醇、硫羧酸或其鹽、二硫羧酸或其鹽、硫代磺酸(thiosulfonic acid)或其鹽、及二硫代磺酸或其鹽所構成之群中之至少一種。 (2) The metal foil with a carrier as described in (1), wherein the compound having two or less mercapto groups in the molecule is selected from the group consisting of a mercaptan, a dithiol, a sulfuric acid or a salt thereof, and a dithiocarboxylic acid. And at least one of the group consisting of a salt thereof, a thiosulfonic acid or a salt thereof, and a dithiosulfonic acid or a salt thereof.
(3)如(1)或(2)記載之附有載體之金屬箔，其中板狀載體與金屬箔之剝離強度為10gf/cm以上且200gf/cm以下。 (3) The metal foil with a carrier as described in (1) or (2), wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less.
(4)如(1)至(3)中任一項記載之附有載體之金屬箔，其中樹脂製之板狀載體包含熱硬化性樹脂。 (4) The carrier-attached metal foil according to any one of (1) to (3) wherein the resin-made plate-shaped carrier contains a thermosetting resin.
(5)如(1)至(4)中任一項記載之附有載體之金屬箔，其中樹脂製之板狀載體為預浸體。 (5) The metal foil with a carrier as described in any one of (1) to (4), wherein the resin-made plate-shaped carrier is a prepreg.
(6)如(4)或(5)記載之附有載體之金屬箔，其中上述樹脂製之板狀載體具有120~320℃之玻璃轉移溫度Tg。 (6) The metal foil with a carrier as described in (4) or (5), wherein the plate-shaped carrier made of the above resin has a glass transition temperature Tg of 120 to 320 °C.
(7)如(1)至(6)中任一項記載之附有載體之金屬箔，其中上述金屬箔之與上述載體接觸之側之表面的十點平均粗糙度(Rz jis)為3.5μm以下。 (7) The carrier-attached metal foil according to any one of (1) to (6), wherein a ten-point average roughness (Rz jis) of a surface of the metal foil on the side in contact with the carrier is 3.5 μm. the following.
(8)如(1)至(7)中任一項記載之附有載體之金屬箔，其中上述金屬箔之不與上述載體接觸之側之表面的十點平均粗糙度(Rz jis)為0.4μm以上且10.0μm以下。 (8) The carrier-attached metal foil according to any one of (1) to (7), wherein a ten-point average roughness (Rz jis) of a surface of the metal foil which is not in contact with the carrier is 0.4 Μm or more and 10.0 μm or less.
(9)如(1)至(8)中任一項記載之附有載體之金屬箔，其中上述金屬箔之厚度為1μm以上且400μm以下。 (9) The metal foil with a carrier as described in any one of (1) to (8), wherein the metal foil has a thickness of 1 μm or more and 400 μm or less.
(10)如(1)至(9)中任一項記載之附有載體之金屬箔，其中於220℃加熱3小時、6小時或9小時中之至少一者後之金屬箔與板狀載體之剝離強度為10gf/cm以上且200gf/cm以下。 (10) The metal foil with a carrier according to any one of (1) to (9), wherein the metal foil and the plate-shaped carrier after heating at 220 ° C for at least one of 3 hours, 6 hours or 9 hours The peel strength is 10 gf/cm or more and 200 gf/cm or less.
(11)如(1)至(10)中任一項記載之附有載體之金屬箔，其中上述金 屬箔為銅箔。 (11) The carrier-attached metal foil according to any one of (1) to (10), wherein the gold The foil is copper foil.
(12)一種印刷配線板用金屬箔，其於金屬箔之表面具有於分子內具有2個以下之巰基之化合物。 (12) A metal foil for a printed wiring board having a compound having two or less sulfhydryl groups in a molecule on a surface of a metal foil.
(13)如(12)記載之印刷配線板用金屬箔，其中上述於分子內具有2個以下之巰基之化合物係選自由硫醇、二硫醇、硫羧酸或其鹽、二硫羧酸或其鹽、硫代磺酸或其鹽、及二硫代磺酸或其鹽所構成之群中之至少一種。 (13) The metal foil for a printed wiring board according to the above aspect, wherein the compound having two or less mercapto groups in the molecule is selected from the group consisting of a mercaptan, a dithiol, a sulfuric acid or a salt thereof, and a dithiocarboxylic acid. And at least one of the group consisting of a salt thereof, a thiosulfonic acid or a salt thereof, and a dithiosulfonic acid or a salt thereof.
(14)如(12)或(13)記載之印刷配線板用金屬箔，其中對上述金屬箔之使分子內具有2個以下之巰基之化合物作用之側之表面，於使該化合物作用之前，進行鉻酸鹽處理。 (14) The metal foil for a printed wiring board according to the above aspect, wherein the surface of the metal foil which has a compound having two or less sulfhydryl groups in the molecule is applied to the surface of the metal foil before the action of the compound Perform chromate treatment.
(15)如(12)至(14)中任一項記載之印刷配線板用金屬箔，其中上述金屬箔之與上述載體接觸之側之表面的十點平均粗糙度(Rz jis)為3.5μm以下。 The metal foil for a printed wiring board according to any one of the above aspects, wherein the surface of the metal foil on the side in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm. the following.
(16)如(12)至(15)中任一項記載之印刷配線板用金屬箔，其中上述金屬箔之不與上述載體接觸之側之表面的十點平均粗糙度(Rz jis)為0.4μm以上且10.0μm以下。 The metal foil for a printed wiring board according to any one of the above aspects, wherein the surface of the side of the metal foil which is not in contact with the carrier has a ten-point average roughness (Rz jis) of 0.4. Μm or more and 10.0 μm or less.
(17)如(12)至(16)中任一項記載之印刷配線板用金屬箔，其中上述金屬箔為銅箔。 The metal foil for a printed wiring board according to any one of (12), wherein the metal foil is a copper foil.
(18)一種金屬箔，其係至少於一表面具有於分子內具有2個以下之巰基之化合物者，且用於使樹脂製之板狀載體可剝離地密接於該表面之用途。 (18) A metal foil which is a compound having at least one surface having at least two fluorenyl groups in a molecule, and is used for peeling and adhering a resin-made plate-shaped carrier to the surface.
(19)如(18)記載之金屬箔，其中上述於分子內具有2個以下之巰基之化合物係選自由硫醇、二硫醇、硫羧酸或其鹽、二硫羧酸或其鹽、硫代磺酸或其鹽、及二硫代磺酸或其鹽所構成之群中之至少一種。 (19) The metal foil according to (18), wherein the compound having two or less mercapto groups in the molecule is selected from the group consisting of a mercaptan, a dithiol, a sulfuric acid or a salt thereof, a dithiocarboxylic acid or a salt thereof, At least one of the group consisting of thiosulfonic acid or a salt thereof, and a dithiosulfonic acid or a salt thereof.
(20)如(18)或(19)記載之金屬箔，其中對上述金屬箔之使分子內具有2個以下之巰基之化合物作用之側之表面，於使該於分子內具有2個以下之巰基之化合物作用之前，進行鉻酸鹽處理。 (20) The metal foil according to (18) or (19), wherein the surface of the metal foil having a side having two or less sulfhydryl groups in the molecule acts on the side of the metal, and has two or less in the molecule. The chromate treatment is carried out before the action of the thiol compound.
(21)如(18)至(20)中任一項記載之金屬箔，其中上述金屬箔之與上述載體接觸之側之表面的十點平均粗糙度(Rz jis)為3.5μm以下。 The metal foil according to any one of (18) to (20), wherein the surface of the side of the metal foil on the side in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less.
(22)一種樹脂製之板狀載體，其至少於一表面具有於分子內具有2個以下之巰基之化合物。 (22) A resin-made plate-shaped carrier having a compound having at least two indenyl groups in a molecule on at least one surface.
(23)一種板狀載體，其係至少於一表面具有於分子內具有2個以下之巰基之化合物之樹脂製者，且用於使金屬箔可剝離地密接於該表面之用途。 (23) A plate-shaped carrier which is a resin having at least one surface having a compound having two or less sulfhydryl groups in a molecule, and is used for adhering the metal foil to the surface in a peelable manner.
(24)如(22)或(23)記載之板狀載體，其中上述於分子內具有2個以下之巰基之化合物係選自由硫醇、二硫醇、硫羧酸或其鹽、二硫羧酸或其鹽、硫代磺酸或其鹽、及二硫代磺酸或其鹽所構成之群中之至少一種。 (24) The plate-shaped carrier according to (22) or (23), wherein the compound having two or less sulfhydryl groups in the molecule is selected from the group consisting of a thiol, a dithiol, a sulfuric acid or a salt thereof, and a dithiocarboxylate. At least one of the group consisting of an acid or a salt thereof, a thiosulfonic acid or a salt thereof, and a dithiosulfonic acid or a salt thereof.
(25)一種多層覆金屬積層板之製造方法，其包含：對(1)至(11)中任一項記載之附有載體之金屬箔之至少一金屬箔側，積層樹脂，繼而重複積層樹脂或金屬箔1次以上。 (25) A method for producing a multilayer metal-clad laminate comprising: at least one metal foil side of the metal foil with a carrier according to any one of (1) to (11), a resin layer, and then a resin layer is repeatedly laminated Or metal foil more than 1 time.
(26)一種多層覆金屬積層板之製造方法，其包含：於(1)至(11)中任一項記載之附有載體之金屬箔之金屬箔側積層樹脂，繼而重複積層樹脂、單面或者兩面覆金屬積層板、或(1)至(11)中任一項記載之附有載體之金屬箔、或金屬箔1次以上。 (26) A method of producing a multi-layer metal-clad laminate comprising the metal foil side-layer resin of the metal foil with a carrier according to any one of (1) to (11), and then repeating the laminated resin, one side Or a double-sided metal-clad laminate, or a metal foil with a carrier described in any one of (1) to (11), or a metal foil may be used once or more.
(27)如(25)或(26)記載之多層覆金屬積層板之製造方法，其進而包含：剝離而分離上述附有載體之金屬箔之板狀載體與金屬箔之步驟。 (27) The method for producing a multilayer metal-clad laminate according to (25) or (26), further comprising the step of separating the plate-shaped carrier and the metal foil of the metal foil with the carrier.
(28)如(27)記載之多層覆金屬積層板之製造方法，其包含：藉由蝕刻除去剝離而分離之金屬箔之一部分或全部之步驟。 (28) The method for producing a multilayer metal-clad laminate according to (27), which comprises the step of removing part or all of the metal foil separated by etching.
(29)一種多層覆金屬積層板，其係藉由(25)至(28)中任一項記載之製造方法而獲得。 (29) A multilayer metal-clad laminate obtained by the production method according to any one of (25) to (28).
(30)一種增層基板之製造方法，其包含：於(1)至(11)中任一項記載之積層體之金屬箔側形成一層以上之增層配線層之步驟。 (30) A method of producing a build-up substrate, comprising the step of forming one or more build-up wiring layers on the metal foil side of the laminate according to any one of (1) to (11).
(31)如(30)記載之增層基板之製造方法，其中增層配線層係使用相 減法或全加成法或半加成法中之至少一者而形成。 (31) The method for producing a build-up substrate according to (30), wherein the build-up wiring layer uses a phase Formed by subtraction or at least one of a full additive process or a semi-additive process.
(32)一種增層基板之製造方法，其包含：於(1)至(11)中任一項記載之附有載體之金屬箔之至少一金屬箔側積層樹脂，繼而重複積層樹脂、單面或者兩面配線基板、單面或者兩面覆金屬積層板、(1)至(11)中任一項記載之附有載體之金屬箔或金屬箔1次以上。 (32) A method for producing a build-up substrate, comprising: at least one metal foil side build-up resin of the metal foil with a carrier according to any one of (1) to (11), and then repeating the laminated resin, one side Or a double-sided wiring board, a single-sided or double-sided metal-clad laminate, or a metal foil or a metal foil with a carrier described in any one of (1) to (11).
(33)如(32)記載之增層基板之製造方法，其進而包含如下步驟：開孔於單面或者兩面配線基板、單面或者兩面覆金屬積層板、附有載體之金屬箔之金屬箔、附有載體之金屬箔之板狀載體、或樹脂，並於該孔之側面及底面進行導通鍍敷。 (33) The method for producing a build-up substrate according to (32), further comprising the steps of: a metal foil having a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, and a metal foil with a carrier; A plate-shaped carrier or a resin with a metal foil attached thereto, and conducting plating on the side surface and the bottom surface of the hole.
(34)如(32)或(33)記載之增層基板之製造方法，其進而包含進行如下步驟1次以上：於構成上述單面或者兩面配線基板之金屬箔、構成單面或者兩面覆金屬積層板之金屬箔、及構成附有載體之金屬箔之金屬箔中之至少一者形成配線。 (34) The method for producing a build-up substrate according to (32) or (33), further comprising the step of performing the following steps one or more times: forming a metal foil of the single-sided or double-sided wiring substrate, forming a single-sided or two-sided metal-clad At least one of the metal foil of the laminate and the metal foil constituting the metal foil with the carrier forms a wiring.
(35)如(32)至(34)中任一項記載之增層基板之製造方法，其進而包含如下步驟：於形成有配線之表面上，使金屬箔密接於單面之(1)至(11)中任一項記載之附有載體之金屬箔之樹脂板側接觸而積層。 The method for producing a build-up substrate according to any one of (32) to (34), further comprising the step of: adhering the metal foil to one side (1) to the surface on which the wiring is formed The resin sheet of the metal foil with a carrier described in any one of (11) is in contact with the side and laminated.
(36)如(32)至(34)中任一項記載之增層基板之製造方法，其進而包含如下步驟：於形成有配線之表面上，積層樹脂，並使金屬箔密接於兩面之(1)至(11)中任一項記載之附有載體之金屬箔之一金屬箔與該樹脂接觸而積層。 The method for producing a build-up substrate according to any one of (32) to (34), further comprising the step of laminating a resin on the surface on which the wiring is formed and adhering the metal foil to both sides ( A metal foil of one of the metal foils with a carrier described in any one of (1) is in contact with the resin to be laminated.
(37)如(32)至(36)中任一項記載之增層基板之製造方法，其中上述樹脂之至少一者為預浸體。 The method for producing a build-up substrate according to any one of (32) to (36), wherein at least one of the resins is a prepreg.
(38)如(30)至(37)中任一項記載之增層基板之製造方法，其進而包含：剝離而分離上述附有載體之金屬箔之板狀載體與金屬箔之步驟。 The method for producing a build-up substrate according to any one of (30) to (37), further comprising the step of separating the plate-shaped carrier and the metal foil of the metal foil with the carrier.
(39)如(38)記載之增層配線板之製造方法，其進而包含：藉由蝕刻 除去與板狀載體密接之金屬箔之一部分或全部之步驟。 (39) The method for producing a build-up wiring board according to (38), further comprising: etching The step of removing part or all of the metal foil in close contact with the plate-shaped carrier.
(40)一種增層配線板，其係藉由(38)或(39)記載之製造方法而獲得。 (40) A build-up wiring board obtained by the production method described in (38) or (39).
(41)一種印刷電路板之製造方法，其包含：藉由(30)至(37)中任一項記載之製造方法製造增層基板之步驟。 (41) A method of producing a printed circuit board, comprising the step of producing a build-up substrate by the production method according to any one of (30) to (37).
(42)一種印刷電路板之製造方法，其包含：藉由(38)或(39)記載之製造方法製造增層配線板之步驟。 (42) A method of producing a printed circuit board, comprising the step of producing a build-up wiring board by the manufacturing method described in (38) or (39).
藉由本發明，可簡便地調節板狀載體與金屬箔之剝離強度。因此，例如，可將習知顯示出過高之剝離強度之附有載體之金屬箔調節至較佳之剝離強度，因此獲得利用附有載體之金屬箔之印刷配線板之生產性提高之優勢。 According to the present invention, the peel strength of the plate-shaped carrier and the metal foil can be easily adjusted. Therefore, for example, the carrier-attached metal foil which exhibits excessive peel strength can be adjusted to a preferable peel strength, and thus the productivity of the printed wiring board using the metal foil with the carrier is improved.
10‧‧‧積層模具 10‧‧‧Laminated mold
11‧‧‧附有載體之金屬箔 11‧‧‧Metal foil with carrier
11a‧‧‧金屬箔 11a‧‧‧metal foil
11b‧‧‧於分子內具有2個以下之巰基之化合物 11b‧‧‧ compounds with two or less sulfhydryl groups in the molecule
11c‧‧‧板狀載體 11c‧‧‧plate carrier
12‧‧‧預浸體 12‧‧‧Prepreg
13‧‧‧內層芯 13‧‧‧ Inner core
14‧‧‧頁 Page 14‧‧‧
15‧‧‧書 15‧‧ books
16‧‧‧增層層 16‧‧‧Additional layer
圖1表示CCL之一構成例。 Fig. 1 shows an example of the configuration of the CCL.
圖2表示本發明之附有載體之金屬箔之一構成例。 Fig. 2 shows an example of the constitution of a metal foil with a carrier of the present invention.
圖3表示利用本發明之附有載體之銅箔(銅箔接合於樹脂板之單面之形態)之多層CCL之組裝例。 Fig. 3 shows an example of assembly of a multilayer CCL using a copper foil with a carrier of the present invention (a form in which a copper foil is bonded to one side of a resin sheet).
圖4表示利用本發明之附有載體之銅箔(銅箔接合於樹脂板之兩面之形態)之多層CCL之組裝例。 Fig. 4 shows an example of assembly of a multilayer CCL using the carrier-attached copper foil (the form in which the copper foil is bonded to both sides of the resin sheet) of the present invention.
於本發明之附有載體之金屬箔之一實施形態中，準備一種附有載體之金屬箔，其由樹脂製之板狀載體與可剝離地密接於該載體之單面 或兩面、較佳為兩面之金屬箔構成。本發明之附有載體之金屬箔之一構成例示於圖2及圖3。尤其是，於圖3之開頭處，顯示出使金屬箔11a可剝離地密接於樹脂製之板狀載體11c之兩面之附有載體之金屬箔11。板狀載體11c與金屬箔11a之間係使用下述之於分子內具有2個以下之巰基之化合物或其鹽11b進行貼合。 In one embodiment of the metal foil with a carrier of the present invention, a metal foil with a carrier is prepared, which is made of a resin-made plate-shaped carrier and is detachably adhered to one side of the carrier. Or two-sided, preferably two-sided metal foil. One of the structures of the metal foil with a carrier of the present invention is illustrated in Figs. 2 and 3. In particular, at the beginning of FIG. 3, the metal foil 11 with the carrier attached to both sides of the resin-made plate-shaped carrier 11c is peelably adhered to the metal foil 11a. Between the plate-shaped carrier 11c and the metal foil 11a, the following compound having two or less sulfhydryl groups in the molecule or a salt thereof 11b is used for bonding.
構造方面而言，與圖1所示之CCL類似，但本發明之附有載體之金屬箔係金屬箔與樹脂最終被分離者，具有可容易地剝離之構造。於該方面，CCL並非使其剝離者，因此為構造與功能完全不同者。 Structurally, it is similar to the CCL shown in Fig. 1, but the metal foil-based metal foil with the carrier of the present invention and the resin are finally separated, and have a structure that can be easily peeled off. In this respect, CCL is not a person who is stripped, so it is completely different in structure and function.
由於本發明所使用之附有載體之金屬箔均必須剝離，故而密接性過高者較不便，但板狀載體與金屬箔必需有於在印刷電路板製作過程所進行之鍍敷等藥液處理步驟中不剝離之程度之密接性。 Since the metal foil with the carrier used in the present invention must be peeled off, the adhesion is too high, and the plate carrier and the metal foil must be treated by a chemical solution such as plating performed during the manufacturing process of the printed circuit board. The degree of adhesion without peeling in the step.
用以實現此種密接性之剝離強度之調節係藉由使用於分子內具有2個以下之巰基之化合物或其鹽而進行。其原因在於，藉由將此種化合物或其鹽用於板狀載體與金屬箔之間而進行貼合，密接性適度地降低，且可將剝離強度調節至上述範圍。於使於分子內具有3個以上之巰基之化合物或其鹽介存於板狀載體與金屬箔之間而貼合之情形時，不適合本案記載之降低剝離強度之目的。其原因在於認為：若巰基過量地存在於分子內，則有藉由巰基彼此、或巰基與板狀載體、或巰基與金屬箔之化學反應而過量地產生硫鍵、雙硫鍵或聚硫鍵，於板狀載體與金屬箔之間形成堅固之三維交聯結構，因此剝離強度上升之情況。此種事例揭示於專利文獻2(日本特開2000-196207)中。 The adjustment of the peel strength for achieving such adhesion is carried out by using a compound having two or less sulfhydryl groups in the molecule or a salt thereof. The reason for this is that the compound or a salt thereof is used for bonding between the plate-shaped carrier and the metal foil, and the adhesion is appropriately lowered, and the peel strength can be adjusted to the above range. When a compound having three or more mercapto groups in a molecule or a salt thereof is interposed between a plate-shaped carrier and a metal foil, it is not suitable for the purpose of reducing the peel strength described in the present invention. The reason for this is that if the sulfhydryl group is excessively present in the molecule, the sulfur bond, the disulfide bond or the polysulfide bond is excessively generated by chemical reaction of the sulfhydryl group with each other, or the sulfhydryl group and the plate-shaped carrier, or the sulfhydryl group and the metal foil. A strong three-dimensional crosslinked structure is formed between the plate-shaped carrier and the metal foil, and thus the peel strength is increased. Such an example is disclosed in Patent Document 2 (JP-A-2000-196207).
作為該於分子內具有2個以下之巰基之化合物，可列舉：硫醇、二硫醇、硫羧酸或其鹽、二硫羧酸或其鹽、硫代磺酸或其鹽、及二硫代磺酸或其鹽，可使用選自該等之中之至少一種。 Examples of the compound having two or less mercapto groups in the molecule include a mercaptan, a dithiol, a sulfuric acid or a salt thereof, a dithiocarboxylic acid or a salt thereof, a thiosulfonic acid or a salt thereof, and a disulfide As the sulfonic acid or a salt thereof, at least one selected from the group consisting of these may be used.
硫醇係於分子內具有一個巰基者，例如由R-SH表示。此處， R表示亦可包含羥基或胺基之脂肪族系或芳香族系烴基或雜環基。 A thiol is one having a fluorenyl group in the molecule, and is represented, for example, by R-SH. Here, R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group.
二硫醇係於分子內具有兩個巰基者，例如由R(SH)2表示。R表示亦可包含羥基或胺基之脂肪族系或芳香族系烴基或雜環基。又，兩個巰基可分別鍵結於相同之碳，亦可互相鍵結於各自之碳或氮。 The dithiol is one having two indenyl groups in the molecule, and is represented, for example, by R(SH) 2 . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the two sulfhydryl groups may be bonded to the same carbon, respectively, or may be bonded to each other to carbon or nitrogen.
硫羧酸係有機羧酸之羥基經巰基取代者，例如由R-CO-SH表示。R表示亦可包含羥基或胺基之脂肪族系或芳香族系烴基或雜環基。又，硫羧酸亦可於鹽之形態下使用。再者，亦可使用具有兩個硫羧酸基之化合物。 The hydroxyl group of the thiocarboxylic acid-based organic carboxylic acid is substituted by a mercapto group, for example, by R-CO-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the thiocarboxylic acid can also be used in the form of a salt. Further, a compound having two thiocarboxylic acid groups can also be used.
二硫羧酸係有機羧酸之羧基中之2個氧原子經硫原子取代者，例如由R-(CS)-SH表示。R表示亦可包含羥基或胺基之脂肪族系或芳香族系烴基或雜環基。又，二硫羧酸亦可於鹽之形態下使用。再者，亦可使用具有兩個二硫羧酸基之化合物。 The two oxygen atoms of the carboxyl group of the dithiocarboxylic acid-based organic carboxylic acid are substituted by a sulfur atom, for example, represented by R-(CS)-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the dithiocarboxylic acid can also be used in the form of a salt. Further, a compound having two dithiocarboxylic acid groups can also be used.
硫代磺酸係有機磺酸之羥基經巰基取代者，例如由R(SO2)-SH表示。R表示亦可包含羥基或胺基之脂肪族系或芳香族系烴基或雜環基。又，硫代磺酸亦可於鹽之形態下使用。 The hydroxyl group of the thiosulfonic acid organic sulfonic acid is substituted with a mercapto group, for example, by R(SO 2 )-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the thiosulfonic acid can also be used in the form of a salt.
二硫代磺酸係有機二磺酸之兩個羥基分別經巰基取代者，例如由R-((SO2)-SH)2表示。R表示亦可包含羥基或胺基之脂肪族系或芳香族系烴基或雜環基。又，兩個硫代磺酸基可分別鍵結於相同之碳，亦可相互鍵結於各自之碳。又，二硫代磺酸亦可於鹽之形態下使用。 The two hydroxyl groups of the dithiosulfonic acid-based organic disulfonic acid are each substituted by a mercapto group, for example, by R-((SO 2 )-SH) 2 . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the two thiosulfonic acid groups may be bonded to the same carbon, respectively, or may be bonded to each other. Further, the dithiosulfonic acid can also be used in the form of a salt.
此處，作為較佳作為R之脂肪族系烴基，可列舉烷基、環烷基，該等烴基亦可包含羥基與胺基中之任一者或兩者。 Here, as the aliphatic hydrocarbon group preferably R, an alkyl group or a cycloalkyl group may be mentioned, and the hydrocarbon group may contain either or both of a hydroxyl group and an amine group.
又，作為烷基，並無限定，可列舉：甲基、乙基、正或異丙基、正、異或第三丁基、正、異或新戊基、正己基、正辛基、正癸基等直鏈狀或支鏈狀之碳數1~20、較佳為碳數1~10、更佳為碳數1~5之烷基。 Further, the alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a normal or an iso-pentyl group, a n-hexyl group, a n-octyl group, and a positive group. The linear or branched carbon number such as a mercapto group is 1 to 20, preferably a carbon number of 1 to 10, more preferably an alkyl group having 1 to 5 carbon atoms.
又，作為環烷基，並無限定，可列舉：環丙基、環丁基、環 戊基、環己基、環庚基、環辛基等碳數3~10、較佳為碳數5~7之環烷基。 Further, the cycloalkyl group is not limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a ring. The pentyl group, the cyclohexyl group, the cycloheptyl group, and the cyclooctyl group have a carbon number of 3 to 10, preferably a cycloalkyl group having 5 to 7 carbon atoms.
又，作為較佳作為R之芳香族烴基，可列舉：苯基、經烷基取代之苯基(例：甲苯基、二甲苯基)、1-或2-萘基、蒽基等碳數6~20、較佳為6~14之芳基，該等烴基亦可包含羥基與胺基中之任一者或兩者。 Further, examples of the aromatic hydrocarbon group preferably represented by R include a phenyl group, a phenyl group substituted by an alkyl group (for example, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, and a fluorenyl group. ~20, preferably 6 to 14 aryl groups, which may also comprise either or both of a hydroxyl group and an amine group.
又，作為較佳作為R之雜環基，可列舉：咪唑、三唑、四唑、苯并咪唑、苯并三唑、噻唑、苯并噻唑，亦可包含羥基與胺基中之任一者或兩者。 Further, examples of the heterocyclic group which is preferably R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, benzothiazole, and may also contain any of a hydroxyl group and an amine group. Or both.
作為於分子內具有2個以下之巰基之化合物之較佳之例，可列舉：3-巰基-1,2-丙二醇、2-巰基乙醇、1,2-乙二硫醇、6-巰基-1-己醇、1-辛硫醇、1-十二烷硫醇、10-羥基-1-十二烷硫醇、10-羧基-1-十二烷硫醇、10-胺基-1-十二烷硫醇、1-十二烷硫醇磺酸鈉、苯硫酚、硫代苯甲酸(thiobenzoic acid)、4-胺基-苯硫酚、對甲苯硫醇、2,4-二甲基苯硫酚、3-巰基-1,2,4-三唑、2-巰基-苯并噻唑。該等之中，就水溶性與廢棄物處理方面之觀點而言，較佳為3-巰基-1,2-丙二醇。 Preferred examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, and 6-mercapto-1- Hexanol, 1-octylthiol, 1-dodecanethiol, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-lane Alkyl mercaptan, sodium 1-dodecyl mercaptan sulfonate, thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluene thiol, 2,4-dimethylbenzene Thiol, 3-mercapto-1,2,4-triazole, 2-mercapto-benzothiazole. Among these, from the viewpoint of water solubility and waste treatment, 3-mercapto-1,2-propanediol is preferred.
附有載體之金屬箔係可利用熱壓使板狀載體與金屬箔密接而製造。例如，可藉由於金屬箔及/或板狀載體之貼合面被覆處理上述於分子內具有2個以下之巰基之化合物之後，對金屬箔之貼合面，熱壓積層B-階段之樹脂製之板狀載體而製造。 The metal foil with a carrier can be manufactured by adhering the plate-shaped carrier to the metal foil by hot pressing. For example, after the above-mentioned compound having two or less sulfhydryl groups in the molecule is coated by the bonding surface of the metal foil and/or the plate-shaped carrier, the bonding surface of the metal foil is made of a resin of the B-stage of the thermocompression layer. It is manufactured by a plate-shaped carrier.
於分子內具有2個以下之巰基之化合物可以水溶液之形態使用。為提高對水之溶解性，亦可添加甲醇或乙醇等醇。醇之添加於使用疏水性較高之於分子內具有2個以下之巰基之化合物時尤其有效。 A compound having two or less sulfhydryl groups in the molecule can be used in the form of an aqueous solution. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is particularly effective when a compound having a higher hydrophobicity and having two or less mercapto groups in the molecule is used.
於分子內具有2個以下之巰基之化合物的水溶液中之濃度較高者有金屬箔與板狀載體之剝離強度降低之傾向，可藉由於分子內具有2個以下之巰基之化合物之濃度調整，而調整剝離強度。雖並無限定，但於分子內具有2個以下之巰基之化合物的水溶液中之濃度可設為0.01~10.0 重量%，典型而言，可設為0.1~5.0重量%。 The higher concentration in the aqueous solution of the compound having two or less sulfhydryl groups in the molecule tends to lower the peel strength of the metal foil and the plate-shaped carrier, and can be adjusted by the concentration of the compound having two or less sulfhydryl groups in the molecule. Adjust the peel strength. Although not limited, the concentration in an aqueous solution of a compound having two or less sulfhydryl groups in the molecule may be set to 0.01 to 10.0. The weight % is typically 0.1 to 5.0% by weight.
於分子內具有2個以下之巰基之化合物的水溶液之pH值並無特別限制，酸性側、鹼性側均可利用。例如可於3.0~10.0之範圍之pH值使用。就無需特別之pH值調整之觀點而言，較佳為設為中性附近即5.0~9.0之範圍之pH值，更佳為設為7.0~9.0之範圍之pH值。 The pH of the aqueous solution of the compound having two or less sulfhydryl groups in the molecule is not particularly limited, and both the acidic side and the alkaline side can be used. For example, it can be used at a pH of from 3.0 to 10.0. From the viewpoint of not requiring a special pH adjustment, it is preferably a pH value in the range of 5.0 to 9.0 in the vicinity of neutral, and more preferably a pH in the range of 7.0 to 9.0.
就使利用於分子內具有2個以下之巰基之化合物的剝離強度之調節變得容易之觀點而言，金屬箔與板狀載體之剝離強度較佳為10gf/cm以上，更佳為30gf/cm以上，進一步較佳為50gf/cm以上，另一方面，較佳為200gf/cm以下，更佳為150gf/cm以下，進一步較佳為80gf/cm以下。藉由將金屬箔與板狀載體之剝離強度設為此種範圍，無於搬送時或加工時剝離之情況，另一方面，可手動容易地剝離即機械剝離之類的剝離強度之調節變得容易。 The peel strength of the metal foil and the plate-shaped carrier is preferably 10 gf/cm or more, and more preferably 30 gf/cm, from the viewpoint of facilitating the adjustment of the peel strength of the compound having two or less sulfhydryl groups in the molecule. The above is more preferably 50 gf/cm or more, and is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, still more preferably 80 gf/cm or less. By setting the peeling strength of the metal foil and the plate-shaped carrier to such a range, it is not peeled off at the time of conveyance or processing, and the peeling strength which can be easily peeled off by hand, that is, mechanical peeling, becomes easily.
又，於多層印刷配線板之製造過程，多數情況為於積層加壓步驟或除膠渣(desmear)步驟中進行加熱處理。因此，附有載體之金屬箔受到之熱歷程係積層數越多越嚴格。因此，尤其是於考慮應用於多層印刷配線板時，較理想為經過所需之熱歷程之後，金屬箔與板狀載體之剝離強度亦在上述範圍內。 Further, in the manufacturing process of the multilayer printed wiring board, in many cases, heat treatment is performed in the laminating press step or the desmear step. Therefore, the more the thermal history of the metal foil with the carrier is, the more stringent it is. Therefore, especially when it is considered to be applied to a multilayer printed wiring board, it is preferable that the peeling strength of the metal foil and the plate-shaped carrier is within the above range after the required heat history.
因此，於本發明之進而較佳之一實施形態中，假定多層印刷配線板之製造過程中之加熱條件的例如於220℃加熱3小時、6小時或9小時中之至少一者後之金屬箔與板狀載體之剝離強度較佳為30gf/cm以上，更佳為50gf/cm以上。又，該剝離強度較佳為200gf/cm以下，更佳為150gf/cm以下，進而更佳為80gf/cm以下。 Therefore, in a further preferred embodiment of the present invention, it is assumed that the metal foil of the heating condition in the manufacturing process of the multilayer printed wiring board is heated at, for example, 220 ° C for at least one of 3 hours, 6 hours or 9 hours. The peeling strength of the plate-shaped carrier is preferably 30 gf/cm or more, more preferably 50 gf/cm or more. Further, the peel strength is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, still more preferably 80 gf/cm or less.
關於220℃之加熱後之剝離強度，就可應對多樣之積層數之觀點而言，較佳為於3小時後及6小時後此兩者、或6小時及9小時後此兩者，剝離強度滿足上述範圍，進而較佳為3小時、6小時及9小時後之全部 之剝離強度滿足上述範圍。 Regarding the peel strength after heating at 220 ° C, it is preferable to treat the two layers after 3 hours and 6 hours, or after 6 hours and 9 hours, from the viewpoint of the number of layers. Satisfying the above range, and further preferably all after 3 hours, 6 hours, and 9 hours The peel strength satisfies the above range.
於本發明中，剝離強度係依據JIS C6481所規定之90度剝離強度測定方法而測定。 In the present invention, the peel strength is measured in accordance with the 90-degree peel strength measuring method specified in JIS C6481.
以下對用以實現此種剝離強度之各材料之具體構成要件進行說明。 The specific constituent elements of each material for achieving such peel strength will be described below.
作為成為板狀載體之樹脂，並無特別限制，可使用酚系樹脂、聚醯亞胺樹脂、環氧樹脂、天然橡膠、松脂等，較佳為熱硬化性樹脂。又，亦可使用預浸體。與金屬箔貼合前之預浸體較佳為處於B-階段之狀態者。由於預浸體(C階段)之線膨脹係數為12~18(×10-6/℃)，與作為基板之構成材料之銅箔之16.5(×10-6/℃)、或SUS加壓板之17.3(×10-6/℃)大致相等，故而就不易產生由加壓前後之基板尺寸與設計時之其不同之現象(定標變化)所引起之電路之位置偏移方面而言較有利。進而，作為該等優點之協同效果，亦能生產多層之極薄無芯基板。此處所使用之預浸體可為與構成電路基板之預浸體相同者，亦可為不同者。 The resin to be a plate-shaped carrier is not particularly limited, and a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, rosin or the like can be used, and a thermosetting resin is preferable. Also, a prepreg can be used. The prepreg before bonding with the metal foil is preferably in the state of the B-stage. Since the linear expansion coefficient of the prepreg (C stage) is 12 to 18 (×10 -6 /°C), 16.5 (×10 -6 /°C) of the copper foil as a constituent material of the substrate, or the SUS pressure plate 17.3 (×10 -6 /°C) is substantially equal, so that it is less advantageous in terms of the positional deviation of the circuit caused by the difference between the size of the substrate before and after the press and the design (variation of calibration). . Further, as a synergistic effect of these advantages, it is also possible to produce a multilayer ultra-thin coreless substrate. The prepreg used herein may be the same as or different from the prepreg constituting the circuit board.
就將加熱後之剝離強度維持於最佳之範圍內之觀點而言，該板狀載體較佳為具有較高之玻璃轉移溫度Tg，例如為120~320℃、較佳為170~240℃之玻璃轉移溫度Tg。再者，將玻璃轉移溫度Tg設為藉由DSC(Differential Scanning Calorimetry，示差掃描熱量測定法)測定之值。 The plate-shaped carrier preferably has a relatively high glass transition temperature Tg, for example, 120 to 320 ° C, preferably 170 to 240 ° C, from the viewpoint of maintaining the peel strength after heating in an optimum range. Glass transfer temperature Tg. Further, the glass transition temperature Tg is a value measured by DSC (Differential Scanning Calorimetry).
又，樹脂之熱膨脹率較理想為金屬箔之熱膨脹率之十10%、-30%以內。藉此，可有效地防止起因於金屬箔與樹脂之熱膨脹差之電路之位置偏移，並可減少不良品產生，提高良率。 Further, the coefficient of thermal expansion of the resin is preferably within 10% or -30% of the thermal expansion coefficient of the metal foil. Thereby, the positional deviation of the circuit which is caused by the difference in thermal expansion between the metal foil and the resin can be effectively prevented, and the occurrence of defective products can be reduced, and the yield can be improved.
板狀載體之厚度並無特別限制，剛性、軟性均可，但若過厚，則對熱壓中之熱分佈造成不良影響，另一方面，若過薄，則變得無法進行彎曲之印刷配線板之製造步驟，因此通常為5μm以上且1000μm以下，較佳為50μm以上且900μm以下，更佳為100μm以上且400μm以下。 The thickness of the plate-shaped carrier is not particularly limited, and may be either rigid or soft. However, if it is too thick, it will adversely affect the heat distribution during hot pressing. On the other hand, if it is too thin, the printed wiring cannot be bent. The production step of the sheet is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.
作為金屬箔，銅或銅合金箔為代表性者，但亦可使用鋁、鎳、鋅等箔。於銅或銅合金箔之情形時，可使用電解箔或壓延箔。金屬箔並無限定，若考慮作為印刷電路基板之配線之用途，則通常為具有1μm以上、較佳為5μm以上、及400μm以下、較佳為120μm以下之厚度。於將金屬箔貼附於板狀載體之兩面之情形時，可使用相同厚度之金屬箔，亦可使用不同厚度之金屬箔。 As the metal foil, copper or a copper alloy foil is representative, but a foil such as aluminum, nickel or zinc may be used. In the case of copper or copper alloy foil, an electrolytic foil or a calendered foil can be used. The metal foil is not limited, and is generally used to have a thickness of 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less, in consideration of the use as a wiring of a printed circuit board. When the metal foil is attached to both sides of the plate-shaped carrier, a metal foil of the same thickness may be used, or a metal foil of a different thickness may be used.
亦可對所使用之金屬箔實施各種表面處理。例如可列舉：以賦予耐熱性為目的之金屬鍍敷(鍍Ni、鍍Ni-Zn合金、鍍Cu-Ni合金、鍍Cu-Zn合金、鍍Zn、鍍Cu-Ni-Zn合金、鍍Co-Ni合金等)、用以賦予防銹性或耐變色性之鉻酸鹽處理(包含於鉻酸鹽處理液中含有1種以上之Zn、P、Ni、Mo、Zr、Ti等合金元素之情形)、用以調整表面粗度之粗化處理(例：利用銅電鍍粒或鍍Cu-Ni-Co合金、鍍Cu-Ni-P合金、鍍Cu-Co合金、鍍Cu-Ni合金、鍍Cu-Co合金、鍍Cu-As合金、鍍Cu-As-W合金等鍍銅合金者)。粗化處理對金屬箔與板狀載體之剝離強度造成影響自不必說，鉻酸鹽處理亦造成較大之影響。就防銹性或耐變色性之觀點而言，鉻酸鹽處理較為重要，但由於見到使剝離強度顯著地上升之傾向，故而作為剝離強度之調整手段亦有意義。 Various surface treatments can also be applied to the metal foil used. For example, metal plating for imparting heat resistance (Ni plating, Ni-Zn alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-plating plating) (N-alloy, etc.), chromate treatment for imparting rust resistance or discoloration resistance (including the case where one or more alloying elements such as Zn, P, Ni, Mo, Zr, Ti are contained in the chromate treatment liquid) ), roughening treatment to adjust the surface roughness (Example: using copper plating or Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu plating) -Co alloy, Cu-As alloy plating, Cu-As-W alloy plating, etc.). The roughening treatment has an effect on the peel strength of the metal foil and the plate-shaped carrier. Needless to say, the chromate treatment also has a large influence. From the viewpoint of rust prevention property and discoloration resistance, chromate treatment is important, but since the peel strength is remarkably increased, it is also considered as a means for adjusting the peel strength.
由於習知之CCL期望樹脂與銅箔之剝離強度較高，故而例如將電解銅箔之無光澤面(M面)設為與樹脂之接著面，並實施粗化處理等表面處理，藉此謀求由化學性及物理性投錨效應所引起之接著力提高。又，於樹脂側，為提高與金屬箔之接著力，亦進行添加各種黏合劑等。如上所述，於本發明中，與CCL不同，金屬箔與樹脂必須最終進行剝離，因此剝離強度過高較不利。 Since the conventional CCL desirably has a high peeling strength between the resin and the copper foil, for example, the matte surface (M surface) of the electrolytic copper foil is placed on the surface of the resin, and a surface treatment such as roughening treatment is performed, thereby achieving The adhesion caused by the chemical and physical anchoring effect is increased. Further, on the resin side, various adhesives and the like are added to increase the adhesion to the metal foil. As described above, in the present invention, unlike the CCL, the metal foil and the resin must be finally peeled off, so that the peel strength is excessively high.
因此，於本發明之附有載體之金屬箔之較佳之一實施形態中，為將金屬箔與板狀載體之剝離強度調節至上述之較佳之範圍內，較佳 為將貼合面之表面粗度，以依據JIS B 0601：2001而測定之金屬箔表面之十點平均粗糙度(Rz jis)表示，設為3.5μm以下、進而3.0μm以下。然而，由於無限度地減小表面粗度成為耗時耗力、成本上升之原因，故而較佳為設為0.1μm以上，更佳為設為0.3μm以上。於使用電解銅箔作為金屬箔之情形時，若調整為此種表面粗度，則亦可使用光澤面(光面、S面)及粗面(無光澤面、M面)中之任一者，使用S面者較容易調整為上述表面粗度。另一方面，上述金屬箔之不與上述載體接觸之側之表面的十點平均粗糙度(Rz jis)較佳為0.4μm以上且10.0μm以下。 Therefore, in a preferred embodiment of the metal foil with a carrier of the present invention, it is preferred to adjust the peel strength of the metal foil and the plate-shaped carrier to the above preferred range. In order to adjust the surface roughness of the bonding surface, the ten-point average roughness (Rz jis) of the surface of the metal foil measured in accordance with JIS B 0601:2001 is 3.5 μm or less and further 3.0 μm or less. However, since the surface roughness is infinitely reduced, it is time-consuming and labor-intensive, and the cost is increased. Therefore, it is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When the electrolytic copper foil is used as the metal foil, if it is adjusted to such a surface roughness, any of a glossy surface (a smooth surface, an S surface) and a rough surface (a matte surface, an M surface) may be used. It is easier to adjust to the above surface roughness using the S surface. On the other hand, the ten-point average roughness (Rz jis) of the surface of the metal foil which is not in contact with the carrier is preferably 0.4 μm or more and 10.0 μm or less.
又，於本發明之附有載體之金屬箔之較佳之一實施形態中，對金屬箔之與樹脂之貼合面，不進行粗化處理等用以提高剝離強度之表面處理。又，於本發明之附有載體之金屬箔之較佳之一實施形態中，於樹脂中，不添加用以提高與金屬箔之接著力之黏合劑。 Further, in a preferred embodiment of the metal foil with a carrier of the present invention, the surface of the bonding surface of the metal foil and the resin is not subjected to a surface treatment for improving the peel strength. Further, in a preferred embodiment of the metal foil with a carrier of the present invention, an adhesive for increasing the adhesion to the metal foil is not added to the resin.
作為用以製造附有載體之金屬箔之熱壓之條件，於使用預浸體作為板狀載體之情形時，較佳為於壓力30~40kg/cm2、高於預浸體之玻璃轉移溫度之溫度進行熱壓。 As a condition for producing hot pressing of the metal foil with a carrier, when a prepreg is used as the plate-shaped carrier, it is preferably at a pressure of 30 to 40 kg/cm 2 , which is higher than the glass transition temperature of the prepreg. The temperature is hot pressed.
就以上之觀點而言，為使樹脂製之板狀載體可剝離地密接，本發明提供一種於成為該密接面之如上述之金屬箔之至少一表面，被覆處理有上述之於分子內具有2個以下之巰基之化合物之金屬箔。又，該金屬箔之表面於利用於分子內具有2個以下之巰基之化合物進行塗佈之前，亦可進行如上述之鉻酸鹽處理等。 In view of the above, in order to make the resin-made plate-shaped carrier peelably adhered, the present invention provides at least one surface of the metal foil as described above which is the adhesion surface, and the coating treatment has the above-mentioned intramolecular 2 A metal foil of the following sulfhydryl compound. Further, the surface of the metal foil may be subjected to chromate treatment as described above before being applied to a compound having two or less sulfhydryl groups in the molecule.
就另一觀點而言，本發明提供一種於成為金屬箔之密接面之板狀載體之至少一表面，具有上述之於分子內具有2個以下之巰基之化合物之板狀載體。該板狀載體可較佳地用於使如上述之金屬箔可剝離地密接之用途。 According to another aspect, the present invention provides a plate-shaped carrier having at least one surface of a plate-shaped carrier which is a contact surface of a metal foil and having the above-described compound having two or less sulfhydryl groups in the molecule. The plate-shaped carrier can be preferably used for the purpose of releasably bonding the metal foil as described above.
進而，就另一觀點而言，本發明提供一種於如上述之金屬箔 之表面，被覆處理有上述之於分子內具有2個以下之巰基之化合物的無芯多層印刷配線板用金屬箔。又，該金屬箔之表面於利用於分子內具有2個以下之巰基之化合物被覆之前，亦可進行如上述之鉻酸鹽處理等。 Further, in another aspect, the present invention provides a metal foil as described above The surface is coated with a metal foil for a coreless multilayer printed wiring board having the above-described compound having two or less sulfhydryl groups in the molecule. Further, the surface of the metal foil may be subjected to chromate treatment as described above before being coated with a compound having two or less sulfhydryl groups in the molecule.
再者，對金屬箔或樹脂之表面利用具備XPS(X-ray Photoelectron Spectroscopy，X射線光電子光譜裝置)、EPMA(Electron Probe Micro Analyser，電子探針微量分析器)、EDX(Energy Dispersive X-ray Analysis，能量分散型X射線分析)之掃描電子顯微鏡等機器進行測定，若檢測出S，則可推斷於金屬箔或樹脂之表面存在於分子內具有2個以下之巰基之化合物。 Further, the surface of the metal foil or resin is provided with XPS (X-ray Photoelectron Spectroscopy), EPMA (Electron Probe Micro Analyser), EDX (Energy Dispersive X-ray Analysis). In a device such as a scanning electron microscope of energy dispersive X-ray analysis, when S is detected, it is estimated that a compound having two or less sulfhydryl groups in the molecule is present on the surface of the metal foil or the resin.
進而，就另一觀點而言，本發明提供上述之附有載體之金屬箔之用途。 Further, in another aspect, the present invention provides the use of the above-described metal foil with a carrier.
第一，提供一種多層覆金屬積層板之製造方法，其包含：對上述之附有載體之金屬箔之至少一金屬箔側，積層樹脂，繼而重複積層樹脂或金屬箔1次以上、例如1~10次。 Firstly, there is provided a method for producing a multi-layer metal-clad laminate comprising: laminating at least one metal foil side of the metal foil with a carrier attached thereto, and then repeatedly laminating a resin or a metal foil one time or more, for example, 1~ 10 times.
第二，提供一種多層覆金屬積層板之製造方法，其包含：於上述之附有載體之金屬箔之金屬箔側積層樹脂，繼而重複積層樹脂、單面或者兩面覆金屬積層板、或本發明之附有載體之金屬箔、或金屬箔1次以上，例如1~10次。 Secondly, there is provided a method for producing a multi-layer metal-clad laminate comprising: the metal foil side-layer resin on the metal foil with the carrier described above, and then repeating the laminated resin, the single-sided or double-sided metal-clad laminate, or the present invention The metal foil or the metal foil with the carrier is attached once or more, for example, 1 to 10 times.
於上述之多層覆金屬積層板之製造方法，可進而包含：剝離而分離上述附有載體之金屬箔之板狀載體與金屬箔之步驟。 The method for producing a multilayer metal-clad laminate according to the above aspect may further comprise the step of separating and separating the plate-shaped carrier and the metal foil of the metal foil with the carrier.
進而，可進而包含：剝離而分離上述板狀載體與金屬箔之後，藉由蝕刻而除去金屬箔之一部分或全部之步驟。 Furthermore, the method further includes the step of removing the part or all of the metal foil by etching after separating the plate-shaped carrier and the metal foil by etching.
第三，提供一種增層(build-up)基板之製造方法，其包含：於上述之附有載體之金屬箔之金屬箔側積層樹脂，繼而重複積層樹脂、單面或者兩面配線基板、單面或者兩面覆金屬積層板、或本發明之附有載體 之金屬箔、或金屬箔1次以上，例如1~10次。 Thirdly, there is provided a method of manufacturing a build-up substrate comprising: laminating a resin on a metal foil side of a metal foil with a carrier, and then repeating a laminated resin, a single-sided or two-sided wiring substrate, and a single side Or a double-sided metal-clad laminate, or a carrier with the invention The metal foil or the metal foil is once or more, for example, 1 to 10 times.
第四，提供一種增層基板之製造方法，其包含：於上述之附有載體之金屬箔之金屬箔側，積層一層以上之增層配線層之步驟。此時，增層配線層可使用相減法或全加成法或半加成法中之至少一者形成。 Fourthly, there is provided a method for producing a build-up substrate comprising the step of laminating one or more build-up wiring layers on the metal foil side of the metal foil with the carrier described above. At this time, the build-up wiring layer may be formed using at least one of a subtractive method or a full additive method or a semi-additive method.
所謂相減法(subtractive method)，係指對覆金屬積層板或配線基板(包含印刷配線板、印刷電路板)上之金屬箔之無用部分，藉由蝕刻等而選擇性地除去，而形成導體圖案之方法。所謂全加成法，係導體層不使用金屬箔，藉由無電解鍍敷或/及電解鍍敷而形成導體圖案之方法，半加成法係例如於由金屬箔構成之晶種層上，併用無電解金屬析出、與電解鍍敷、蝕刻、或該兩者而形成導體圖案之後，蝕刻而除去無用之晶種層，藉此獲得導體圖案之方法。 The subtractive method refers to a useless portion of a metal foil on a metal-clad laminate or a wiring board (including a printed wiring board or a printed circuit board), which is selectively removed by etching or the like to form a conductor pattern. The method. The full addition method is a method in which a conductor pattern is formed by electroless plating or/and electrolytic plating without using a metal foil, and the semi-additive method is, for example, on a seed layer composed of a metal foil. After the conductor pattern is formed by electroless metal deposition, electrolytic plating, etching, or both, etching is performed to remove the useless seed layer, thereby obtaining a conductor pattern.
於上述之增層基板之製造方法中，可進而包含如下步驟：開孔於單面或者兩面配線基板、單面或者兩面覆金屬積層板、附有載體之金屬箔之金屬箔、附有載體之金屬箔之板狀載體、或樹脂，並於該孔之側面及底面進行導通鍍敷。又，可進而包含進行如下步驟1次以上：於構成上述單面或者兩面配線基板之金屬箔、構成單面或者兩面覆金屬積層板之金屬箔、及構成附有載體之金屬箔之金屬箔中之至少一者形成配線。 In the above method for manufacturing a build-up substrate, the method further includes the steps of: opening a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier-attached metal foil, and a carrier A plate-shaped carrier or a resin of a metal foil is electrically plated on the side and bottom surfaces of the hole. Further, the method further includes performing the following steps one or more times on the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal foil constituting the metal foil with the carrier; At least one of them forms a wiring.
於上述之增層基板之製造方法中，亦可進而包含如下步驟：於形成有配線之表面上，使金屬箔密接於單面，進而積層本發明之附有載體之金屬箔之載體側。又，亦可進而包含如下步驟：於形成有配線之表面上，積層樹脂，並於該樹脂積層使金屬箔密接於兩面之本發明之附有載體之金屬箔。 In the method for producing a build-up substrate described above, the method further includes the step of adhering the metal foil to one surface on the surface on which the wiring is formed, and further laminating the carrier side of the metal foil with the carrier of the present invention. Further, the method further includes the step of laminating a resin on the surface on which the wiring is formed, and adhering the metal foil to the metal foil with the carrier of the present invention in which the metal foil is adhered to both surfaces.
再者，所謂「形成有配線之表面」，意指於在進行增層之過程中每次露出之表面形成有配線之部分，作為增層基板，成品、半成品均包含在內。 In addition, the "surface on which the wiring is formed" means a portion in which wiring is formed on each surface exposed during the layering process, and the finished product and the semi-finished product are included as the build-up substrate.
於上述之增層基板之製造方法中，亦可進而包含：剝離而分 離上述附有載體之金屬箔之板狀載體與金屬箔之步驟。 In the method for producing a build-up substrate described above, the method further includes: stripping The step of separating the plate-shaped carrier and the metal foil of the metal foil with the carrier described above.
進而，亦可進而包含：於剝離而分離上述之板狀載體與金屬箔之後，藉由蝕刻而除去金屬箔之一部分或整個面之步驟。 Furthermore, the method further includes the step of removing one or the entire surface of the metal foil by etching after separating the plate-shaped carrier and the metal foil by peeling.
再者，於上述之多層覆金屬積層板之製造方法及增層基板之製造方法中，各層彼此可藉由進行熱壓接而積層。該熱壓接可每一層一層積層地進行，亦可使積層一定程度之後集中進行，亦可最後一次性集中進行。 Further, in the above-described method for producing a multilayer metal-clad laminate and the method for producing a build-up substrate, the layers may be laminated by thermocompression bonding. The thermocompression bonding can be carried out layer by layer on each layer, or the laminate can be concentrated after a certain degree, or can be concentrated at one time.
尤其是，本發明提供一種增層基板之製造方法，其係於上述之增層基板之製造方法中，其至少進行如下步驟1次以上：開孔於單面或者兩面配線基板、單面或者兩面覆銅積層板、金屬箔或樹脂，並於該孔之側面及底面進行導通鍍敷，進而於構成上述單面或者兩面配線基板之金屬箔及電路部分、構成單面或者兩面覆銅積層板之金屬箔、金屬箔形成電路。 In particular, the present invention provides a method for producing a build-up substrate, which is characterized in that at least the following steps are performed in the method for manufacturing a build-up substrate: opening a single-sided or two-sided wiring substrate, one-sided or two-sided a copper clad laminate, a metal foil or a resin, and conducting plating on the side surface and the bottom surface of the hole, and further forming a metal foil and a circuit portion of the single-sided or double-sided wiring substrate to form a single-sided or double-sided copper-clad laminate The metal foil and the metal foil form a circuit.
以下作為上述之用途之具體例，說明利用本發明之附有載體之金屬箔之4層CCL之製法。此處所使用之附有載體之金屬箔係使銅箔11a密接於板狀載體11c之單面之附有載體之銅箔11。於該附有載體之銅箔11，依序重疊所需片數之預浸體12、繼而稱為內層芯13之2層印刷電路基板或2層覆銅積層板、繼而預浸體12、進而附有載體之銅箔11，藉此完成1組4層CCL之組裝單元。繼而，重複該單元14(通稱為「頁」)10次左右，構成加壓組裝物15(通稱為「書」)(圖3)。其後，利用積層模具10夾持該書15並設置於熱壓機，於特定之溫度及壓力進行加壓成型，藉此可同時製造多個4層CCL。作為積層模具10，例如可使用不銹鋼製板。板並無限定，例如可使用1~10mm左右之厚板。關於4層以上之CCL，一般而言亦可藉由增加內層芯之層數，以同樣之步驟生產。 Hereinafter, a method of producing a four-layer CCL using the metal foil of the carrier of the present invention will be described as a specific example of the above-described use. The metal foil with a carrier used here is such that the copper foil 11a is in close contact with the copper foil 11 with the carrier attached to one side of the plate-shaped carrier 11c. In the copper foil 11 with a carrier, the required number of prepregs 12, a two-layer printed circuit board, which is referred to as an inner core 13, or a two-layer copper clad laminate, and then a prepreg 12, are sequentially stacked. Further, a copper foil 11 of a carrier is attached, whereby an assembly unit of one set of four layers of CCL is completed. Then, the unit 14 (generally referred to as "page") is repeated about 10 times to constitute a pressurized assembly 15 (generally referred to as "book") (Fig. 3). Thereafter, the book 15 is held by the build-up mold 10 and placed in a hot press, and press-molded at a specific temperature and pressure, whereby a plurality of four-layer CCL can be simultaneously produced. As the laminated mold 10, for example, a stainless steel plate can be used. The plate is not limited, and for example, a thick plate of about 1 to 10 mm can be used. With regard to CCL of 4 or more layers, it is generally possible to produce in the same manner by increasing the number of layers of the inner core.
以下，作為上述之用途之具體例，例示地說明利用本發明之使銅箔密接於樹脂板之板狀載體11c之兩面的附有載體之銅箔11的無芯增 層基板之製法。於該方法中，於附有載體之銅箔11之兩側積層必要數量之增層層16之後，自附有載體之銅箔11剝離兩面之銅箔(參照圖4)。 Hereinafter, as a specific example of the above-described use, the coreless addition of the carrier-attached copper foil 11 using the copper foil adhered to the both sides of the plate-shaped carrier 11c of the resin sheet of the present invention will be exemplarily described. The method of making a layer substrate. In this method, after a necessary number of build-up layers 16 are laminated on both sides of the copper foil 11 with the carrier, the copper foil 11 having the carrier is peeled off from both sides (see FIG. 4).
例如，於本發明之附有載體之金屬箔之金屬箔側，依序重疊作為絕緣層之樹脂、2層電路基板、作為絕緣層之樹脂，並使金屬箔側與樹脂板接觸，於其上進而依序重疊本發明之附有載體之金屬箔之金屬箔，藉此可製造增層基板。 For example, on the metal foil side of the metal foil with a carrier of the present invention, a resin as an insulating layer, a two-layer circuit substrate, a resin as an insulating layer, and a metal foil side are brought into contact with the resin sheet, respectively. Further, the metal foil of the metal foil with a carrier of the present invention is sequentially superposed, whereby the build-up substrate can be manufactured.
又，作為另一方法，對使金屬箔密接於樹脂製之板狀載體11c之兩面或單面之附有載體之金屬箔之至少一金屬箔側，依序積層作為絕緣層之樹脂、作為導體層之金屬箔，並於該電路形成用之金屬箔及樹脂板開孔，於該孔之側面及底面實施導通鍍敷，而形成通孔，進而，於該電路形成用之金屬箔之剩餘部分，藉由圖案化技術等形成電路，藉此亦可製造增層基板。亦可進行數次之前之步驟。 Further, as another method, a metal foil is adhered to at least one metal foil side of a metal foil with a carrier on both sides or a single side of a resin-made plate-shaped carrier 11c, and a resin as an insulating layer is sequentially laminated as a conductor. a metal foil of a layer, and a metal foil and a resin plate for forming the circuit, and performing conduction plating on the side surface and the bottom surface of the hole to form a through hole, and further, a remaining portion of the metal foil for forming the circuit The circuit is formed by a patterning technique or the like, whereby the build-up substrate can also be manufactured. You can also perform several previous steps.
繼而，視需要亦可包含對金屬箔之整個面進行半蝕刻而調整厚度之步驟。繼而，於所積層之金屬箔之特定位置實施雷射加工而形成貫通金屬箔與樹脂之通孔，並實施除去通孔中之污跡(smear)之除膠渣處理之後，於通孔底部、側面及金屬箔之整個面或一部分實施無電解鍍敷而形成層間連接，視需要進而進行電解鍍敷。直至對金屬箔上之無電解鍍敷或電解鍍敷為無用之部分進行各自之鍍敷之前，亦可預先形成電鍍阻劑。又，於無電解鍍敷、電解鍍敷、電鍍阻劑與金屬箔之密接性不充分之情形時，亦可預先化學性地粗化金屬箔之表面。於使用電鍍阻劑之情形時，於鍍敷後除去電鍍阻劑。繼而，藉由蝕刻除去金屬箔及無電解鍍敷部、電解鍍敷部之無用部分，藉此形成電路。藉此，獲得增層基板。亦可重複進行數次自樹脂、銅箔之積層直至電路形成之步驟，進而製成多層之增層基板。 Then, if necessary, the step of half etching the entire surface of the metal foil to adjust the thickness may be included. Then, laser processing is performed at a specific position of the metal foil of the laminated layer to form a through hole penetrating the metal foil and the resin, and the desmear process for removing the smear in the through hole is performed, and then at the bottom of the through hole, Electroless plating is applied to the entire surface or a part of the metal foil to form an interlayer connection, and electrolytic plating is performed as needed. The plating resist may be formed in advance until the electroless plating or electrolytic plating on the metal foil is used for plating. Further, when the adhesion between the electroless plating, the electrolytic plating, and the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. In the case of using a plating resist, the plating resist is removed after plating. Then, the metal foil, the electroless plating portion, and the unnecessary portion of the electrolytic plating portion are removed by etching to form an electric circuit. Thereby, a build-up substrate is obtained. It is also possible to repeat the steps of laminating the resin and the copper foil several times until the circuit is formed, thereby forming a multilayer build-up substrate.
進而，於該增層基板之最表面，可使本發明之使金屬箔密接於單面之附有載體之金屬箔之金屬箔之樹脂側接觸而積層，亦可於暫時積層樹脂板 之後，使本發明之使金屬箔密接於兩面之附有載體之金屬箔之一金屬箔接觸而積層。 Further, on the outermost surface of the build-up substrate, the metal foil of the present invention may be adhered to the resin side of the metal foil of the metal foil with the carrier on one side and laminated, or the resin sheet may be temporarily laminated. Thereafter, the metal foil of the present invention in which the metal foil is adhered to both sides of the carrier-attached metal foil is brought into contact to be laminated.
此處，作為製作增層基板所使用之樹脂板，可使用預浸體，又，可較佳地使用含有熱硬化性樹脂之預浸體。 Here, as the resin sheet used for producing the build-up substrate, a prepreg can be used, and a prepreg containing a thermosetting resin can be preferably used.
又，作為另一方法，於本發明之將金屬箔、例如銅箔貼合於板狀載體之單面或兩面而獲得之積層體之金屬箔之露出表面，積層作為絕緣層之樹脂，例如預浸體或感光性樹脂。其後，於樹脂之特定位置形成通孔。於例如使用預浸體作為樹脂之情形時，通孔可藉由雷射加工或利用鑽孔器之加工而形成。雷射加工或利用鑽孔器之加工之後，較佳為實施除去該通孔中之污跡之除膠渣處理。又，於使用感光性樹脂作為樹脂之情形時，可藉由光微影法而除去形成通孔部之樹脂。進而，於通孔底部、側面及樹脂之整個面或一部分實施無電解鍍敷，而形成層間連接，視需要進而進行電解鍍敷。直至對樹脂上之無電解鍍敷或電解鍍敷為無用之部分進行各自之鍍敷之前，亦可預先形成電鍍阻劑。又，於無電解鍍敷、電解鍍敷、電鍍阻劑與樹脂之密接性不充分之情形時，亦可預先化學性地粗化樹脂之表面。於使用電鍍阻劑之情形時，於鍍敷後除去電鍍阻劑。進而，藉由蝕刻而除去無電解鍍敷部或電解鍍敷部之無用部分，藉此形成電路。藉此，獲得增層基板。亦可重複進行數次自樹脂之積層直至電路形成之步驟，進而製成多層之增層基板。 Further, as another method, in the exposed surface of the metal foil of the laminate obtained by laminating a metal foil, for example, a copper foil, on one side or both sides of the plate-shaped carrier, a resin as an insulating layer is laminated, for example, Dip or photosensitive resin. Thereafter, a through hole is formed at a specific position of the resin. For example, in the case where a prepreg is used as the resin, the through holes can be formed by laser processing or processing using a drill. After laser processing or processing using a drill, it is preferred to carry out a desmear treatment for removing stains in the through holes. Further, when a photosensitive resin is used as the resin, the resin forming the through-hole portion can be removed by photolithography. Further, electroless plating is applied to the bottom surface, the side surface, and the entire surface or part of the resin to form an interlayer connection, and further electrolytic plating is performed as needed. The plating resist may be formed in advance until the electroless plating on the resin or the electroless plating is performed on the unused portion. Further, in the case where electroless plating, electrolytic plating, or adhesion between the plating resist and the resin is insufficient, the surface of the resin may be chemically roughened in advance. In the case of using a plating resist, the plating resist is removed after plating. Further, an unnecessary portion of the electroless plating portion or the electrolytic plating portion is removed by etching to form an electric circuit. Thereby, a build-up substrate is obtained. It is also possible to repeat the steps from the lamination of the resin to the formation of the circuit, thereby forming a multilayer build-up substrate.
進而，於該增層基板之最表面，可使本發明之使金屬箔密接於單面之積層體之樹脂側、或使金屬箔密接於單面之附有載體之金屬箔之樹脂側接觸而積層，亦可於暫時積層樹脂之後，使本發明之使金屬箔密接於兩面之積層體之一金屬箔、或使金屬箔密接於兩面之附有載體之金屬箔之一金屬箔接觸而積層。 Further, on the outermost surface of the buildup substrate, the metal foil of the present invention may be adhered to the resin side of the laminate of one side, or the metal foil may be in close contact with the resin side of the metal foil with the carrier on one side. The laminate may be laminated after the resin is temporarily laminated, and the metal foil of the present invention is adhered to one of the laminates on both sides, or the metal foil is adhered to the metal foil of the metal foil with the carrier on both sides.
對藉由此種方式製作之無芯增層基板，經過鍍敷步驟及/或 蝕刻步驟而於表面形成配線，進而於載體樹脂與銅箔之間，使其剝離分離，藉此完成多層增層配線板。於剝離分離後對金屬箔之剝離面，可形成配線，亦可藉由蝕刻而除去金屬箔整個面而製成增層配線板。進而，藉由於增層配線板上搭載電子零件類，完成印刷電路板。又，即便直接於樹脂剝離前之無芯增層基板上搭載電子零件，亦可獲得印刷電路板。 The coreless build-up substrate produced in this manner is subjected to a plating step and/or In the etching step, wiring is formed on the surface, and the carrier resin and the copper foil are separated and separated, thereby completing the multilayer build-up wiring board. A wiring can be formed on the peeled surface of the metal foil after the separation and separation, and the entire surface of the metal foil can be removed by etching to form a build-up wiring board. Further, the printed circuit board is completed by mounting electronic components on the build-up wiring board. Further, a printed circuit board can be obtained even if an electronic component is mounted directly on the coreless build-up substrate before the resin is peeled off.
[實施例] [Examples]
以下表示實驗例作為本發明之實施例及比較例，該等實施例係為更好地理解本發明及其優勢而提供者，並非意圖限定發明者。 The following are examples of the invention and the comparative examples, which are intended to provide a better understanding of the invention and its advantages, and are not intended to limit the invention.
(附有載體之金屬箔) (metal foil with carrier)
<實驗例1~19> <Experimental Examples 1 to 19>
準備複數個電解銅箔(厚度12μm，粗面表面粗糙度Rz jis 3.7μm)，對各個電解銅箔之光(S)面，實施下述條件之鍍鎳-鋅(Ni-Zn)合金處理及鉻酸鹽(Cr-Zn鉻酸鹽)處理，將貼合面(此處為S面)之十點平均粗糙度(Rz jis：依據JIS B 0601：2001而測定)設為1.5μm之後，將作為樹脂之南亞塑膠公司製造之預浸體(FR-4Resin：玻璃轉移溫度Tg=170℃；厚度200μm)與該電解銅箔之S面貼合，並於190℃進行熱壓加工100分鐘，而製作附有載體之銅箔。 Preparing a plurality of electrolytic copper foils (thickness 12 μm, rough surface roughness Rz jis 3.7 μm), and subjecting the light (S) surface of each of the electrolytic copper foils to nickel-zinc (Ni-Zn) alloy treatment under the following conditions and After the chromate (Cr-Zn chromate) treatment, the ten-point average roughness (Rz jis: measured according to JIS B 0601:2001) of the bonding surface (here, the S surface) is set to 1.5 μm, A prepreg (FR-4 Resin: glass transition temperature Tg = 170 ° C; thickness: 200 μm) manufactured by Nanya Plastics Co., Ltd. as a resin is bonded to the S surface of the electrolytic copper foil, and hot pressed at 190 ° C for 100 minutes. A copper foil with a carrier is produced.
(鍍鎳-鋅合金) (nickel-zinc alloy plating)
Ni濃度17g/L(以NiSO4之形式添加) Ni concentration 17g / L (added in the form of NiSO 4 )
Zn濃度4g/L(以ZnSO4之形式添加) Zn concentration 4g / L (added as ZnSO 4 )
pH值3.1 pH 3.1
液溫40℃ Liquid temperature 40 ° C
電流密度0.1~10A/dm2 Current density 0.1~10A/dm 2
鍍敷時間0.1~10秒 Plating time 0.1~10 seconds
(鉻酸鹽處理) (chromate treatment)
Cr濃度1.4g/L(以CrO3或K2CrO7之形式添加) Cr concentration of 1.4g / L (added as CrO 3 or of K 2 CrO 7)
Zn濃度0.01~1.0g/L(以ZnSO4之形式添加) Zn concentration 0.01~1.0g/L (added as ZnSO 4 )
Na2SO4濃度10g/L Na 2 SO 4 concentration 10g / L
pH值4.8 pH 4.8
液溫55℃ Liquid temperature 55 ° C
電流密度0.1~10A/dm2 Current density 0.1~10A/dm 2
鍍敷時間0.1~10秒 Plating time 0.1~10 seconds
再者，於該S面或上述預浸體，使用噴霧塗佈機塗佈表1所示之於分子內具有2個以下之巰基之化合物之水溶液之後，於100℃之空氣中使其乾燥，之後進行預浸體與銅箔之貼合。關於在分子內具有2個以下之巰基之化合物之使用條件，如表1所示，將水溶液中之於分子內具有2個以下之巰基之化合物之濃度設為3重量%(wt%)，將水溶液之pH值設為5~9。 Further, on the S surface or the prepreg, an aqueous solution of a compound having two or less sulfhydryl groups in the molecule shown in Table 1 is applied by a spray coater, and then dried in air at 100 ° C. Thereafter, the prepreg is bonded to the copper foil. With respect to the use conditions of the compound having two or less sulfhydryl groups in the molecule, as shown in Table 1, the concentration of the compound having two or less sulfhydryl groups in the aqueous solution in the aqueous solution is 3% by weight (wt%). The pH of the aqueous solution is set to 5-9.
又，假定對附有載體之銅箔中之幾個，於對該附有載體之銅箔進行電路形成等進一步之加熱處理時施加熱歷程，進行表1中記載之條件(此處，於190℃ 3小時、6小時、9小時)之熱處理。 Further, it is assumed that a heat history is applied to a copper foil with a carrier to perform further heat treatment such as circuit formation on the copper foil with a carrier, and the conditions described in Table 1 are performed (here, at 190). Heat treatment at °C for 3 hours, 6 hours, and 9 hours).
對藉由熱壓獲得之附有載體之銅箔、及其後進行3小時、6小時、9小時之各個熱處理後之附有載體之銅箔的銅箔與板狀載體(加熱後之樹脂)之剝離強度進行測定。將各個結果示於表1。 a copper foil with a carrier obtained by hot pressing, and a copper foil with a carrier-attached copper foil after heat treatment for 3 hours, 6 hours, and 9 hours, and a plate-shaped carrier (heated resin) The peel strength was measured. The respective results are shown in Table 1.
又，為對剝離作業性進行評價，分別對每單位個數之人手之作業時間(時間/個)進行評價。將結果示於表2。 Moreover, in order to evaluate the peeling workability, the work time (time/number) of the hand per unit number was evaluated. The results are shown in Table 2.
<實驗例20> <Experimental Example 20>
於實驗例1中，於貼合銅箔與預浸體時，不利用於分子內具有2個以下之巰基之化合物對該銅箔之S面進行處理，除此以外，於與實驗例1相同之條件，製作附有載體之銅箔，對各階段之剝離強度、及作業時間進行 評價。將各個結果示於表1及表2。 In Experimental Example 1, when the copper foil and the prepreg were bonded together, it was disadvantageously applied to the S surface of the copper foil by a compound having two or less sulfhydryl groups in the molecule, and otherwise the same as in Experimental Example 1. Under the conditions, copper foil with carrier is prepared, and the peel strength and working time of each stage are performed. Evaluation. The respective results are shown in Tables 1 and 2.
雖然表中未記載，但得知：於分子內具有2個以下之巰基之化合物不論對銅箔之表面進行處理，或對預浸體之表面進行處理，只要為利用相同之化合物於相同之條件處理者，則於其後之積層體之剝離強度、加熱後之剝離強度、剝離作業性，獲得同等之結果。 Although not described in the table, it is known that a compound having two or less sulfhydryl groups in the molecule is treated on the surface of the copper foil or the surface of the prepreg is treated as long as the same compound is used under the same conditions. The processor obtained the same result on the peel strength of the laminated body, the peeling strength after heating, and the peeling workability.
(增層配線板) (Additional wiring board)
於藉由此種方式製作之附有載體之銅箔之兩側，依序重疊FR-4預浸體(南亞塑膠公司製造)、銅箔(JX日礦日石金屬股份有限公司製造，JTC12μm(產品名))，於3MPa之壓力於各表所示之加熱條件進行熱壓，製作4層覆銅積層板。 FR-4 prepreg (made by Nanya Plastics Co., Ltd.) and copper foil (made by JX Nippon Mining & Metal Co., Ltd., JTC12μm) are sequentially superposed on both sides of the copper foil with carrier formed by this method. The product name)) was hot-pressed under the heating conditions shown in the respective tables under a pressure of 3 MPa to prepare a four-layer copper-clad laminate.
繼而，使用雷射加工機開出貫通上述4層覆銅積層板表面之銅箔與其下之絕緣層(硬化之預浸體)之直徑100μm之孔。繼而，於在上述孔之底部露出之附有載體之銅箔上之銅箔表面、與上述孔之側面、上述4層覆銅積層板表面之銅箔上藉由無電解鍍銅、銅電鍍進行鍍銅，於附有載體之銅箔上之銅箔、與4層覆銅積層板表面之銅箔之間形成電性連接。繼而，使用氯化鐵系之蝕刻液蝕刻4層覆銅積層板表面之銅箔之一部分，形成電路。藉由此種方式，獲得4層增層基板。 Then, a hole of 100 μm in diameter of the copper foil penetrating the surface of the above-mentioned four-layer copper clad laminate and the insulating layer (hardened prepreg) therethrough was opened using a laser processing machine. Then, the surface of the copper foil on the copper foil with the carrier exposed at the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper-clad laminate are subjected to electroless copper plating or copper plating. Copper plating is performed to form an electrical connection between the copper foil on the copper foil with the carrier and the copper foil on the surface of the four-layer copper clad laminate. Then, a portion of the copper foil on the surface of the four-layer copper clad laminate was etched using an iron chloride-based etching solution to form an electric circuit. In this way, four layers of build-up substrates were obtained.
繼而，於上述4層增層基板，剝離而分離上述附有載體之銅箔之板狀載體與銅箔，藉此獲得2組2層增層配線板。 Then, the above-mentioned four-layer build-up substrate was peeled off to separate the plate-shaped carrier of the copper foil with the carrier and the copper foil, thereby obtaining two sets of two-layer build-up wiring boards.
繼而，蝕刻上述2組2層增層配線板上之與板狀載體密接者之銅箔，形成配線，而獲得2組2層增層配線板。 Then, the copper foil of the two sets of the two-layer build-up wiring board which is in contact with the plate-shaped carrier is etched to form wiring, and two sets of two-layer build-up wiring boards are obtained.
各實驗例均製作複數個4層增層基板，針對各自，以目視確認增層基板製作步驟中之構成附有載體之銅箔之預浸體與銅箔之密接情況，結果為使用於在表1將剝離強度及加熱後之剝離強度評價為「G」之條件製作之附有載體之銅箔的增層配線板係於增層時附有載體之銅箔之樹脂(板狀載體)未破裂而可剝離。 In each of the experimental examples, a plurality of four-layer build-up substrates were produced, and the adhesion between the prepreg and the copper foil constituting the copper foil with the carrier in the step of producing the build-up substrate was visually confirmed. (1) The build-up wiring board of the copper foil with a carrier prepared by evaluating the peeling strength and the peeling strength after heating as a condition of "G" is a resin (plate-shaped carrier) which is attached to the copper foil of the carrier at the time of layering is not broken. It can be peeled off.
又，關於評價為「N」之條件，於增層時於附有載體之銅箔的銅箔之剝離操作時樹脂破裂，或者未剝離而於銅箔表面殘留有樹脂。 Further, regarding the condition of evaluation of "N", the resin was broken during the peeling operation of the copper foil with the carrier-attached copper foil at the time of layering, or the resin remained on the surface of the copper foil without being peeled off.
Claims (47)
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| JP2012174453 | 2012-08-06 |
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| TW (1) | TWI627876B (en) |
| WO (1) | WO2014024878A1 (en) |
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| JP5826322B2 (en) * | 2014-03-25 | 2015-12-02 | Jx日鉱日石金属株式会社 | Surface-treated copper foil, copper-clad laminate, printed wiring board, electronic device, circuit forming substrate for semiconductor package, semiconductor package, and printed wiring board manufacturing method |
| JP6438370B2 (en) * | 2015-08-03 | 2018-12-12 | Ｊｘ金属株式会社 | Printed wiring board manufacturing method, surface-treated copper foil, laminate, printed wiring board, semiconductor package, and electronic device |
| WO2017022807A1 (en) * | 2015-08-03 | 2017-02-09 | Ｊｘ金属株式会社 | Printed wiring board production method, surface-treated copper foil, laminate, printed wiring board, semiconductor package, and electronic device |
| JP5897755B2 (en) * | 2015-08-11 | 2016-03-30 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper clad laminate, printed wiring board, electronic device, semiconductor package, printed wiring board manufacturing method, electronic device manufacturing method, semiconductor package manufacturing method, resin substrate manufacturing method, copper foil surface Method of transferring profile to resin substrate |
| JPWO2017051897A1 (en) * | 2015-09-24 | 2018-08-30 | Ｊｘ金属株式会社 | Metal foil, metal foil with release layer, laminate, printed wiring board, semiconductor package, electronic device and method for manufacturing printed wiring board |
| JP6031624B2 (en) * | 2016-02-29 | 2016-11-24 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper-clad laminate, printed wiring board manufacturing method, semiconductor package manufacturing method, and electronic device manufacturing method |
| CN113923965A (en) * | 2021-10-14 | 2022-01-11 | 深圳市汉嵙新材料技术有限公司 | Ultrathin copper foil with high softness and toughness as well as preparation method and application thereof |
| WO2023210285A1 (en) * | 2022-04-27 | 2023-11-02 | 株式会社ダイセル | Joined body, and method for manufacturing joined body |
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|---|---|---|---|---|
| JP2000156563A (en) * | 1998-11-19 | 2000-06-06 | Matsushita Electric Ind Co Ltd | Printed wiring board |
| JP2000196207A (en) * | 1998-12-25 | 2000-07-14 | Nikko Materials Co Ltd | Printed board and copper foil therefor |
| JP2002353614A (en) * | 2001-05-29 | 2002-12-06 | Fujitsu Ltd | Substrate having multilayer interconnection layer and method of manufacturing the same |
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|---|---|---|---|---|
| JPS5687694A (en) * | 1979-12-19 | 1981-07-16 | Nippon Mining Co Ltd | Manufacture of copper foil for printed circuit |
| JPS6058698A (en) * | 1983-09-12 | 1985-04-04 | 古河サ−キツトフオイル株式会社 | Copper foil for printed circuit and method of producing same |
| JPH08309918A (en) * | 1995-05-22 | 1996-11-26 | Nippon Denkai Kk | Copper clad laminated sheet, printed circuit board using the same and production of them |
| JP2002292788A (en) * | 2001-03-30 | 2002-10-09 | Nippon Denkai Kk | Composite copper foil and method for manufacturing the same |
| JP2003198123A (en) * | 2001-12-27 | 2003-07-11 | Fujikura Ltd | Flexible printed wiring board |
| WO2009082005A1 (en) * | 2007-12-26 | 2009-07-02 | Denki Kagaku Kogyo Kabushiki Kaisha | Surface reactive support body, wiring board that uses same, and fabrication method therefor |
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2013
- 2013-08-02 TW TW102127743A patent/TWI627876B/en not_active IP Right Cessation
- 2013-08-06 WO PCT/JP2013/071241 patent/WO2014024878A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000156563A (en) * | 1998-11-19 | 2000-06-06 | Matsushita Electric Ind Co Ltd | Printed wiring board |
| JP2000196207A (en) * | 1998-12-25 | 2000-07-14 | Nikko Materials Co Ltd | Printed board and copper foil therefor |
| JP2002353614A (en) * | 2001-05-29 | 2002-12-06 | Fujitsu Ltd | Substrate having multilayer interconnection layer and method of manufacturing the same |
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| JP6205361B2 (en) | 2017-09-27 |
| TW201427497A (en) | 2014-07-01 |
| WO2014024878A1 (en) | 2014-02-13 |
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