WO2023085246A1 - Nonphotosensitive surface modifying agent, laminate, printed circuit board, and electronic device - Google Patents
Nonphotosensitive surface modifying agent, laminate, printed circuit board, and electronic device Download PDFInfo
- Publication number
- WO2023085246A1 WO2023085246A1 PCT/JP2022/041485 JP2022041485W WO2023085246A1 WO 2023085246 A1 WO2023085246 A1 WO 2023085246A1 JP 2022041485 W JP2022041485 W JP 2022041485W WO 2023085246 A1 WO2023085246 A1 WO 2023085246A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- layer
- laminate
- heterocyclic compound
- resin
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 claims abstract description 109
- 239000002184 metal Substances 0.000 claims abstract description 109
- 229920005989 resin Polymers 0.000 claims abstract description 87
- 239000011347 resin Substances 0.000 claims abstract description 87
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 53
- 125000001424 substituent group Chemical group 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 125000003368 amide group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000004185 ester group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011342 resin composition Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 201
- 238000000034 method Methods 0.000 description 26
- 239000010949 copper Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 230000003993 interaction Effects 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- -1 nitrogen-containing compound Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004643 cyanate ester Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- the present invention relates to a non-photosensitive surface modifier, a laminate, a printed circuit board, and an electronic device, and in particular, a non-photosensitive surface modifier that can further improve the adhesion between a metal layer and a resin layer. Regarding.
- printed wiring boards also referred to as “printed boards” having high-density and high-definition wiring are in demand.
- a resin material such as an etching resist, a plating resist, a solder resist, or a prepreg is bonded to the surface of a metal layer or metal wiring.
- High adhesiveness is required between the metal layer and the resin layer in the manufacturing process of the printed wiring board and in the manufactured product.
- Patent Document 1 a method of forming a film for improving adhesiveness for improving the adhesiveness with the resin layer on the surface of the metal layer (see, for example, Patent Document 1), a method of incorporating a sulfur-containing compound and a nitrogen-containing compound into a photosensitive resin to improve adhesiveness (see, for example, Patent Document 2).
- Patent Documents 1 and 2 Although the adhesion between the metal layer and the resin layer is improved to some extent, sufficient adhesion has not yet been obtained.
- 5G mobile communication and high-density mounting technology for semiconductor packages have progressed, and the demand for low-roughness metal layers on printed wiring boards and narrower metal wiring lines has increased. is required more than ever before.
- the present invention has been made in view of the above problems and circumstances, and the problem to be solved is a non-photosensitive surface modifier that can further improve the adhesion between the metal layer and the resin layer.
- An object of the present invention is to provide a laminate, a printed circuit board and an electronic device using a photosensitive surface modifier.
- the present inventors in the process of studying the causes of the above problems, found that a specific The present inventors have found that the adhesion between the metal layer and the resin layer can be further improved by including a heterocyclic compound having a structure, and have completed the present invention. That is, the above problems related to the present invention are solved by the following means.
- a non-photosensitive surface modifier that forms a surface modification layer between the metal layer and the resin layer A non-photosensitive surface modifier containing at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
- R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
- R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
- each substituent R 2 may be the same or different.
- each n may be the same or different, and when there are multiple m's, each m may be the same or different. may ]
- a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer A laminate in which the surface-modified layer contains at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
- R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
- R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
- each substituent R 2 may be the same or different.
- each n may be the same or different, and when having a plurality of m, each m may be the same or different. good too. ]
- heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5).
- R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
- the non-photosensitive surface modifier of the present invention contains at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4).
- a nitrogen atom (N atom) present in the structure of the ring compound interacts with the metal, and a phenolic hydroxy group interacts with the resin.
- the presence of the surface-modified layer formed by such a non-photosensitive surface-modifying agent between the metal layer and the resin layer allows the metal layer and the resin layer to form a surface having the above interaction. Adhesion is improved by the modified layer.
- Phenolic hydroxy groups can form covalent bonds with polar groups present in resins and polymerizable resins represented by hydrogen bonds or epoxy groups, with stronger interaction forces than ⁇ - ⁇ interactions and van der Waals forces. can adhere.
- the heterocyclic compound for example, the exemplary compound (1- The molecular skeleton of 1)
- the nitrogen atoms (N) interact with the metal of the metal layer 10
- the phenolic hydroxyl groups (OH) It is presumed that the resin layer 20 can be approached and a stronger interaction can be obtained.
- FIG. 1 represents the same as in FIG.
- Diagram showing the process of forming a metal wiring pattern (metal-clad laminate) A diagram showing the formation process of a metal wiring pattern (formation of a surface modification layer)
- a diagram showing a process of forming a metal wiring pattern formation of a resist layer
- a diagram showing a process of forming a metal wiring pattern pattern (patterning of a resist layer)
- the non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
- This feature is a technical feature common to or corresponding to each of the following embodiments.
- the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (1).
- a heterocyclic compound having a structure represented by is preferable from the viewpoint of improving the adhesion between the metal layer and the resin layer. In terms of solubility, it is preferable to contain at least water or alcohols.
- the laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
- the surface-modifying layer contains at least one heterocyclic compound having a structure represented by formula (1), (2), (3) or (4). This makes it possible to provide a laminate with improved adhesion between the metal layer and the resin layer.
- the resin layer is a photosensitive resin composition containing an alkali-soluble resin, or a thermosetting resin composition containing at least a resin having an epoxy structure, and the phenolic hydroxyl group contained in the heterocyclic compound. is preferable from the point of view of improvement in adhesion due to the interaction of
- the laminate of the present invention can be suitably used for printed circuit boards or electronic devices.
- the non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the following general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
- R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
- substituents include a hydroxy group and an amide group.
- R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a halogen atom, or a heteroaryl group; In particular, it is preferable to represent an alkyl group.
- n and m are each an integer of 0 to 5
- n + m an integer of 0 to 5 (however, with respect to general formula (1), an integer of 0 to 4) represents Moreover, in each general formula, when having a plurality of substituents R 2 , the respective substituents R 2 may be the same or different from each other. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may
- the heterocyclic compound according to the present invention is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4). This is preferable in that the adhesion between the metal layer and the resin layer is improved as a result of the interaction between the metal layer and the surface modified layer and between the surface modified layer and the resin layer.
- heterocyclic compound according to the present invention is preferably a heterocyclic compound having a structure represented by the following general formula (5) from the viewpoint of improving adhesion between the metal layer and the resin layer.
- R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
- substituents include a hydroxy group and an amide group.
- heterocyclic compounds having structures represented by the general formulas (1) to (5) are listed below, but the heterocyclic compound according to the present invention is not limited to these.
- the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention may be one type or two or more types.
- the non-photosensitive surface modifier of the present invention preferably contains at least water or alcohol as a solvent.
- the alcohol include methanol, ethanol, 2-propanol and the like. Two or more kinds of water or alcohols may be used in combination as the solvent.
- the mass ratio (% by mass) of water and alcohol is preferably in the range of 100:0 to 50:50, more preferably in the range of 100:0 to 75:25.
- the aromatic heterocyclic compound is contained in the range of 0.00001 (0.1 ppm) to 0.1 (1000 ppm) mass% with respect to the total non-photosensitive surface modifier from the viewpoint of film formation. Preferably, it is contained within the range of 0.00001 (0.1 ppm) to 0.01 (100 ppm) mass %.
- non-photosensitive surface modifier of the present invention may contain other components other than the above, but does not contain polymers, polymerizable monomers or oligomers, that is, does not contain resins. shall consist only of non-polymeric materials;
- the other components include surfactants, preservatives, stabilizers, acids, bases, pH adjusters and the like.
- the laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer, wherein the surface-modified layer comprises at least the general formulas (1), (2), and (3). or contains one or more heterocyclic compounds having a structure represented by (4).
- heterocyclic compounds having the structures represented by the general formulas (1) to (4) are omitted because they are as described above.
- the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4).
- the interaction between the metal layer and the modified surface layer and between the modified surface layer and the resin layer results in improved adhesion between the metal layer and the resin layer.
- the heterocyclic compound is preferably a heterocyclic compound having the structure represented by the general formula (5) from the viewpoint of improving the adhesion between the metal layer and the resin layer.
- the heterocycle of the heterocyclic compound is oriented substantially perpendicularly to the metal layer, and the phenolic hydroxy group of the heterocyclic compound is oriented substantially perpendicularly to the resin layer.
- Orientation is preferable in that the phenolic hydroxy groups can be brought closer to the resin layer, a stronger interaction can be obtained, and the adhesion can be improved.
- quantum chemical calculation software Gaussian16 (manufactured by Gaussian) is used to optimize the structure using B3LYP (density functional theory) in DFT calculation.
- SDD Stttgart/Dresden ECP
- 6-31G(d) is used for other elements.
- the Grid scan module of the soft Material Science Suite manufactured by Schrodinger in the space around the ligand, the position at which the copper ion is restabilized is set as the initial configuration.
- the optimum structure calculated above will be explained by taking, for example, the exemplary compound (1-1) as an example. As shown in FIG.
- the interaction between the compound (exemplary compound (1-1)) and copper (Cu) When a central line A perpendicular to the axial direction is drawn at the center position of the compound with the site as the axial direction, the interaction site with copper (Cu) and the phenolic It is preferred that the hydroxy groups (OH) are oriented in opposite directions to each other. Specifically, when the optimized structure calculated above is presented in Winmostar, at least one angle shown by selecting a copper atom (Cu)-nitrogen atom (N)-oxygen atom (O)-is 140 ° The above is preferable (see FIG. 2).
- the angle formed by the copper atom-nitrogen atom-oxygen atom is 169° in Exemplified Compound (1-1), 168° in Exemplified Compound (2-2), and 71° in Exemplified Compound (3-8).
- the nitrogen atom (N) and the phenolic hydroxy group (OH) in the structure of the heterocyclic compound are present on the diagonal of the molecular skeleton, so that the nitrogen atom (N) 10, the phenolic hydroxy group (OH) can be brought closer to the resin layer 20, resulting in a stronger interaction (see FIG. 1).
- the laminate of the present invention can be applied to printed circuit boards (printed wiring boards) or electronic devices, for example.
- the printed circuit board can be formed by a method of forming a metal wiring pattern by photolithography, as will be described later.
- examples of the electronic devices include smartphones, tablet terminals, personal computers, servers, routers, communication base stations, display devices, home appliances, and the like.
- the laminate of the present invention is a laminate obtained by sequentially providing a surface-modified layer and a resin layer on a metal layer. That is, the metal layer and the surface modification layer are adjacent, and the surface modification layer and the resin layer are adjacent.
- the metal layer is a layer containing metal as a main component.
- the main component means a component containing 50% by mass or more.
- metals used for the metal layer include gold, silver, platinum, zinc, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, indium, Metals such as aluminum, lead, molybdenum, or alloys thereof can be used. Among these, from the viewpoint of workability and conductivity, it is preferable to use copper or a copper alloy as a main component.
- the metal layer can be formed by metal foil, plating, or a vacuum film forming method.
- the thickness of the metal layer is not particularly limited, and may be set according to the thickness of the metal wiring pattern to be formed, for example.
- the laminate of the present invention preferably has an insulating layer under the metal layer.
- the insulating layer is not particularly limited, and a resin sheet or prepreg that is generally used as an insulating layer can be used.
- the laminated body having the insulating layer as described above corresponds to the laminated body 6 in FIG. 5 showing the resist layer forming process described later.
- the surface-modifying layer can be formed by applying the non-photosensitive surface-modifying agent of the present invention to the surface of the metal layer and drying.
- the thickness of the surface-modified layer is not particularly limited, it is preferably within the range of 0.1 to 20 nm from the viewpoint of the effects of the present invention.
- the resin layer used in the present invention is not particularly limited, but acrylonitrile/styrene copolymer resin (AS resin), acrylonitrile/butadiene/styrene copolymer resin (ABS resin), fluororesin, polyamide, polyethylene, polyethylene terephthalate, polychlorinated Thermoplastic resins such as vinylidene, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide/triazine resin, modified polyphenylene ether, cyanate ester, etc. thermosetting resins, or UV-curable resins such as UV-curable epoxy resins and UV-curable acrylic resins. These resins may be modified with functional groups, and may be reinforced with glass fibers, aramid fibers, other fibers, or the like
- the laminate of the present invention is a printed circuit board laminate (when it is a printed circuit board laminate), a commercially available resin film or prepreg (a sheet-like fiber impregnated with a liquid resin) can be used as the resin layer.
- a commercially available resin film or prepreg a sheet-like fiber impregnated with a liquid resin
- fluorine resins, cyclopolyolefin resins, liquid crystal polymers, epoxy resins, phenol resins, polyimides, bismaleimide-triazine resins, modified polyphenylene ethers, and cyanate esters when the laminate of the present invention forms the wiring of a printed circuit board (when it is a metal wiring pattern), the resin layer can be a commercially available liquid resist or dry film resist, and contains an alkali-soluble resin. UV-curable epoxy resins, UV-curable acrylic resins, and polyimides are preferably used.
- the method for forming a metal wiring pattern according to the present invention is a method for forming a metal wiring pattern by photolithography, wherein the non-photosensitive surface modifier of the present invention is used to form a surface modified layer between the metal layer and the resist. It is preferable to have a step of forming
- a metal wiring pattern is formed by having the following steps (A) to (F).
- step (A) the metal-clad laminate 5 (see FIG. 3) in which the metal layer 2 is formed on the insulating layer 1 is washed with an acid.
- an acid cleaning liquid is not particularly limited, and conventionally known liquids can be used. Moreover, you may wash with water after acid washing.
- the insulating layer 1 is an insulating layer that serves as a base material for metal wiring patterns.
- the insulating layer 1 is made of an insulating material such as resin, and may be a prepreg in which a base material such as paper or glass is impregnated with resin.
- the metal layer 2 is the same as the metal layer of the laminate.
- step (B) the surface-modified layer 3 is formed on the metal layer 2 of the metal-clad laminate 5 using the non-photosensitive surface-modifying agent of the present invention (see FIG. 4). Specifically, a non-photosensitive surface modifier is applied onto the metal layer 2 to form the surface modified layer 3 .
- the thickness of the surface modification layer 3 is not particularly limited, it is preferably within the range of 0.1 to 20 nm from the viewpoint of the effects of the present invention.
- step (B) and the next step (C) it is preferable to have a step of washing the metal-clad laminate 5 with the surface-modified layer 3 formed thereon. This allows removal of excess non-photosensitive surface modifiers that interact poorly with the metal layer.
- step (C) a resist layer 4 containing a photosensitive resin is formed on the surface modified layer 3 (see FIG. 5). Since the laminate 6 in this state includes the metal layer 2, the surface modification layer 3 and the resist layer 4, it corresponds to the laminate of the present invention.
- the resist layer 4 is not particularly limited as long as it contains a photosensitive resin that can be patterned by photolithography in the same manner as the resist layer of the laminate. can be formed by applying
- step (D) the resist layer 4 is patterned by exposure and development (see FIG. 6). Specifically, by exposing the resist layer 4 using a photomask that can expose the resist layer 4 in an arbitrary pattern, and then dissolving and removing unnecessary portions of the resist layer 4 using a developer, Patterning. It is preferable to wash with water after development.
- the exposure conditions and development conditions are not particularly limited, and conventionally known conditions can be applied.
- step (E) the surface modification layer 3 and the metal layer 2 are etched through the resist layer 4 (see FIG. 7). Specifically, the surface modification layer 3 and the metal layer 2 are patterned by dissolving the surface modification layer 3 and the metal layer 2 in the portions where the resist layer 4 has been removed by wet etching using an etchant. .
- the etching conditions are not particularly limited, and conventionally known conditions can be applied.
- step (F) the resist layer 4 is peeled off from the metal-clad laminate 5 (see FIG. 8).
- the surface-modified layer 3 is easily separated from the resist layer 4, so the surface-modified layer 3 is likely to remain on the metal layer 2 of the metal-clad laminate 5.
- the surface modification layer 3 may remain on the metal layer 2 or may be peeled off together with the resist layer 4 .
- the method for removing the resist layer 4 is not particularly limited, it is preferable to remove it using a remover.
- the stripping liquid is not particularly limited, and conventionally known ones can be applied.
- the metal wiring pattern 7 can be formed.
- the method for forming a metal wiring pattern it is possible to form a high-density and high-definition metal wiring pattern. It becomes possible to manufacture the printed circuit board (printed wiring board) of the present invention.
- the method for forming a laminate (printed circuit board laminate) according to the present invention is a method for forming a resin layer on a metal layer, wherein the non-photosensitive surface modifier of the present invention is used to form a metal layer and a resin layer. a step of forming a surface modified layer between The metal layer may be solid or patterned with wiring, and a known method such as hot pressing can be used as the lamination method.
- the resin layer a commercially available resin film or prepreg (sheet-like fiber impregnated with liquid resin) can be used, and fluorine resin, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, bismaleimide resin, etc.
- a resin containing a triazine resin, a modified polyphenylene ether, or a cyanate ester is preferably used, and surface treatment such as corona treatment or plasma treatment may be performed on the bonding surface of the resin layer before lamination.
- Example 1 The orientation of each compound shown in Tables I and II below was evaluated. Specifically, quantum chemical calculation software Gaussian16 (manufactured by Gaussian) was used to perform structure optimization using B3LYP (density functional theory) in DFT calculation. As a basis function for copper, SDD (Stuttgart/Dresden ECP) was used for calculation, and 6-31G(d) was used for other elements. In the Grid scan module of the soft Material Science Suite manufactured by Schrodinger, the position where the copper ion is restabilized in the space around the ligand was set as the initial configuration.
- Gaussian16 quantum chemical calculation software
- B3LYP density functional theory
- SDD Sttgart/Dresden ECP
- Example 2 ⁇ Preparation of non-photosensitive surface modifier> Each compound in Table I below was added to a solvent consisting of 20% by mass of ethanol and 80% by mass of ion-exchanged water so as to be 20 ppm by mass, and non-photosensitive surface modifiers 1 to 8 and 12 to 15 were prepared, respectively. bottom. Further, for non-photosensitive surface modifiers 10 and 11, the ratio of ethanol and ion-exchanged water was changed as shown in Table I below. It was prepared in the same manner except that the concentration was changed as shown in Table I below.
- a metal wiring pattern 1 was formed by performing the following steps (A) to (F).
- Step (A) A copper clad laminate (Megtron 7 R-5785 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device. and then washed with water.
- an acid cleaning solution CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.
- Step (B) The non-photosensitive surface modifier 1 prepared above was applied onto the metal layer of the copper-clad laminate that had been acid-washed and water-washed using a spray-type applicator, and was then washed with water. After washing with water, water was removed with a PVA roller and dried with an air knife at 80° C. to form a surface modified layer with a thickness of 5 nm.
- Step (C) A dry film resist (AK-4034 manufactured by Asahi Kasei Co., Ltd.) (a photocurable acrylic resin containing an alkali-soluble resin) was applied as a resin layer on the surface-modified layer by a hot roll laminator at a roll temperature of 105° C. and an air pressure of 0.5°C. A resist layer was formed by lamination under conditions of 35 MPa and a lamination speed of 1.5 m/min.
- the dry film resist used (AK-4034 manufactured by Asahi Kasei Co., Ltd.) has a support made of a polyethylene terephthalate film on one side and a protective layer made of a polyethylene film on the other side. Lamination was carried out by allowing the surface on which the protective layer was present to adhere to the metal layer via the surface-modified layer while peeling off the protective layer.
- Step (D) Using a chromium glass mask, the resist layer was exposed by a parallel light exposure machine (HMW-801 manufactured by ORC Co., Ltd.). As the exposure condition, 60 mj/cm 2 , which is the recommended condition for dry film resist, was adopted. The support was peeled off from the resist layer after exposure. After that, the unexposed portions of the resist layer are dissolved and removed at 30°C using a developer consisting of an aqueous solution of 1% by mass of sodium carbonate (Na 2 CO 3 ) and an alkaline developer, and then washed with water. Developed. The resist layer was patterned by the above operation.
- a parallel light exposure machine HMW-801 manufactured by ORC Co., Ltd.
- As the exposure condition 60 mj/cm 2 , which is the recommended condition for dry film resist, was adopted.
- the support was peeled off from the resist layer after exposure. After that, the unexposed portions of the resist layer are dissolved and removed at 30°C using a
- Step (E) In a dip method, using an etchant consisting of an aqueous solution of 2% by mass of hydrochloric acid (HCl) and 2% by mass of ferric chloride (FeCl 3 ), the surface was reformed under the conditions of a temperature of 30 ° C. and a dipping time of 1 minute. The quality layer and the metal layer were etched.
- HCl hydrochloric acid
- FeCl 3 ferric chloride
- Step (F) The resist layer was stripped from the copper-clad laminate at a temperature of 50° C. using a stripping solution consisting of an aqueous solution of 3% by mass of sodium hydroxide (NaOH).
- metal wiring patterns 2 to 15 were formed in the same manner except that the non-photosensitive surface modifier 1 was changed to each of the non-photosensitive surface modifiers 2 to 15 shown in Table I below. formed.
- Example 3 ⁇ Preparation of non-photosensitive surface modifier>
- Non-photosensitive surface modifiers 1-15 similar to Example 2 were prepared.
- a printed circuit board laminate 1 was formed by carrying out the following steps (I) to (III).
- Step (I) A copper clad laminate (R-1766 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device, It was then washed with water.
- an acid cleaning solution CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.
- Step (II) The non-photosensitive surface modifier 1 prepared above was applied onto the metal layer of the copper-clad laminate that had been acid-washed and water-washed using a spray-type applicator, and was then washed with water. After washing with water, water was removed with a PVA roller and dried with an air knife at 80° C. to form a surface modifier layer with a thickness of 5 nm.
- Step (III) A prepreg (Panasonic R-1661) (epoxy resin) is laminated on the surface modifier layer, and the temperature is increased from room temperature (25 ° C.) to 10 ° C./min at a pressure of 3.0 MPa. was heated to 120° C. and held for 30 minutes, and heated to 190° C. at a rate of temperature increase of 10° C./min and held for 2 hours for lamination and adhesion, thereby fabricating a printed circuit board laminate 1 .
- the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention has a nitrogen atom and a phenolic hydroxy group in its structure that are diagonally opposite to each other. It can be seen that is coordinated in the vertical direction.
- the resist adhesion and prepreg adhesion are improved as compared with the case of using the surface modifier of the comparative example. It is recognized that it is superior to
- the present invention can be used for non-photosensitive surface modifiers, laminates, printed circuit boards, and electronic devices that can further improve the adhesion between a metal layer and a resin layer.
Abstract
A nonphotosensitive surface modifying agent according to the present invention is for forming a surface modification layer between a metal layer and a resin layer, and contains at least one heterocyclic compound having a structure represented at least by general formula (1), (2), (3), or (4). [R1 represents a hydrogen atom, an aryl group, or a heteroaryl group, and optionally further has a substituent group. R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group, or a halogen atom. n and m each represent an integer of 0-5, but n+m equals an integer of 0-5 (however, an integer of 0-4 for general formula (1)).]
Description
本発明は、非感光性表面改質剤、積層体、プリント基板及び電子デバイスに関し、特に、金属層と樹脂層との間の密着性をより向上させることができる非感光性表面改質剤等に関する。
TECHNICAL FIELD The present invention relates to a non-photosensitive surface modifier, a laminate, a printed circuit board, and an electronic device, and in particular, a non-photosensitive surface modifier that can further improve the adhesion between a metal layer and a resin layer. Regarding.
近年、データ社会化の進展により、配線が高密度かつ高精細であるプリント配線板（「プリント基板」ともいう。）が求められている。
プリント配線板の製造工程においては、金属層や金属配線の表面に、エッチングレジスト、めっきレジスト、ソルダーレジスト、プリプレグ等の樹脂材料が接合される。プリント配線板の製造工程及び製造後の製品においては、金属層と樹脂層との間に高い接着性が求められる。
そこで、金属層と樹脂層との接着性を高めるために、金属層の表面に樹脂層との接着性を向上する接着性向上用の被膜を形成する方法（例えば、特許文献１参照。）や、含硫黄化合物及び含窒素化合物を感光性樹脂中に含有させて接着性を向上させる方法（例えば、特許文献２参照。）が知られている。 2. Description of the Related Art In recent years, due to the development of a data society, printed wiring boards (also referred to as “printed boards”) having high-density and high-definition wiring are in demand.
In the process of manufacturing a printed wiring board, a resin material such as an etching resist, a plating resist, a solder resist, or a prepreg is bonded to the surface of a metal layer or metal wiring. High adhesiveness is required between the metal layer and the resin layer in the manufacturing process of the printed wiring board and in the manufactured product.
Therefore, in order to increase the adhesiveness between the metal layer and the resin layer, a method of forming a film for improving adhesiveness for improving the adhesiveness with the resin layer on the surface of the metal layer (see, for example, Patent Document 1), , a method of incorporating a sulfur-containing compound and a nitrogen-containing compound into a photosensitive resin to improve adhesiveness (see, for example, Patent Document 2).
プリント配線板の製造工程においては、金属層や金属配線の表面に、エッチングレジスト、めっきレジスト、ソルダーレジスト、プリプレグ等の樹脂材料が接合される。プリント配線板の製造工程及び製造後の製品においては、金属層と樹脂層との間に高い接着性が求められる。
そこで、金属層と樹脂層との接着性を高めるために、金属層の表面に樹脂層との接着性を向上する接着性向上用の被膜を形成する方法（例えば、特許文献１参照。）や、含硫黄化合物及び含窒素化合物を感光性樹脂中に含有させて接着性を向上させる方法（例えば、特許文献２参照。）が知られている。 2. Description of the Related Art In recent years, due to the development of a data society, printed wiring boards (also referred to as “printed boards”) having high-density and high-definition wiring are in demand.
In the process of manufacturing a printed wiring board, a resin material such as an etching resist, a plating resist, a solder resist, or a prepreg is bonded to the surface of a metal layer or metal wiring. High adhesiveness is required between the metal layer and the resin layer in the manufacturing process of the printed wiring board and in the manufactured product.
Therefore, in order to increase the adhesiveness between the metal layer and the resin layer, a method of forming a film for improving adhesiveness for improving the adhesiveness with the resin layer on the surface of the metal layer (see, for example, Patent Document 1), , a method of incorporating a sulfur-containing compound and a nitrogen-containing compound into a photosensitive resin to improve adhesiveness (see, for example, Patent Document 2).
しかしながら、上記特許文献１及び２の技術では、金属層と樹脂層との密着性はある程度は向上するものの、未だ十分な密着性が得られていなかった。特に、近年携帯通信の５Ｇや半導体パッケージの高密度実装技術が進み、プリント配線板の金属層の低粗面化や金属配線の狭ライン化の要求が高まっており、それに伴い金属層と樹脂層の密着性が従来以上に求められている。
However, with the techniques of Patent Documents 1 and 2, although the adhesion between the metal layer and the resin layer is improved to some extent, sufficient adhesion has not yet been obtained. In particular, in recent years, 5G mobile communication and high-density mounting technology for semiconductor packages have progressed, and the demand for low-roughness metal layers on printed wiring boards and narrower metal wiring lines has increased. is required more than ever before.
本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、金属層と樹脂層との間の密着性をより向上させることができる非感光性表面改質剤、当該非感光性表面改質剤を用いた積層体、プリント基板及び電子デバイスを提供することである。
The present invention has been made in view of the above problems and circumstances, and the problem to be solved is a non-photosensitive surface modifier that can further improve the adhesion between the metal layer and the resin layer. An object of the present invention is to provide a laminate, a printed circuit board and an electronic device using a photosensitive surface modifier.
本発明者は、上記課題を解決すべく、上記問題の原因等について検討する過程において、金属層と樹脂層との間の表面改質層を形成する非感光性表面改質剤として、特定の構造を有する複素環化合物を含有させることにより、金属層と樹脂層との密着性をより向上させることができることを見いだし本発明に至った。
すなわち、本発明に係る上記課題は、以下の手段により解決される。 In order to solve the above problems, the present inventors, in the process of studying the causes of the above problems, found that a specific The present inventors have found that the adhesion between the metal layer and the resin layer can be further improved by including a heterocyclic compound having a structure, and have completed the present invention.
That is, the above problems related to the present invention are solved by the following means.
すなわち、本発明に係る上記課題は、以下の手段により解決される。 In order to solve the above problems, the present inventors, in the process of studying the causes of the above problems, found that a specific The present inventors have found that the adhesion between the metal layer and the resin layer can be further improved by including a heterocyclic compound having a structure, and have completed the present invention.
That is, the above problems related to the present invention are solved by the following means.
１．金属層と樹脂層の間に表面改質層を形成する非感光性表面改質剤であって、
少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する非感光性表面改質剤。
［式中、Ｒ１は、水素原子、アリール基又はヘテロアリール基を表し、さらに置換基を有してもよい。
Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基、ヘテロアリール基又はハロゲン原子を表す。
ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合は、それぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。］ 1. A non-photosensitive surface modifier that forms a surface modification layer between the metal layer and the resin layer,
A non-photosensitive surface modifier containing at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
[In the formula, R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
Each of n and m is an integer of 0 to 5, and n+m=an integer of 0 to 5 (however, an integer of 0 to 4 for general formula (1)). When having multiple substituents R 2 , each substituent R 2 may be the same or different. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may ]
少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する非感光性表面改質剤。
Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基、ヘテロアリール基又はハロゲン原子を表す。
ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合は、それぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。］ 1. A non-photosensitive surface modifier that forms a surface modification layer between the metal layer and the resin layer,
A non-photosensitive surface modifier containing at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
Each of n and m is an integer of 0 to 5, and n+m=an integer of 0 to 5 (however, an integer of 0 to 4 for general formula (1)). When having multiple substituents R 2 , each substituent R 2 may be the same or different. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may ]
２．前記複素環化合物が、前記一般式（１）で表される構造を有する第１項に記載の非感光性表面改質剤。
2. 2. The non-photosensitive surface modifier according to item 1, wherein the heterocyclic compound has a structure represented by the general formula (1).
３．前記複素環化合物が、下記一般式（５）で表される構造を有する複素環化合物である第２項に記載の非感光性表面改質剤。
［式中、Ｒ１は、水素原子、アリール基又はヘテロアリール基を表し、さらに置換基を有してもよい。］
3. 3. The non-photosensitive surface modifier according to item 2, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5).
[In the formula, R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent. ]
４．少なくとも水又はアルコール類を含有する第１項から第３項までのいずれか一項に記載の非感光性表面改質剤。
4. 4. The non-photosensitive surface modifier according to any one of items 1 to 3, containing at least water or alcohols.
５．金属層上に表面改質層及び樹脂層を順次設けた積層体であって、
前記表面改質層が、少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する積層体。
［式中、Ｒ１は、水素原子、アリール基又はヘテロアリール基を表し、さらに置換基を有してもよい。
Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基、ヘテロアリール基又はハロゲン原子を表す。
ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合はそれぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。］ 5. A laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
A laminate in which the surface-modified layer contains at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
[In the formula, R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent.
R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
Each of n and m is an integer of 0 to 5, and n+m=an integer of 0 to 5 (however, an integer of 0 to 4 for general formula (1)). When having multiple substituents R 2 , each substituent R 2 may be the same or different. Further, when having a plurality of n, each n may be the same or different, and when having a plurality of m, each m may be the same or different. good too. ]
前記表面改質層が、少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する積層体。
Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基、ヘテロアリール基又はハロゲン原子を表す。
ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合はそれぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。］ 5. A laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
A laminate in which the surface-modified layer contains at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
Each of n and m is an integer of 0 to 5, and n+m=an integer of 0 to 5 (however, an integer of 0 to 4 for general formula (1)). When having multiple substituents R 2 , each substituent R 2 may be the same or different. Further, when having a plurality of n, each n may be the same or different, and when having a plurality of m, each m may be the same or different. good too. ]
６．前記複素環化合物が、前記一般式（１）で表される構造を有する複素環化合物である第５項に記載の積層体。
6. 6. The laminate according to Item 5, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1).
７．前記複素環化合物が、下記一般式（５）で表される構造を有する複素環化合物である第６項に記載の積層体。
［式中、Ｒ１は、水素原子、アリール基又はヘテロアリール基を表し、さらに置換基を有してもよい。］
7. 7. The laminate according to item 6, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5).
[In the formula, R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may further have a substituent. ]
８．前記樹脂層が、アルカリ可溶性樹脂を含有する感光性樹脂組成物である第５項から第７項までのいずれか一項に記載の積層体。
8. 8. The laminate according to any one of items 5 to 7, wherein the resin layer is a photosensitive resin composition containing an alkali-soluble resin.
９．前記樹脂層が、少なくともエポキシ構造を有する樹脂を含有する熱硬化性樹脂組成物である第５項から第７項までのいずれか一項に記載の積層体。
9. 8. The laminate according to any one of items 5 to 7, wherein the resin layer is a thermosetting resin composition containing at least a resin having an epoxy structure.
１０．第５項から第９項までのいずれか一項に記載の積層体を用いたプリント基板。
10. A printed circuit board using the laminate according to any one of items 5 to 9.
１１．第５項から第９項までのいずれか一項に記載の積層体を用いた電子デバイス。
11. An electronic device using the laminate according to any one of items 5 to 9.
本発明の上記手段により、金属層と樹脂層との間の密着性をより向上させることができる非感光性表面改質剤、当該非感光性表面改質剤を用いた積層体、プリント基板及び電子デバイスを提供することができる。
本発明の効果の発現機構又は作用機構については、明確にはなっていないが、以下のように推察している。
本発明の非感光性表面改質剤は、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有するので、前記複素環化合物の構造中に存在する窒素原子（Ｎ原子）が金属と相互作用し、フェノール性ヒドロキシ基が樹脂と相互作用する。したがって、このような非感光性表面改質剤により形成された表面改質層が、金属層と樹脂層との間に存在することで、金属層と樹脂層とが、前記相互作用を有する表面改質層により密着性が向上する。
フェノール性ヒドロキシ基は、樹脂に存在する極性基と水素結合又はエポキシ基に代表される重合性樹脂と共有結合することができ、π－π相互作用やファンデルワールス力よりも強い相互作用力で密着することができる。
特に、前記複素環化合物の構造中における窒素原子とフェノール性ヒドロキシ基が分子骨格の対角に存在することにより、図１に示すように、前記複素環化合物（例えば図１の例示化合物（１－１））の分子骨格が、垂直方向（表面改質層３０の厚さ方向）に配位し、窒素原子（Ｎ）が金属層１０の金属と相互作用し、フェノール性ヒドロキシ基（ＯＨ）が樹脂層２０に近づくことができ、さらに強い相互作用が得られると推察される。
なお、図１に示す各原子は、図２と同様のものを表す。 By the means of the present invention, a non-photosensitive surface modifier that can further improve the adhesion between a metal layer and a resin layer, a laminate using the non-photosensitive surface modifier, a printed circuit board, and An electronic device can be provided.
Although the expression mechanism or action mechanism of the effects of the present invention has not been clarified, it is speculated as follows.
The non-photosensitive surface modifier of the present invention contains at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4). A nitrogen atom (N atom) present in the structure of the ring compound interacts with the metal, and a phenolic hydroxy group interacts with the resin. Therefore, the presence of the surface-modified layer formed by such a non-photosensitive surface-modifying agent between the metal layer and the resin layer allows the metal layer and the resin layer to form a surface having the above interaction. Adhesion is improved by the modified layer.
Phenolic hydroxy groups can form covalent bonds with polar groups present in resins and polymerizable resins represented by hydrogen bonds or epoxy groups, with stronger interaction forces than π-π interactions and van der Waals forces. can adhere.
In particular, since the nitrogen atom and the phenolic hydroxy group in the structure of the heterocyclic compound are present on the diagonal of the molecular skeleton, the heterocyclic compound (for example, the exemplary compound (1- The molecular skeleton of 1)) is coordinated in the vertical direction (thickness direction of the surface modified layer 30), the nitrogen atoms (N) interact with the metal of themetal layer 10, and the phenolic hydroxyl groups (OH) It is presumed that the resin layer 20 can be approached and a stronger interaction can be obtained.
Each atom shown in FIG. 1 represents the same as in FIG.
本発明の効果の発現機構又は作用機構については、明確にはなっていないが、以下のように推察している。
本発明の非感光性表面改質剤は、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有するので、前記複素環化合物の構造中に存在する窒素原子（Ｎ原子）が金属と相互作用し、フェノール性ヒドロキシ基が樹脂と相互作用する。したがって、このような非感光性表面改質剤により形成された表面改質層が、金属層と樹脂層との間に存在することで、金属層と樹脂層とが、前記相互作用を有する表面改質層により密着性が向上する。
フェノール性ヒドロキシ基は、樹脂に存在する極性基と水素結合又はエポキシ基に代表される重合性樹脂と共有結合することができ、π－π相互作用やファンデルワールス力よりも強い相互作用力で密着することができる。
特に、前記複素環化合物の構造中における窒素原子とフェノール性ヒドロキシ基が分子骨格の対角に存在することにより、図１に示すように、前記複素環化合物（例えば図１の例示化合物（１－１））の分子骨格が、垂直方向（表面改質層３０の厚さ方向）に配位し、窒素原子（Ｎ）が金属層１０の金属と相互作用し、フェノール性ヒドロキシ基（ＯＨ）が樹脂層２０に近づくことができ、さらに強い相互作用が得られると推察される。
なお、図１に示す各原子は、図２と同様のものを表す。 By the means of the present invention, a non-photosensitive surface modifier that can further improve the adhesion between a metal layer and a resin layer, a laminate using the non-photosensitive surface modifier, a printed circuit board, and An electronic device can be provided.
Although the expression mechanism or action mechanism of the effects of the present invention has not been clarified, it is speculated as follows.
The non-photosensitive surface modifier of the present invention contains at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4). A nitrogen atom (N atom) present in the structure of the ring compound interacts with the metal, and a phenolic hydroxy group interacts with the resin. Therefore, the presence of the surface-modified layer formed by such a non-photosensitive surface-modifying agent between the metal layer and the resin layer allows the metal layer and the resin layer to form a surface having the above interaction. Adhesion is improved by the modified layer.
Phenolic hydroxy groups can form covalent bonds with polar groups present in resins and polymerizable resins represented by hydrogen bonds or epoxy groups, with stronger interaction forces than π-π interactions and van der Waals forces. can adhere.
In particular, since the nitrogen atom and the phenolic hydroxy group in the structure of the heterocyclic compound are present on the diagonal of the molecular skeleton, the heterocyclic compound (for example, the exemplary compound (1- The molecular skeleton of 1)) is coordinated in the vertical direction (thickness direction of the surface modified layer 30), the nitrogen atoms (N) interact with the metal of the
Each atom shown in FIG. 1 represents the same as in FIG.
本発明の非感光性表面改質剤は、金属層と樹脂層の間に表面改質層を形成する非感光性表面改質剤であって、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。
この特徴は、下記各実施形態に共通又は対応する技術的特徴である。 The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
This feature is a technical feature common to or corresponding to each of the following embodiments.
この特徴は、下記各実施形態に共通又は対応する技術的特徴である。 The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
This feature is a technical feature common to or corresponding to each of the following embodiments.
本発明の実施態様としては、前記複素環化合物が、前記一般式（１）で表される構造を有する複素環化合物であることが好ましく、特に、前記複素環化合物が、前記一般式（５）で表される構造を有する複素環化合物であることが、金属層と樹脂層との密着性向上の点で好ましい。
また、少なくとも水又はアルコール類を含有することが、溶解性の点で好ましい。 As an embodiment of the present invention, the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (1). A heterocyclic compound having a structure represented by is preferable from the viewpoint of improving the adhesion between the metal layer and the resin layer.
In terms of solubility, it is preferable to contain at least water or alcohols.
また、少なくとも水又はアルコール類を含有することが、溶解性の点で好ましい。 As an embodiment of the present invention, the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (1). A heterocyclic compound having a structure represented by is preferable from the viewpoint of improving the adhesion between the metal layer and the resin layer.
In terms of solubility, it is preferable to contain at least water or alcohols.
本発明の積層体は、金属層上に表面改質層及び樹脂層を順次設けた積層体であって、
前記表面改質層が、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。これにより、金属層と樹脂層との間の密着性が向上した積層体を提供することができる。 The laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
The surface-modifying layer contains at least one heterocyclic compound having a structure represented by formula (1), (2), (3) or (4). This makes it possible to provide a laminate with improved adhesion between the metal layer and the resin layer.
前記表面改質層が、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。これにより、金属層と樹脂層との間の密着性が向上した積層体を提供することができる。 The laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
The surface-modifying layer contains at least one heterocyclic compound having a structure represented by formula (1), (2), (3) or (4). This makes it possible to provide a laminate with improved adhesion between the metal layer and the resin layer.
前記樹脂層が、アルカリ可溶性樹脂を含有する感光性樹脂組成物、もしくは、少なくともエポキシ構造を有する樹脂を含有する熱硬化性樹脂組成物であることが、前記複素環化合物に含まれるフェノール性水酸基との相互作用による密着性向上の点で好ましい。
The resin layer is a photosensitive resin composition containing an alkali-soluble resin, or a thermosetting resin composition containing at least a resin having an epoxy structure, and the phenolic hydroxyl group contained in the heterocyclic compound. is preferable from the point of view of improvement in adhesion due to the interaction of
また、本発明の積層体は、プリント基板又は電子デバイスに好適に用いることができる。
In addition, the laminate of the present invention can be suitably used for printed circuit boards or electronic devices.
以下、本発明とその構成要素及び本発明を実施するための形態・態様について説明をする。なお、本願において、「～」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。
The following describes the present invention, its constituent elements, and the forms and modes for carrying out the present invention. In the present application, "-" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.
［非感光性表面改質剤］
本発明の非感光性表面改質剤は、金属層と樹脂層の間に表面改質層を形成する非感光性表面改質剤であって、少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。 [Non-photosensitive surface modifier]
The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the following general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
本発明の非感光性表面改質剤は、金属層と樹脂層の間に表面改質層を形成する非感光性表面改質剤であって、少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。 [Non-photosensitive surface modifier]
The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier that forms a surface modification layer between a metal layer and a resin layer, and comprises at least the following general formulas (1), (2), It contains one or more heterocyclic compounds having a structure represented by (3) or (4).
前記一般式（１）において、Ｒ１は、水素原子、アリール基又はヘテロアリール基を表し、特に、アリール基を表すことが好ましく、さらに置換基を有してもよい。
前記置換基としては、例えば、ヒドロキシ基、アミド基等が挙げられる。 In the general formula (1), R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
Examples of the substituent include a hydroxy group and an amide group.
前記置換基としては、例えば、ヒドロキシ基、アミド基等が挙げられる。 In the general formula (1), R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
Examples of the substituent include a hydroxy group and an amide group.
前記一般式（１）～（４）において、Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基又はハロゲン原子、ヘテロアリール基を表し、特に、アルキル基を表すことが好ましい。
In the general formulas (1) to (4), R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a halogen atom, or a heteroaryl group; In particular, it is preferable to represent an alkyl group.
前記一般式（１）～（４）において、前記ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。
また、各一般式において、複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合は、それぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。 In the general formulas (1) to (4), n and m are each an integer of 0 to 5, and n + m = an integer of 0 to 5 (however, with respect to general formula (1), an integer of 0 to 4) represents
Moreover, in each general formula, when having a plurality of substituents R 2 , the respective substituents R 2 may be the same or different from each other. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may
また、各一般式において、複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合は、それぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。 In the general formulas (1) to (4), n and m are each an integer of 0 to 5, and n + m = an integer of 0 to 5 (however, with respect to general formula (1), an integer of 0 to 4) represents
Moreover, in each general formula, when having a plurality of substituents R 2 , the respective substituents R 2 may be the same or different from each other. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may
本発明に係る複素環化合物は、前記一般式（１）～（４）で表される構造を有する複素環化合物のうち、前記一般式（１）で表される構造を有する複素環化合物であることが、金属層と表面改質層及び表面改質層と樹脂層との相互作用により、結果として金属層と樹脂層の密着性向上の点で好ましい。
The heterocyclic compound according to the present invention is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4). This is preferable in that the adhesion between the metal layer and the resin layer is improved as a result of the interaction between the metal layer and the surface modified layer and between the surface modified layer and the resin layer.
また、本発明に係る複素環化合物は、下記一般式（５）で表される構造を有する複素環化合物であることが、金属層と樹脂層との密着性向上の点で好ましい。
Further, the heterocyclic compound according to the present invention is preferably a heterocyclic compound having a structure represented by the following general formula (5) from the viewpoint of improving adhesion between the metal layer and the resin layer.
前記一般式（５）において、Ｒ１は、水素原子、アリール基又はヘテロアリール基を表し、特に、アリール基を表すことが好ましく、さらに置換基を有してもよい。
前記置換基としては、例えば、ヒドロキシ基、アミド基等が挙げられる。 In the general formula (5), R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
Examples of the substituent include a hydroxy group and an amide group.
前記置換基としては、例えば、ヒドロキシ基、アミド基等が挙げられる。 In the general formula (5), R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, preferably an aryl group, and may further have a substituent.
Examples of the substituent include a hydroxy group and an amide group.
前記一般式（１）～（５）で表される構造を有する複素環化合物の例を以下に挙げるが、本発明に係る複素環化合物はこれらに限定されるものではない。
Examples of the heterocyclic compounds having structures represented by the general formulas (1) to (5) are listed below, but the heterocyclic compound according to the present invention is not limited to these.
本発明の非感光性表面改質剤が含有する前記複素環化合物は、１種のみでもよいし、２種以上でもよい。
The heterocyclic compound contained in the non-photosensitive surface modifier of the present invention may be one type or two or more types.
本発明の非感光性表面改質剤は、溶解性の観点から、溶媒として少なくとも水又はアルコール類を含有することが好ましい。当該アルコールは、例えばメタノール、エタノール、２－プロパノール等が挙げられる。溶媒には、水又はアルコール類を２種以上併用してもよい。
具体的には、水とアルコールの質量比（質量％）を１００：０～５０：５０の範囲内とすることが好ましく、１００：０～７５：２５の範囲内とすることがより好ましい。 From the viewpoint of solubility, the non-photosensitive surface modifier of the present invention preferably contains at least water or alcohol as a solvent. Examples of the alcohol include methanol, ethanol, 2-propanol and the like. Two or more kinds of water or alcohols may be used in combination as the solvent.
Specifically, the mass ratio (% by mass) of water and alcohol is preferably in the range of 100:0 to 50:50, more preferably in the range of 100:0 to 75:25.
具体的には、水とアルコールの質量比（質量％）を１００：０～５０：５０の範囲内とすることが好ましく、１００：０～７５：２５の範囲内とすることがより好ましい。 From the viewpoint of solubility, the non-photosensitive surface modifier of the present invention preferably contains at least water or alcohol as a solvent. Examples of the alcohol include methanol, ethanol, 2-propanol and the like. Two or more kinds of water or alcohols may be used in combination as the solvent.
Specifically, the mass ratio (% by mass) of water and alcohol is preferably in the range of 100:0 to 50:50, more preferably in the range of 100:0 to 75:25.
前記芳香族複素環化合物は、非感光性表面改質剤全体に対して０．００００１（０．１ｐｐｍ）～０．１（１０００ｐｐｍ）質量％の範囲内で含有することが皮膜形成性の点で好ましく、特に、０．００００１（０．１ｐｐｍ）～０．０１（１００ｐｐｍ）質量％の範囲内で含有することが好ましい。
The aromatic heterocyclic compound is contained in the range of 0.00001 (0.1 ppm) to 0.1 (1000 ppm) mass% with respect to the total non-photosensitive surface modifier from the viewpoint of film formation. Preferably, it is contained within the range of 0.00001 (0.1 ppm) to 0.01 (100 ppm) mass %.
また、本発明の非感光性表面改質剤は、上記以外の他の成分が含まれていてもよいが、ポリマー、重合性モノマー又はオリゴマーを含有しない、すなわち、樹脂を含有しない、
非重合性の材料のみからなるものとする。
前記他の成分としては、界面活性剤、防腐剤、安定化剤、酸、塩基、ｐＨ調整剤等が挙げられる。 In addition, the non-photosensitive surface modifier of the present invention may contain other components other than the above, but does not contain polymers, polymerizable monomers or oligomers, that is, does not contain resins.
shall consist only of non-polymeric materials;
The other components include surfactants, preservatives, stabilizers, acids, bases, pH adjusters and the like.
非重合性の材料のみからなるものとする。
前記他の成分としては、界面活性剤、防腐剤、安定化剤、酸、塩基、ｐＨ調整剤等が挙げられる。 In addition, the non-photosensitive surface modifier of the present invention may contain other components other than the above, but does not contain polymers, polymerizable monomers or oligomers, that is, does not contain resins.
shall consist only of non-polymeric materials;
The other components include surfactants, preservatives, stabilizers, acids, bases, pH adjusters and the like.
［積層体］
本発明の積層体は、金属層上に表面改質層及び樹脂層を順次設けた積層体であって、前記表面改質層が、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。 [Laminate]
The laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer, wherein the surface-modified layer comprises at least the general formulas (1), (2), and (3). or contains one or more heterocyclic compounds having a structure represented by (4).
本発明の積層体は、金属層上に表面改質層及び樹脂層を順次設けた積層体であって、前記表面改質層が、少なくとも前記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する。 [Laminate]
The laminate of the present invention is a laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer, wherein the surface-modified layer comprises at least the general formulas (1), (2), and (3). or contains one or more heterocyclic compounds having a structure represented by (4).
前記一般式（１）～（４）で表される構造を有する複素環化合物は、前記したとおりのためその説明を省略する。
The description of the heterocyclic compounds having the structures represented by the general formulas (1) to (4) is omitted because they are as described above.
また、前記複素環化合物は、前記一般式（１）～（４）で表される構造を有する複素環化合物のうち、前記一般式（１）で表される構造を有する複素環化合物であることが、金属層と表面改質層及び表面改質層と樹脂層との相互作用により、結果として金属層と樹脂層の密着性向上の点で好ましい。
特に、前記複素環化合物が、前記一般式（５）で表される構造を有する複素環化合物であることが、金属層と樹脂層との密着性向上の点で好ましい。 Further, the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4). However, the interaction between the metal layer and the modified surface layer and between the modified surface layer and the resin layer results in improved adhesion between the metal layer and the resin layer.
In particular, the heterocyclic compound is preferably a heterocyclic compound having the structure represented by the general formula (5) from the viewpoint of improving the adhesion between the metal layer and the resin layer.
特に、前記複素環化合物が、前記一般式（５）で表される構造を有する複素環化合物であることが、金属層と樹脂層との密着性向上の点で好ましい。 Further, the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having the structures represented by the general formulas (1) to (4). However, the interaction between the metal layer and the modified surface layer and between the modified surface layer and the resin layer results in improved adhesion between the metal layer and the resin layer.
In particular, the heterocyclic compound is preferably a heterocyclic compound having the structure represented by the general formula (5) from the viewpoint of improving the adhesion between the metal layer and the resin layer.
本発明の積層体は、前記複素環化合物の複素環が、前記金属層に対して略垂直方向に配向し、前記複素環化合物のフェノール性ヒドロキシ基が、前記樹脂層に対して略垂直方向に配向していることが、フェノール性ヒドロキシ基が樹脂層により近づくことができ、さらに強い相互作用が得られ、密着性向上の点で好ましい。
In the laminate of the present invention, the heterocycle of the heterocyclic compound is oriented substantially perpendicularly to the metal layer, and the phenolic hydroxy group of the heterocyclic compound is oriented substantially perpendicularly to the resin layer. Orientation is preferable in that the phenolic hydroxy groups can be brought closer to the resin layer, a stronger interaction can be obtained, and the adhesion can be improved.
前記複素環化合物の配向性については、例えば、量子化学計算ソフトＧａｕｓｓｉａｎ１６（Ｇａｕｓｓｉａｎ社製）を用いて、ＤＦＴ計算でＢ３ＬＹＰ（密度汎関数法）を用いて構造最適化を行う。
銅には基底関数として、ＳＤＤ（Ｓｔｕｔｔｇａｒｔ／Ｄｒｅｓｄｅｎ ＥＣＰ）を用いて計算し、その他の元素は６－３１Ｇ（ｄ）を用いる。そして、ｓｃｈｒｏｄｉｎｇｅｒ社製のソフトＭａｔｅｒｉａｌ Ｓｃｉｅｎｃｅ ＳｕｉｔｅのＧｒｉｄ ｓｃａｎモジュールで配位子周りの空間で、銅イオンが再安定になる位置を初期配置とする。
上記で計算した最適構造について、例えば例示化合物（１－１）を例に挙げて説明すると、図２に示すように、化合物（例示化合物（１－１））と銅（Ｃｕ）との相互作用部位を軸方向として、化合物の中心位置に前記軸方向に対して垂直となる中心線Ａを引いた場合に、当該中心線Ａに対して、銅（Ｃｕ）との相互作用部位と、フェノール性ヒドロキシ基（ＯＨ）とが互いに反対側に配向していることが好ましい。
具体的には、上記で計算した最適化構造をＷｉｎｍｏｓｔａｒにおいて提示した時、銅原子（Ｃｕ）－窒素原子（Ｎ）－酸素原子（Ｏ）－を選択して示す角度が少なくとも一つは１４０°以上であることが好ましい（図２参照）。
例えば、例示化合物（１－１）では、銅原子－窒素原子－酸素原子による角度が１６９°、例示化合物（２－２）では１６８°、例示化合物（３－８）では７１°である。
このように配位することにより、前記複素環化合物の構造中における窒素原子（Ｎ）とフェノール性ヒドロキシ基（ＯＨ）が分子骨格の対角に存在することから、窒素原子（Ｎ）が金属層１０に対して垂直方向に存在し、フェノール性ヒドロキシ基（ＯＨ）が樹脂層２０により近づくことができ、さらに強い相互作用が得られる（図１参照。）。 For the orientation of the heterocyclic compound, for example, quantum chemical calculation software Gaussian16 (manufactured by Gaussian) is used to optimize the structure using B3LYP (density functional theory) in DFT calculation.
SDD (Stuttgart/Dresden ECP) is used as a basis function for copper, and 6-31G(d) is used for other elements. Then, in the Grid scan module of the soft Material Science Suite manufactured by Schrodinger, in the space around the ligand, the position at which the copper ion is restabilized is set as the initial configuration.
The optimum structure calculated above will be explained by taking, for example, the exemplary compound (1-1) as an example. As shown in FIG. 2, the interaction between the compound (exemplary compound (1-1)) and copper (Cu) When a central line A perpendicular to the axial direction is drawn at the center position of the compound with the site as the axial direction, the interaction site with copper (Cu) and the phenolic It is preferred that the hydroxy groups (OH) are oriented in opposite directions to each other.
Specifically, when the optimized structure calculated above is presented in Winmostar, at least one angle shown by selecting a copper atom (Cu)-nitrogen atom (N)-oxygen atom (O)-is 140 ° The above is preferable (see FIG. 2).
For example, the angle formed by the copper atom-nitrogen atom-oxygen atom is 169° in Exemplified Compound (1-1), 168° in Exemplified Compound (2-2), and 71° in Exemplified Compound (3-8).
By coordinating in this way, the nitrogen atom (N) and the phenolic hydroxy group (OH) in the structure of the heterocyclic compound are present on the diagonal of the molecular skeleton, so that the nitrogen atom (N) 10, the phenolic hydroxy group (OH) can be brought closer to theresin layer 20, resulting in a stronger interaction (see FIG. 1).
銅には基底関数として、ＳＤＤ（Ｓｔｕｔｔｇａｒｔ／Ｄｒｅｓｄｅｎ ＥＣＰ）を用いて計算し、その他の元素は６－３１Ｇ（ｄ）を用いる。そして、ｓｃｈｒｏｄｉｎｇｅｒ社製のソフトＭａｔｅｒｉａｌ Ｓｃｉｅｎｃｅ ＳｕｉｔｅのＧｒｉｄ ｓｃａｎモジュールで配位子周りの空間で、銅イオンが再安定になる位置を初期配置とする。
上記で計算した最適構造について、例えば例示化合物（１－１）を例に挙げて説明すると、図２に示すように、化合物（例示化合物（１－１））と銅（Ｃｕ）との相互作用部位を軸方向として、化合物の中心位置に前記軸方向に対して垂直となる中心線Ａを引いた場合に、当該中心線Ａに対して、銅（Ｃｕ）との相互作用部位と、フェノール性ヒドロキシ基（ＯＨ）とが互いに反対側に配向していることが好ましい。
具体的には、上記で計算した最適化構造をＷｉｎｍｏｓｔａｒにおいて提示した時、銅原子（Ｃｕ）－窒素原子（Ｎ）－酸素原子（Ｏ）－を選択して示す角度が少なくとも一つは１４０°以上であることが好ましい（図２参照）。
例えば、例示化合物（１－１）では、銅原子－窒素原子－酸素原子による角度が１６９°、例示化合物（２－２）では１６８°、例示化合物（３－８）では７１°である。
このように配位することにより、前記複素環化合物の構造中における窒素原子（Ｎ）とフェノール性ヒドロキシ基（ＯＨ）が分子骨格の対角に存在することから、窒素原子（Ｎ）が金属層１０に対して垂直方向に存在し、フェノール性ヒドロキシ基（ＯＨ）が樹脂層２０により近づくことができ、さらに強い相互作用が得られる（図１参照。）。 For the orientation of the heterocyclic compound, for example, quantum chemical calculation software Gaussian16 (manufactured by Gaussian) is used to optimize the structure using B3LYP (density functional theory) in DFT calculation.
SDD (Stuttgart/Dresden ECP) is used as a basis function for copper, and 6-31G(d) is used for other elements. Then, in the Grid scan module of the soft Material Science Suite manufactured by Schrodinger, in the space around the ligand, the position at which the copper ion is restabilized is set as the initial configuration.
The optimum structure calculated above will be explained by taking, for example, the exemplary compound (1-1) as an example. As shown in FIG. 2, the interaction between the compound (exemplary compound (1-1)) and copper (Cu) When a central line A perpendicular to the axial direction is drawn at the center position of the compound with the site as the axial direction, the interaction site with copper (Cu) and the phenolic It is preferred that the hydroxy groups (OH) are oriented in opposite directions to each other.
Specifically, when the optimized structure calculated above is presented in Winmostar, at least one angle shown by selecting a copper atom (Cu)-nitrogen atom (N)-oxygen atom (O)-is 140 ° The above is preferable (see FIG. 2).
For example, the angle formed by the copper atom-nitrogen atom-oxygen atom is 169° in Exemplified Compound (1-1), 168° in Exemplified Compound (2-2), and 71° in Exemplified Compound (3-8).
By coordinating in this way, the nitrogen atom (N) and the phenolic hydroxy group (OH) in the structure of the heterocyclic compound are present on the diagonal of the molecular skeleton, so that the nitrogen atom (N) 10, the phenolic hydroxy group (OH) can be brought closer to the
本発明の積層体は、例えば、プリント基板（プリント配線板）又は電子デバイスに適用することができる。
前記プリント基板は、後述するように、フォトリソグラフィによる金属配線パターンの形成方法により形成することができる。
また、前記電子デバイスとしては、例えば、スマートフォン、タブレット端末、パーソナルコンピュータ、サーバ、ルーター、通信基地局、表示デバイス、家電等を挙げることができる。 The laminate of the present invention can be applied to printed circuit boards (printed wiring boards) or electronic devices, for example.
The printed circuit board can be formed by a method of forming a metal wiring pattern by photolithography, as will be described later.
Further, examples of the electronic devices include smartphones, tablet terminals, personal computers, servers, routers, communication base stations, display devices, home appliances, and the like.
前記プリント基板は、後述するように、フォトリソグラフィによる金属配線パターンの形成方法により形成することができる。
また、前記電子デバイスとしては、例えば、スマートフォン、タブレット端末、パーソナルコンピュータ、サーバ、ルーター、通信基地局、表示デバイス、家電等を挙げることができる。 The laminate of the present invention can be applied to printed circuit boards (printed wiring boards) or electronic devices, for example.
The printed circuit board can be formed by a method of forming a metal wiring pattern by photolithography, as will be described later.
Further, examples of the electronic devices include smartphones, tablet terminals, personal computers, servers, routers, communication base stations, display devices, home appliances, and the like.
以下、本発明の積層体の構成について説明する。
本発明の積層体は、金属層上に表面改質層及び樹脂層を順次設けた積層体である。すなわち、金属層と表面改質層が隣接し、表面改質層と樹脂層が隣接している。 The structure of the laminate of the present invention will be described below.
The laminate of the present invention is a laminate obtained by sequentially providing a surface-modified layer and a resin layer on a metal layer. That is, the metal layer and the surface modification layer are adjacent, and the surface modification layer and the resin layer are adjacent.
本発明の積層体は、金属層上に表面改質層及び樹脂層を順次設けた積層体である。すなわち、金属層と表面改質層が隣接し、表面改質層と樹脂層が隣接している。 The structure of the laminate of the present invention will be described below.
The laminate of the present invention is a laminate obtained by sequentially providing a surface-modified layer and a resin layer on a metal layer. That is, the metal layer and the surface modification layer are adjacent, and the surface modification layer and the resin layer are adjacent.
＜金属層＞
金属層は、金属を主成分とする層である。ここで、主成分とは５０質量％以上含有される成分のことをいう。 <Metal layer>
The metal layer is a layer containing metal as a main component. Here, the main component means a component containing 50% by mass or more.
金属層は、金属を主成分とする層である。ここで、主成分とは５０質量％以上含有される成分のことをいう。 <Metal layer>
The metal layer is a layer containing metal as a main component. Here, the main component means a component containing 50% by mass or more.
前記金属層に用いられる金属としては、例えば、金、銀、白金、亜鉛、パラジウム、ロジウム、オスミウム、ルテニウム、イリジウム、銅、ニッケル、コバルト、鉄、スズ、クロム、チタン、タンタル、タングステン、インジウム、アルミニウム、鉛、モリブデンなどの金属、又はこれらの合金を用いることができる。これら中でも、加工性や導電性の観点から、銅又は銅合金を主成分とすることが好ましい。
Examples of metals used for the metal layer include gold, silver, platinum, zinc, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, indium, Metals such as aluminum, lead, molybdenum, or alloys thereof can be used. Among these, from the viewpoint of workability and conductivity, it is preferable to use copper or a copper alloy as a main component.
前記金属層は、金属箔や、めっき、真空成膜法により形成することができる。
The metal layer can be formed by metal foil, plating, or a vacuum film forming method.
金属層の厚さは特に限定されず、例えば、形成する金属配線パターン等の厚さに応じた厚さとすればよい。
The thickness of the metal layer is not particularly limited, and may be set according to the thickness of the metal wiring pattern to be formed, for example.
前記金属配線パターンの形成においては、絶縁層の上に金属層が形成された金属張積層板を用いることから、本発明の積層体は、金属層の下に絶縁層を有することが好ましい。絶縁層は、特に限定されず、一般的に絶縁層として使用される樹脂シートやプリプレグを使用することができる。
Since a metal-clad laminate in which a metal layer is formed on an insulating layer is used in forming the metal wiring pattern, the laminate of the present invention preferably has an insulating layer under the metal layer. The insulating layer is not particularly limited, and a resin sheet or prepreg that is generally used as an insulating layer can be used.
上記のような、絶縁層を有する積層体は、図に示すと、後述するレジスト層形成工程を示す図５における積層体６に該当する。
The laminated body having the insulating layer as described above corresponds to the laminated body 6 in FIG. 5 showing the resist layer forming process described later.
＜表面改質層＞
表面改質層は、前記金属層の表面に、本発明の非感光性表面改質剤を塗布し、乾燥させることで形成することができる。 <Surface modification layer>
The surface-modifying layer can be formed by applying the non-photosensitive surface-modifying agent of the present invention to the surface of the metal layer and drying.
表面改質層は、前記金属層の表面に、本発明の非感光性表面改質剤を塗布し、乾燥させることで形成することができる。 <Surface modification layer>
The surface-modifying layer can be formed by applying the non-photosensitive surface-modifying agent of the present invention to the surface of the metal layer and drying.
表面改質層の厚さは、特に限定されないが、本発明の効果の観点から、０．１～２０ｎｍの範囲内であることが好ましい。
Although the thickness of the surface-modified layer is not particularly limited, it is preferably within the range of 0.1 to 20 nm from the viewpoint of the effects of the present invention.
＜樹脂層＞
本発明で用いられる樹脂層は、特に限定しないが、アクリロニトリル／スチレン共重合樹脂（ＡＳ樹脂）、アクリロニトリル／ブタジエン／スチレン共重合樹脂（ＡＢＳ樹脂）、フッ素樹脂、ポリアミド、ポリエチレン、ポリエチレンテレフタレート、ポリ塩化ビニリデン、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリサルホン、ポリプロピレン、シクロポリオレフィン樹脂、液晶ポリマー等の熱可塑性樹脂や、エポキシ樹脂、フェノール樹脂、ポリイミド、ポリウレタン、ビスマレイミド・トリアジン樹脂、変性ポリフェニレンエーテル、シアネートエステル等の熱硬化性樹脂、あるいは紫外線硬化性エポキシ樹脂、紫外線硬化性アクリル樹脂等の紫外線硬化性樹脂等を挙げることができる。これらの樹脂は官能基によって変性されていてもよく、ガラス繊維、アラミド繊維、その他の繊維等で強化されていてもよい。 <Resin layer>
The resin layer used in the present invention is not particularly limited, but acrylonitrile/styrene copolymer resin (AS resin), acrylonitrile/butadiene/styrene copolymer resin (ABS resin), fluororesin, polyamide, polyethylene, polyethylene terephthalate, polychlorinated Thermoplastic resins such as vinylidene, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide/triazine resin, modified polyphenylene ether, cyanate ester, etc. thermosetting resins, or UV-curable resins such as UV-curable epoxy resins and UV-curable acrylic resins. These resins may be modified with functional groups, and may be reinforced with glass fibers, aramid fibers, other fibers, or the like.
本発明で用いられる樹脂層は、特に限定しないが、アクリロニトリル／スチレン共重合樹脂（ＡＳ樹脂）、アクリロニトリル／ブタジエン／スチレン共重合樹脂（ＡＢＳ樹脂）、フッ素樹脂、ポリアミド、ポリエチレン、ポリエチレンテレフタレート、ポリ塩化ビニリデン、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリサルホン、ポリプロピレン、シクロポリオレフィン樹脂、液晶ポリマー等の熱可塑性樹脂や、エポキシ樹脂、フェノール樹脂、ポリイミド、ポリウレタン、ビスマレイミド・トリアジン樹脂、変性ポリフェニレンエーテル、シアネートエステル等の熱硬化性樹脂、あるいは紫外線硬化性エポキシ樹脂、紫外線硬化性アクリル樹脂等の紫外線硬化性樹脂等を挙げることができる。これらの樹脂は官能基によって変性されていてもよく、ガラス繊維、アラミド繊維、その他の繊維等で強化されていてもよい。 <Resin layer>
The resin layer used in the present invention is not particularly limited, but acrylonitrile/styrene copolymer resin (AS resin), acrylonitrile/butadiene/styrene copolymer resin (ABS resin), fluororesin, polyamide, polyethylene, polyethylene terephthalate, polychlorinated Thermoplastic resins such as vinylidene, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide/triazine resin, modified polyphenylene ether, cyanate ester, etc. thermosetting resins, or UV-curable resins such as UV-curable epoxy resins and UV-curable acrylic resins. These resins may be modified with functional groups, and may be reinforced with glass fibers, aramid fibers, other fibers, or the like.
本発明の積層体が、プリント基板積層時（プリント基板積層体である時）には、樹脂層は市販の樹脂フィルム又はプリプレグ（液状の樹脂を含浸させたシート状の繊維）を用いることができ、フッ素樹脂やシクロポリオレフィン樹脂、液晶ポリマー、エポキシ樹脂、フェノール樹脂、ポリイミド、ビスマレイミド・トリアジン樹脂、変性ポリフェニレンエーテル、シアネートエステルを含む樹脂が好ましく用いられる。
また、本発明の積層体が、プリント基板の配線を形成する場合（金属配線パターンである場合）には、樹脂層は市販の液体レジストやドライフィルムレジストを用いることができ、アルカリ可溶性樹脂を含む紫外線硬化性エポキシ樹脂、紫外線硬化性アクリル樹脂、ポリイミドが好ましく用いられる。 When the laminate of the present invention is a printed circuit board laminate (when it is a printed circuit board laminate), a commercially available resin film or prepreg (a sheet-like fiber impregnated with a liquid resin) can be used as the resin layer. , fluorine resins, cyclopolyolefin resins, liquid crystal polymers, epoxy resins, phenol resins, polyimides, bismaleimide-triazine resins, modified polyphenylene ethers, and cyanate esters.
Further, when the laminate of the present invention forms the wiring of a printed circuit board (when it is a metal wiring pattern), the resin layer can be a commercially available liquid resist or dry film resist, and contains an alkali-soluble resin. UV-curable epoxy resins, UV-curable acrylic resins, and polyimides are preferably used.
また、本発明の積層体が、プリント基板の配線を形成する場合（金属配線パターンである場合）には、樹脂層は市販の液体レジストやドライフィルムレジストを用いることができ、アルカリ可溶性樹脂を含む紫外線硬化性エポキシ樹脂、紫外線硬化性アクリル樹脂、ポリイミドが好ましく用いられる。 When the laminate of the present invention is a printed circuit board laminate (when it is a printed circuit board laminate), a commercially available resin film or prepreg (a sheet-like fiber impregnated with a liquid resin) can be used as the resin layer. , fluorine resins, cyclopolyolefin resins, liquid crystal polymers, epoxy resins, phenol resins, polyimides, bismaleimide-triazine resins, modified polyphenylene ethers, and cyanate esters.
Further, when the laminate of the present invention forms the wiring of a printed circuit board (when it is a metal wiring pattern), the resin layer can be a commercially available liquid resist or dry film resist, and contains an alkali-soluble resin. UV-curable epoxy resins, UV-curable acrylic resins, and polyimides are preferably used.
本発明に係る金属配線パターンの形成方法は、フォトリソグラフィによる金属配線パターンの形成方法であって、本発明の非感光性表面改質剤を用いて、金属層とレジストの間に表面改質層を形成する工程を有することが好ましい。
The method for forming a metal wiring pattern according to the present invention is a method for forming a metal wiring pattern by photolithography, wherein the non-photosensitive surface modifier of the present invention is used to form a surface modified layer between the metal layer and the resist. It is preferable to have a step of forming
＜金属配線パターンの形成方法＞
具体的には、以下の工程（Ａ）～（Ｆ）を有することで金属配線パターンを形成する。
工程（Ａ）：絶縁層の上に金属層が形成された金属張積層板を酸洗浄する工程
工程（Ｂ）：前記金属張積層板の前記金属層の上に、本発明の非感光性表面改質剤を用いて表面改質層を形成する工程
工程（Ｃ）：前記表面改質層の上に、感光性樹脂を含有するレジスト層を形成する工程
工程（Ｄ）：前記レジスト層を、露光及び現像によりパターニングする工程
工程（Ｅ）：前記レジスト層を介して、前記表面改質層及び前記金属層をエッチングする工程
工程（Ｆ）：前記金属張積層板から前記レジスト層を剥離する工程 <Method for Forming Metal Wiring Pattern>
Specifically, a metal wiring pattern is formed by having the following steps (A) to (F).
Step (A): A step of acid cleaning a metal-clad laminate having a metal layer formed on an insulating layer. Step (B): A non-photosensitive surface of the present invention is applied onto the metal layer of the metal-clad laminate. Forming a surface modified layer using a modifier Step (C): Forming a resist layer containing a photosensitive resin on the surface modified layer Step (D): Forming the resist layer, Patterning by exposure and development Step (E): Etching the surface modification layer and the metal layer through the resist layer Step (F): Stripping the resist layer from the metal-clad laminate
具体的には、以下の工程（Ａ）～（Ｆ）を有することで金属配線パターンを形成する。
工程（Ａ）：絶縁層の上に金属層が形成された金属張積層板を酸洗浄する工程
工程（Ｂ）：前記金属張積層板の前記金属層の上に、本発明の非感光性表面改質剤を用いて表面改質層を形成する工程
工程（Ｃ）：前記表面改質層の上に、感光性樹脂を含有するレジスト層を形成する工程
工程（Ｄ）：前記レジスト層を、露光及び現像によりパターニングする工程
工程（Ｅ）：前記レジスト層を介して、前記表面改質層及び前記金属層をエッチングする工程
工程（Ｆ）：前記金属張積層板から前記レジスト層を剥離する工程 <Method for Forming Metal Wiring Pattern>
Specifically, a metal wiring pattern is formed by having the following steps (A) to (F).
Step (A): A step of acid cleaning a metal-clad laminate having a metal layer formed on an insulating layer. Step (B): A non-photosensitive surface of the present invention is applied onto the metal layer of the metal-clad laminate. Forming a surface modified layer using a modifier Step (C): Forming a resist layer containing a photosensitive resin on the surface modified layer Step (D): Forming the resist layer, Patterning by exposure and development Step (E): Etching the surface modification layer and the metal layer through the resist layer Step (F): Stripping the resist layer from the metal-clad laminate
各工程を図３～図８を用いながら説明する。
Each process will be explained using FIGS. 3 to 8.
工程（Ａ）では、絶縁層１の上に金属層２が形成された金属張積層板５（図３参照。）を、酸洗浄する。これによって、非感光性表面改質剤と金属層との相互作用の阻害となる、金属表面に付着している汚れや酸化防止剤、酸化被膜などを除去できる。酸洗浄液は特に限定されず、従来公知のもの用いることができる。また、酸洗浄後に水洗してもよい。
In step (A), the metal-clad laminate 5 (see FIG. 3) in which the metal layer 2 is formed on the insulating layer 1 is washed with an acid. As a result, stains, antioxidants, oxide films, etc. adhering to the metal surface, which hinder interaction between the non-photosensitive surface modifier and the metal layer, can be removed. The acid cleaning liquid is not particularly limited, and conventionally known liquids can be used. Moreover, you may wash with water after acid washing.
絶縁層１は、金属配線パターンの基材となる絶縁性の層である。絶縁層１は、樹脂等の絶縁材からなり、紙やガラスなどの基材に樹脂を含浸させたプリプレグであってもよい。
The insulating layer 1 is an insulating layer that serves as a base material for metal wiring patterns. The insulating layer 1 is made of an insulating material such as resin, and may be a prepreg in which a base material such as paper or glass is impregnated with resin.
金属層２は、上記積層体の金属層と同様である。
The metal layer 2 is the same as the metal layer of the laminate.
工程（Ｂ）では、金属張積層板５の金属層２の上に、本発明の非感光性表面改質剤を用いて表面改質層３を形成する（図４参照。）。具体的には、金属層２の上に非感光性表面改質剤を塗布して、表面改質層３を形成する。表面改質層３の厚さは特に限定されないが、本発明の効果の観点から、０．１～２０ｎｍの範囲内であることが好ましい。
In step (B), the surface-modified layer 3 is formed on the metal layer 2 of the metal-clad laminate 5 using the non-photosensitive surface-modifying agent of the present invention (see FIG. 4). Specifically, a non-photosensitive surface modifier is applied onto the metal layer 2 to form the surface modified layer 3 . Although the thickness of the surface modification layer 3 is not particularly limited, it is preferably within the range of 0.1 to 20 nm from the viewpoint of the effects of the present invention.
工程（Ｂ）と次の工程（Ｃ）の間に、表面改質層３が形成された金属張積層板５を水洗する工程を有することが好ましい。これによって、金属層との相互作用が不十分であり余分な非感光性表面改質剤を除去できる。
Between the step (B) and the next step (C), it is preferable to have a step of washing the metal-clad laminate 5 with the surface-modified layer 3 formed thereon. This allows removal of excess non-photosensitive surface modifiers that interact poorly with the metal layer.
工程（Ｃ）では、表面改質層３の上に、感光性樹脂を含有するレジスト層４を形成する（図５参照。）。この状態の積層体６は、金属層２、表面改質層３及びレジスト層４を備えているため、本発明の積層体に該当する。
In step (C), a resist layer 4 containing a photosensitive resin is formed on the surface modified layer 3 (see FIG. 5). Since the laminate 6 in this state includes the metal layer 2, the surface modification layer 3 and the resist layer 4, it corresponds to the laminate of the present invention.
レジスト層４は、上記積層体のレジスト層と同様に、フォトリソグラフィによるパターニングが可能な感光性樹脂を含有するものであれば特に限定されず、ドライフィルムレジストを貼合したり、液状のレジスト材料を塗布することで形成することができる。
The resist layer 4 is not particularly limited as long as it contains a photosensitive resin that can be patterned by photolithography in the same manner as the resist layer of the laminate. can be formed by applying
工程（Ｄ）では、レジスト層４を、露光及び現像によりパターニングする（図６参照。）。具体的には、レジスト層４を任意のパターン状に露光できるフォトマスクを用いてレジスト層４を露光し、その後、現像液を用いてレジスト層４のうち不要な部分を溶解除去することで、パターニングする。現像後には水洗することが好ましい。
In step (D), the resist layer 4 is patterned by exposure and development (see FIG. 6). Specifically, by exposing the resist layer 4 using a photomask that can expose the resist layer 4 in an arbitrary pattern, and then dissolving and removing unnecessary portions of the resist layer 4 using a developer, Patterning. It is preferable to wash with water after development.
露光条件及び現像条件は、特に限定されず、従来公知のものを適用することができる。
The exposure conditions and development conditions are not particularly limited, and conventionally known conditions can be applied.
工程（Ｅ）では、レジスト層４を介して、表面改質層３及び金属層２をエッチングする（図７参照。）。具体的には、エッチング液を用いたウェットエッチングにより、レジスト層４が除去された部分の表面改質層３及び金属層２を溶解することで、表面改質層３及び金属層２をパターニングする。
In step (E), the surface modification layer 3 and the metal layer 2 are etched through the resist layer 4 (see FIG. 7). Specifically, the surface modification layer 3 and the metal layer 2 are patterned by dissolving the surface modification layer 3 and the metal layer 2 in the portions where the resist layer 4 has been removed by wet etching using an etchant. .
エッチング条件は、特に限定されず、従来公知のものを適用することができる。
The etching conditions are not particularly limited, and conventionally known conditions can be applied.
工程（Ｆ）では、金属張積層板５からレジスト層４を剥離する（図８参照。）。このとき、本発明の効果により、表面改質層３はレジスト層４と剥離しやすくなっているため、表面改質層３は金属張積層板５の金属層２上に残りやすくなっているが、表面改質層３は金属層２上に残っていてもよく、レジスト層４とともに剥離されていてもよい。
In step (F), the resist layer 4 is peeled off from the metal-clad laminate 5 (see FIG. 8). At this time, due to the effect of the present invention, the surface-modified layer 3 is easily separated from the resist layer 4, so the surface-modified layer 3 is likely to remain on the metal layer 2 of the metal-clad laminate 5. , the surface modification layer 3 may remain on the metal layer 2 or may be peeled off together with the resist layer 4 .
レジスト層４の剥離方法は特に限定されないが、剥離液を用いて剥離することが好ましい。当該剥離液は特に限定されず、従来公知のものを適用することができる。
Although the method for removing the resist layer 4 is not particularly limited, it is preferable to remove it using a remover. The stripping liquid is not particularly limited, and conventionally known ones can be applied.
以上の工程により、金属配線パターン７を形成することができる。
Through the above steps, the metal wiring pattern 7 can be formed.
前記金属配線パターンの形成方法では、高密度かつ高精細な金属配線パターンを形成することが可能となるため、当該金属配線パターンに必要に応じた電子部品を取り付けることによって、高密度かつ高精細な本発明のプリント基板（プリント配線板）を製造することが可能となる。
In the method for forming a metal wiring pattern, it is possible to form a high-density and high-definition metal wiring pattern. It becomes possible to manufacture the printed circuit board (printed wiring board) of the present invention.
＜プリント基板積層体の形成方法＞
本発明に係る積層体（プリント基板積層体）の形成方法は、金属層上に樹脂層を形成する方法であって、本発明の非感光性表面改質剤を用いて、金属層と樹脂層の間に表面改質層を形成する工程を有する。
金属層はベタでも配線パターニングされていてもよく、積層方法はホットプレス等公知の方法を用いることができる。
樹脂層としては市販の樹脂フィルム又はプリプレグ（液状の樹脂を含浸させたシート状の繊維）を用いることができ、フッ素樹脂やシクロポリオレフィン樹脂、液晶ポリマー、エポキシ樹脂、フェノール樹脂、ポリイミド、ビスマレイミド・トリアジン樹脂、変性ポリフェニレンエーテル、シアネートエステルを含む樹脂が好ましく用いられ、積層前に樹脂層の貼合面に対してコロナ処理やプラズマ処理等の表面処理を実施してもよい。 <Method for Forming Printed Circuit Board Laminate>
The method for forming a laminate (printed circuit board laminate) according to the present invention is a method for forming a resin layer on a metal layer, wherein the non-photosensitive surface modifier of the present invention is used to form a metal layer and a resin layer. a step of forming a surface modified layer between
The metal layer may be solid or patterned with wiring, and a known method such as hot pressing can be used as the lamination method.
As the resin layer, a commercially available resin film or prepreg (sheet-like fiber impregnated with liquid resin) can be used, and fluorine resin, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, bismaleimide resin, etc. A resin containing a triazine resin, a modified polyphenylene ether, or a cyanate ester is preferably used, and surface treatment such as corona treatment or plasma treatment may be performed on the bonding surface of the resin layer before lamination.
本発明に係る積層体（プリント基板積層体）の形成方法は、金属層上に樹脂層を形成する方法であって、本発明の非感光性表面改質剤を用いて、金属層と樹脂層の間に表面改質層を形成する工程を有する。
金属層はベタでも配線パターニングされていてもよく、積層方法はホットプレス等公知の方法を用いることができる。
樹脂層としては市販の樹脂フィルム又はプリプレグ（液状の樹脂を含浸させたシート状の繊維）を用いることができ、フッ素樹脂やシクロポリオレフィン樹脂、液晶ポリマー、エポキシ樹脂、フェノール樹脂、ポリイミド、ビスマレイミド・トリアジン樹脂、変性ポリフェニレンエーテル、シアネートエステルを含む樹脂が好ましく用いられ、積層前に樹脂層の貼合面に対してコロナ処理やプラズマ処理等の表面処理を実施してもよい。 <Method for Forming Printed Circuit Board Laminate>
The method for forming a laminate (printed circuit board laminate) according to the present invention is a method for forming a resin layer on a metal layer, wherein the non-photosensitive surface modifier of the present invention is used to form a metal layer and a resin layer. a step of forming a surface modified layer between
The metal layer may be solid or patterned with wiring, and a known method such as hot pressing can be used as the lamination method.
As the resin layer, a commercially available resin film or prepreg (sheet-like fiber impregnated with liquid resin) can be used, and fluorine resin, cyclopolyolefin resin, liquid crystal polymer, epoxy resin, phenol resin, polyimide, bismaleimide resin, etc. A resin containing a triazine resin, a modified polyphenylene ether, or a cyanate ester is preferably used, and surface treatment such as corona treatment or plasma treatment may be performed on the bonding surface of the resin layer before lamination.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、下記実施例において、特記しない限り、操作は室温（２５℃）で行われた。また、特記しない限り、「％」及び「部」は、それぞれ、「質量％」及び「質量部」を意味する。
実施例で用いた化合物を下記に示す。
EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. In the following examples, unless otherwise specified, operations were performed at room temperature (25°C). Moreover, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass" respectively.
Compounds used in Examples are shown below.
実施例で用いた化合物を下記に示す。
Compounds used in Examples are shown below.
［実施例１］
下記表Ｉ及び表IIに記載の各化合物について、配向性を評価した。
具体的には、量子化学計算ソフトＧａｕｓｓｉａｎ１６（Ｇａｕｓｓｉａｎ社製）を用いて、ＤＦＴ計算でＢ３ＬＹＰ（密度汎関数法）を用いて構造最適化を行った。銅には基底関数として、ＳＤＤ（Ｓｔｕｔｔｇａｒｔ／Ｄｒｅｓｄｅｎ ＥＣＰ）を用いて計算し、その他の元素は６－３１Ｇ（ｄ）を用いた。
ｓｃｈｒｏｄｉｎｇｅｒ社製のソフトＭａｔｅｒｉａｌ Ｓｃｉｅｎｃｅ ＳｕｉｔｅのＧｒｉｄ ｓｃａｎモジュールで配位子周りの空間で、銅イオンが再安定になる位置を初期配置とした。上記で計算した最適構造をＷｉｎｍｏｓｔａｒにおいて提示した時、銅原子（Ｃｕ）－窒素原子（Ｎ）－酸素原子（Ｏ）を選択して示す角度を下記の基準にしたがって配向性を評価した。
（基準）
ＡＡ：銅原子－窒素原子－酸素原子の角度：１４０°以上
Ａ：銅原子－窒素原子－酸素原子の角度が０°以上１４０°未満
Ｂ：化合物の構造内にフェノール性ヒドロキシ基がない。 [Example 1]
The orientation of each compound shown in Tables I and II below was evaluated.
Specifically, quantum chemical calculation software Gaussian16 (manufactured by Gaussian) was used to perform structure optimization using B3LYP (density functional theory) in DFT calculation. As a basis function for copper, SDD (Stuttgart/Dresden ECP) was used for calculation, and 6-31G(d) was used for other elements.
In the Grid scan module of the soft Material Science Suite manufactured by Schrodinger, the position where the copper ion is restabilized in the space around the ligand was set as the initial configuration. When the optimum structure calculated above was presented in Winmostar, the orientation was evaluated according to the following criteria for the angles shown by selecting the copper atom (Cu)-nitrogen atom (N)-oxygen atom (O).
(standard)
AA: The angle of copper atom-nitrogen atom-oxygen atom: 140° or more A: The angle of copper atom-nitrogen atom-oxygen atom is 0° or more and less than 140° B: There is no phenolic hydroxy group in the structure of the compound.
下記表Ｉ及び表IIに記載の各化合物について、配向性を評価した。
具体的には、量子化学計算ソフトＧａｕｓｓｉａｎ１６（Ｇａｕｓｓｉａｎ社製）を用いて、ＤＦＴ計算でＢ３ＬＹＰ（密度汎関数法）を用いて構造最適化を行った。銅には基底関数として、ＳＤＤ（Ｓｔｕｔｔｇａｒｔ／Ｄｒｅｓｄｅｎ ＥＣＰ）を用いて計算し、その他の元素は６－３１Ｇ（ｄ）を用いた。
ｓｃｈｒｏｄｉｎｇｅｒ社製のソフトＭａｔｅｒｉａｌ Ｓｃｉｅｎｃｅ ＳｕｉｔｅのＧｒｉｄ ｓｃａｎモジュールで配位子周りの空間で、銅イオンが再安定になる位置を初期配置とした。上記で計算した最適構造をＷｉｎｍｏｓｔａｒにおいて提示した時、銅原子（Ｃｕ）－窒素原子（Ｎ）－酸素原子（Ｏ）を選択して示す角度を下記の基準にしたがって配向性を評価した。
（基準）
ＡＡ：銅原子－窒素原子－酸素原子の角度：１４０°以上
Ａ：銅原子－窒素原子－酸素原子の角度が０°以上１４０°未満
Ｂ：化合物の構造内にフェノール性ヒドロキシ基がない。 [Example 1]
The orientation of each compound shown in Tables I and II below was evaluated.
Specifically, quantum chemical calculation software Gaussian16 (manufactured by Gaussian) was used to perform structure optimization using B3LYP (density functional theory) in DFT calculation. As a basis function for copper, SDD (Stuttgart/Dresden ECP) was used for calculation, and 6-31G(d) was used for other elements.
In the Grid scan module of the soft Material Science Suite manufactured by Schrodinger, the position where the copper ion is restabilized in the space around the ligand was set as the initial configuration. When the optimum structure calculated above was presented in Winmostar, the orientation was evaluated according to the following criteria for the angles shown by selecting the copper atom (Cu)-nitrogen atom (N)-oxygen atom (O).
(standard)
AA: The angle of copper atom-nitrogen atom-oxygen atom: 140° or more A: The angle of copper atom-nitrogen atom-oxygen atom is 0° or more and less than 140° B: There is no phenolic hydroxy group in the structure of the compound.
［実施例２］
＜非感光性表面改質剤の調製＞
エタノール２０質量％及びイオン交換水８０質量％からなる溶媒に、下記表Ｉの各化合物を２０質量ｐｐｍとなるように添加し、非感光性表面改質剤１～８及び１２～１５をそれぞれ調製した。また、非感光性表面改質剤１０及び１１については、エタノール及びイオン交換水の比率を下記表Ｉとなるように変更し、非感光性表面改質剤９は、化合物（１－１）の濃度を下記表Ｉとなるように変更した以外は同様にして調製した。 [Example 2]
<Preparation of non-photosensitive surface modifier>
Each compound in Table I below was added to a solvent consisting of 20% by mass of ethanol and 80% by mass of ion-exchanged water so as to be 20 ppm by mass, andnon-photosensitive surface modifiers 1 to 8 and 12 to 15 were prepared, respectively. bottom. Further, for non-photosensitive surface modifiers 10 and 11, the ratio of ethanol and ion-exchanged water was changed as shown in Table I below. It was prepared in the same manner except that the concentration was changed as shown in Table I below.
＜非感光性表面改質剤の調製＞
エタノール２０質量％及びイオン交換水８０質量％からなる溶媒に、下記表Ｉの各化合物を２０質量ｐｐｍとなるように添加し、非感光性表面改質剤１～８及び１２～１５をそれぞれ調製した。また、非感光性表面改質剤１０及び１１については、エタノール及びイオン交換水の比率を下記表Ｉとなるように変更し、非感光性表面改質剤９は、化合物（１－１）の濃度を下記表Ｉとなるように変更した以外は同様にして調製した。 [Example 2]
<Preparation of non-photosensitive surface modifier>
Each compound in Table I below was added to a solvent consisting of 20% by mass of ethanol and 80% by mass of ion-exchanged water so as to be 20 ppm by mass, and
＜金属配線パターン（積層体）１の形成＞
下記工程（Ａ）～（Ｆ）を行い、金属配線パターン１を形成した。
（工程（Ａ））
絶縁層の上に金属層が形成された銅張積層板（パナソニック社製 メグトロン７ Ｒ－５７８５）を、酸洗浄液（サンワ化学工業社製ＣＰ－３０）とスプレー型の洗浄装置を用いて酸洗浄し、次いで水洗した。 <Formation of Metal Wiring Pattern (Laminate) 1>
Ametal wiring pattern 1 was formed by performing the following steps (A) to (F).
(Step (A))
A copper clad laminate (Megtron 7 R-5785 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device. and then washed with water.
下記工程（Ａ）～（Ｆ）を行い、金属配線パターン１を形成した。
（工程（Ａ））
絶縁層の上に金属層が形成された銅張積層板（パナソニック社製 メグトロン７ Ｒ－５７８５）を、酸洗浄液（サンワ化学工業社製ＣＰ－３０）とスプレー型の洗浄装置を用いて酸洗浄し、次いで水洗した。 <Formation of Metal Wiring Pattern (Laminate) 1>
A
(Step (A))
A copper clad laminate (Megtron 7 R-5785 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device. and then washed with water.
（工程（Ｂ））
酸洗浄及び水洗をした銅張積層板の金属層の上に、上記調製した非感光性表面改質剤１を、スプレー方式の塗布装置を用いて塗布し、その後、水洗を行った。水洗後、ＰＶＡローラーにて水切りし、８０℃のエアナイフにて乾燥させて、厚さ５ｎｍの表面改質層を形成した。 (Step (B))
Thenon-photosensitive surface modifier 1 prepared above was applied onto the metal layer of the copper-clad laminate that had been acid-washed and water-washed using a spray-type applicator, and was then washed with water. After washing with water, water was removed with a PVA roller and dried with an air knife at 80° C. to form a surface modified layer with a thickness of 5 nm.
酸洗浄及び水洗をした銅張積層板の金属層の上に、上記調製した非感光性表面改質剤１を、スプレー方式の塗布装置を用いて塗布し、その後、水洗を行った。水洗後、ＰＶＡローラーにて水切りし、８０℃のエアナイフにて乾燥させて、厚さ５ｎｍの表面改質層を形成した。 (Step (B))
The
（工程（Ｃ））
表面改質層の上に、樹脂層としてドライフィルムレジスト（旭化成社製 ＡＫ－４０３４）（アルカリ可溶性樹脂含む光硬化性のアクリル樹脂）を、ホットロールラミネーターにより、ロール温度１０５℃、エアー圧力０．３５ＭＰａ、及びラミネート速度１．５ｍ／ｍｉｎの条件でラミネートして、レジスト層を形成した。なお、使用したドライフィルムレジスト（旭化成社製ＡＫ－４０３４）は、一方の面にポリエチレンテレフタレートフィルムからなる支持体を有し、もう一方の面にポリエチレンフィルムからなる保護層を有するものである。ラミネートは、保護層を剥離しながら、保護層があった面を表面改質層を介して金属層と接着させるようにして行った。 (Step (C))
A dry film resist (AK-4034 manufactured by Asahi Kasei Co., Ltd.) (a photocurable acrylic resin containing an alkali-soluble resin) was applied as a resin layer on the surface-modified layer by a hot roll laminator at a roll temperature of 105° C. and an air pressure of 0.5°C. A resist layer was formed by lamination under conditions of 35 MPa and a lamination speed of 1.5 m/min. The dry film resist used (AK-4034 manufactured by Asahi Kasei Co., Ltd.) has a support made of a polyethylene terephthalate film on one side and a protective layer made of a polyethylene film on the other side. Lamination was carried out by allowing the surface on which the protective layer was present to adhere to the metal layer via the surface-modified layer while peeling off the protective layer.
表面改質層の上に、樹脂層としてドライフィルムレジスト（旭化成社製 ＡＫ－４０３４）（アルカリ可溶性樹脂含む光硬化性のアクリル樹脂）を、ホットロールラミネーターにより、ロール温度１０５℃、エアー圧力０．３５ＭＰａ、及びラミネート速度１．５ｍ／ｍｉｎの条件でラミネートして、レジスト層を形成した。なお、使用したドライフィルムレジスト（旭化成社製ＡＫ－４０３４）は、一方の面にポリエチレンテレフタレートフィルムからなる支持体を有し、もう一方の面にポリエチレンフィルムからなる保護層を有するものである。ラミネートは、保護層を剥離しながら、保護層があった面を表面改質層を介して金属層と接着させるようにして行った。 (Step (C))
A dry film resist (AK-4034 manufactured by Asahi Kasei Co., Ltd.) (a photocurable acrylic resin containing an alkali-soluble resin) was applied as a resin layer on the surface-modified layer by a hot roll laminator at a roll temperature of 105° C. and an air pressure of 0.5°C. A resist layer was formed by lamination under conditions of 35 MPa and a lamination speed of 1.5 m/min. The dry film resist used (AK-4034 manufactured by Asahi Kasei Co., Ltd.) has a support made of a polyethylene terephthalate film on one side and a protective layer made of a polyethylene film on the other side. Lamination was carried out by allowing the surface on which the protective layer was present to adhere to the metal layer via the surface-modified layer while peeling off the protective layer.
（工程（Ｄ））
クロムガラスマスクを用いて、平行光露光機（オーク社製ＨＭＷ－８０１）により、レジスト層に露光した。露光条件には、ドライフィルムレジストの推奨条件である、６０ｍｊ／ｃｍ２を採用した。
露光後のレジスト層から支持体を剥離した。その後、炭酸ナトリウム（Ｎａ２ＣＯ３）１質量％の水溶液からなる現像液、及びアルカリ現像機を用いて、３０℃の条件で、レジスト層の未露光部分を溶解除去し、次いで水洗して、現像した。
以上の操作により、レジスト層をパターニングした。 (Step (D))
Using a chromium glass mask, the resist layer was exposed by a parallel light exposure machine (HMW-801 manufactured by ORC Co., Ltd.). As the exposure condition, 60 mj/cm 2 , which is the recommended condition for dry film resist, was adopted.
The support was peeled off from the resist layer after exposure. After that, the unexposed portions of the resist layer are dissolved and removed at 30°C using a developer consisting of an aqueous solution of 1% by mass of sodium carbonate (Na 2 CO 3 ) and an alkaline developer, and then washed with water. Developed.
The resist layer was patterned by the above operation.
クロムガラスマスクを用いて、平行光露光機（オーク社製ＨＭＷ－８０１）により、レジスト層に露光した。露光条件には、ドライフィルムレジストの推奨条件である、６０ｍｊ／ｃｍ２を採用した。
露光後のレジスト層から支持体を剥離した。その後、炭酸ナトリウム（Ｎａ２ＣＯ３）１質量％の水溶液からなる現像液、及びアルカリ現像機を用いて、３０℃の条件で、レジスト層の未露光部分を溶解除去し、次いで水洗して、現像した。
以上の操作により、レジスト層をパターニングした。 (Step (D))
Using a chromium glass mask, the resist layer was exposed by a parallel light exposure machine (HMW-801 manufactured by ORC Co., Ltd.). As the exposure condition, 60 mj/cm 2 , which is the recommended condition for dry film resist, was adopted.
The support was peeled off from the resist layer after exposure. After that, the unexposed portions of the resist layer are dissolved and removed at 30°C using a developer consisting of an aqueous solution of 1% by mass of sodium carbonate (Na 2 CO 3 ) and an alkaline developer, and then washed with water. Developed.
The resist layer was patterned by the above operation.
（工程（Ｅ））
ディップ方式にて、塩酸（ＨＣｌ）２質量％及び塩化第二鉄（ＦｅＣｌ３）２質量％の水溶液からなるエッチング液を用いて、温度３０℃、ディップ時間（１分）の条件で、表面改質層及び金属層をエッチングした。 (Step (E))
In a dip method, using an etchant consisting of an aqueous solution of 2% by mass of hydrochloric acid (HCl) and 2% by mass of ferric chloride (FeCl 3 ), the surface was reformed under the conditions of a temperature of 30 ° C. and a dipping time of 1 minute. The quality layer and the metal layer were etched.
ディップ方式にて、塩酸（ＨＣｌ）２質量％及び塩化第二鉄（ＦｅＣｌ３）２質量％の水溶液からなるエッチング液を用いて、温度３０℃、ディップ時間（１分）の条件で、表面改質層及び金属層をエッチングした。 (Step (E))
In a dip method, using an etchant consisting of an aqueous solution of 2% by mass of hydrochloric acid (HCl) and 2% by mass of ferric chloride (FeCl 3 ), the surface was reformed under the conditions of a temperature of 30 ° C. and a dipping time of 1 minute. The quality layer and the metal layer were etched.
（工程（Ｆ））
水酸化ナトリウム（ＮａＯＨ）３質量％の水溶液からなる剥離液を用いて、温度５０℃の条件で、銅張積層板からレジスト層を剥離した。 (Step (F))
The resist layer was stripped from the copper-clad laminate at a temperature of 50° C. using a stripping solution consisting of an aqueous solution of 3% by mass of sodium hydroxide (NaOH).
水酸化ナトリウム（ＮａＯＨ）３質量％の水溶液からなる剥離液を用いて、温度５０℃の条件で、銅張積層板からレジスト層を剥離した。 (Step (F))
The resist layer was stripped from the copper-clad laminate at a temperature of 50° C. using a stripping solution consisting of an aqueous solution of 3% by mass of sodium hydroxide (NaOH).
＜金属配線パターン２～１５の形成＞
前記金属配線パターン１の形成において、非感光性表面改質剤１を下記表Ｉに示す各非感光性表面改質剤２～１５にそれぞれ変更した以外は同様にして、金属配線パターン２～１５を形成した。 <Formation ofmetal wiring patterns 2 to 15>
In the formation of themetal wiring pattern 1, metal wiring patterns 2 to 15 were formed in the same manner except that the non-photosensitive surface modifier 1 was changed to each of the non-photosensitive surface modifiers 2 to 15 shown in Table I below. formed.
前記金属配線パターン１の形成において、非感光性表面改質剤１を下記表Ｉに示す各非感光性表面改質剤２～１５にそれぞれ変更した以外は同様にして、金属配線パターン２～１５を形成した。 <Formation of
In the formation of the
［評価］
＜レジスト接着性＞
上記で形成した各金属配線パターンを、顕微鏡にて観察を行い、下記の基準でレジスト接着性（細線形成性）を評価した。評価した結果は下記表Ｉに示すとおりである。下記基準の「ＡＡＡ」、「ＡＡ」及び「Ａ」を実用上問題ないとした。
（基準）
ＡＡＡ：金属配線の残存率が９９％以上である。
ＡＡ：金属配線の残存率が９７％以上９９％未満である。
Ａ：金属配線の残存率が９５％以上９７％未満である。
Ｂ：金属配線の残存率が９５％未満である。 [evaluation]
<Resist Adhesion>
Each metal wiring pattern formed above was observed with a microscope, and resist adhesion (thin line formability) was evaluated according to the following criteria. The evaluation results are shown in Table I below. "AAA", "AA" and "A" in the following criteria were regarded as practically acceptable.
(standard)
AAA: The residual rate of metal wiring is 99% or more.
AA: The residual rate of metal wiring is 97% or more and less than 99%.
A: The residual rate of metal wiring is 95% or more and less than 97%.
B: The residual rate of metal wiring is less than 95%.
＜レジスト接着性＞
上記で形成した各金属配線パターンを、顕微鏡にて観察を行い、下記の基準でレジスト接着性（細線形成性）を評価した。評価した結果は下記表Ｉに示すとおりである。下記基準の「ＡＡＡ」、「ＡＡ」及び「Ａ」を実用上問題ないとした。
（基準）
ＡＡＡ：金属配線の残存率が９９％以上である。
ＡＡ：金属配線の残存率が９７％以上９９％未満である。
Ａ：金属配線の残存率が９５％以上９７％未満である。
Ｂ：金属配線の残存率が９５％未満である。 [evaluation]
<Resist Adhesion>
Each metal wiring pattern formed above was observed with a microscope, and resist adhesion (thin line formability) was evaluated according to the following criteria. The evaluation results are shown in Table I below. "AAA", "AA" and "A" in the following criteria were regarded as practically acceptable.
(standard)
AAA: The residual rate of metal wiring is 99% or more.
AA: The residual rate of metal wiring is 97% or more and less than 99%.
A: The residual rate of metal wiring is 95% or more and less than 97%.
B: The residual rate of metal wiring is less than 95%.
［実施例３］
＜非感光性表面改質剤の調製＞
実施例２と同様の、非感光性表面改質剤１～１５を調製した。 [Example 3]
<Preparation of non-photosensitive surface modifier>
Non-photosensitive surface modifiers 1-15 similar to Example 2 were prepared.
＜非感光性表面改質剤の調製＞
実施例２と同様の、非感光性表面改質剤１～１５を調製した。 [Example 3]
<Preparation of non-photosensitive surface modifier>
Non-photosensitive surface modifiers 1-15 similar to Example 2 were prepared.
＜プリント基板積層体（積層体）１の形成＞
下記工程（Ｉ）～（III）を行い、プリント基板積層体１を形成した。
（工程（Ｉ））
絶縁層の上に金属層が形成された銅張積層板（パナソニック社製 Ｒ－１７６６）を、酸洗浄液（サンワ化学工業社製ＣＰ－３０）とスプレー型の洗浄装置を用いて酸洗浄し、次いで水洗した。 <Formation of printed circuit board laminate (laminate) 1>
A printedcircuit board laminate 1 was formed by carrying out the following steps (I) to (III).
(Step (I))
A copper clad laminate (R-1766 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device, It was then washed with water.
下記工程（Ｉ）～（III）を行い、プリント基板積層体１を形成した。
（工程（Ｉ））
絶縁層の上に金属層が形成された銅張積層板（パナソニック社製 Ｒ－１７６６）を、酸洗浄液（サンワ化学工業社製ＣＰ－３０）とスプレー型の洗浄装置を用いて酸洗浄し、次いで水洗した。 <Formation of printed circuit board laminate (laminate) 1>
A printed
(Step (I))
A copper clad laminate (R-1766 manufactured by Panasonic Corporation) in which a metal layer is formed on an insulating layer is acid-cleaned using an acid cleaning solution (CP-30 manufactured by Sanwa Chemical Industry Co., Ltd.) and a spray-type cleaning device, It was then washed with water.
（工程（II））
酸洗浄及び水洗をした銅張積層板の金属層の上に、上記調製した非感光性表面改質剤１を、スプレー方式の塗布装置を用いて塗布し、その後、水洗を行った。水洗後、ＰＶＡローラーにて水切りし、８０℃のエアナイフにて乾燥させて、厚さ５ｎｍの表面改質剤層を形成した。 (Step (II))
Thenon-photosensitive surface modifier 1 prepared above was applied onto the metal layer of the copper-clad laminate that had been acid-washed and water-washed using a spray-type applicator, and was then washed with water. After washing with water, water was removed with a PVA roller and dried with an air knife at 80° C. to form a surface modifier layer with a thickness of 5 nm.
酸洗浄及び水洗をした銅張積層板の金属層の上に、上記調製した非感光性表面改質剤１を、スプレー方式の塗布装置を用いて塗布し、その後、水洗を行った。水洗後、ＰＶＡローラーにて水切りし、８０℃のエアナイフにて乾燥させて、厚さ５ｎｍの表面改質剤層を形成した。 (Step (II))
The
（工程（III））
表面改質剤層の上に、プリプレグ（パナソニック社製 Ｒ－１６６１）（エポキシ系樹脂）を合わさるように積層し、３．０ＭＰａの圧力で常温（２５℃）から１０℃／ｍｉｎの昇温速度で１２０℃まで加熱し３０分ホールドしたのと、１０℃／ｍｉｎの昇温速度で１９０℃まで加熱し２時間保持することにより積層接着し、プリント基板積層体１を作製した。 (Step (III))
A prepreg (Panasonic R-1661) (epoxy resin) is laminated on the surface modifier layer, and the temperature is increased from room temperature (25 ° C.) to 10 ° C./min at a pressure of 3.0 MPa. was heated to 120° C. and held for 30 minutes, and heated to 190° C. at a rate of temperature increase of 10° C./min and held for 2 hours for lamination and adhesion, thereby fabricating a printedcircuit board laminate 1 .
表面改質剤層の上に、プリプレグ（パナソニック社製 Ｒ－１６６１）（エポキシ系樹脂）を合わさるように積層し、３．０ＭＰａの圧力で常温（２５℃）から１０℃／ｍｉｎの昇温速度で１２０℃まで加熱し３０分ホールドしたのと、１０℃／ｍｉｎの昇温速度で１９０℃まで加熱し２時間保持することにより積層接着し、プリント基板積層体１を作製した。 (Step (III))
A prepreg (Panasonic R-1661) (epoxy resin) is laminated on the surface modifier layer, and the temperature is increased from room temperature (25 ° C.) to 10 ° C./min at a pressure of 3.0 MPa. was heated to 120° C. and held for 30 minutes, and heated to 190° C. at a rate of temperature increase of 10° C./min and held for 2 hours for lamination and adhesion, thereby fabricating a printed
＜プリント基板積層体２～１５の作製＞
前記プリント基板積層体１の作製において、非感光性表面改質剤１を下記表IIに示す各非感光性表面改質剤２～１５にそれぞれ変更した以外は同様にして、プリント基板積層体２～１５を作製した。 <Production of printedcircuit board laminates 2 to 15>
In the production of the printedcircuit board laminate 1, printed circuit board laminate 2 ~15 were made.
前記プリント基板積層体１の作製において、非感光性表面改質剤１を下記表IIに示す各非感光性表面改質剤２～１５にそれぞれ変更した以外は同様にして、プリント基板積層体２～１５を作製した。 <Production of printed
In the production of the printed
［評価］
＜プリプレグ接着性の評価＞
上記で作製した各プリント基板積層体を、１０ｍｍ幅の短冊に切り出し、テンシロン（株式会社オリエンテック社製）を使用し、９０度剥離で剥離強度を測定し、下記の基準にしたがいプリプレグ接着性を評価した。評価した結果は下記表IIに示すとおりである。
下記基準の「ＡＡ」及び「Ａ」を実用上問題ないとした。
（基準）
ＡＡ：接着強度 ０．６５ｋＮ／ｍ以上
Ａ：接着強度 ０．５ｋＮ／ｍ以上０．６５ｋＮ／ｍ未満
Ｂ：接着強度 ０．５ｋＮ／ｍ未満 [evaluation]
<Evaluation of prepreg adhesion>
Each printed circuit board laminate prepared above was cut into strips with a width of 10 mm, and using Tensilon (manufactured by Orientec Co., Ltd.), the peel strength was measured by peeling at 90 degrees, and the prepreg adhesiveness was measured according to the following criteria. evaluated. The evaluation results are shown in Table II below.
"AA" and "A" in the following criteria were regarded as practically acceptable.
(standard)
AA: Adhesive strength 0.65 kN/m or more A: Adhesive strength 0.5 kN/m or more and less than 0.65 kN/m B: Adhesive strength less than 0.5 kN/m
＜プリプレグ接着性の評価＞
上記で作製した各プリント基板積層体を、１０ｍｍ幅の短冊に切り出し、テンシロン（株式会社オリエンテック社製）を使用し、９０度剥離で剥離強度を測定し、下記の基準にしたがいプリプレグ接着性を評価した。評価した結果は下記表IIに示すとおりである。
下記基準の「ＡＡ」及び「Ａ」を実用上問題ないとした。
（基準）
ＡＡ：接着強度 ０．６５ｋＮ／ｍ以上
Ａ：接着強度 ０．５ｋＮ／ｍ以上０．６５ｋＮ／ｍ未満
Ｂ：接着強度 ０．５ｋＮ／ｍ未満 [evaluation]
<Evaluation of prepreg adhesion>
Each printed circuit board laminate prepared above was cut into strips with a width of 10 mm, and using Tensilon (manufactured by Orientec Co., Ltd.), the peel strength was measured by peeling at 90 degrees, and the prepreg adhesiveness was measured according to the following criteria. evaluated. The evaluation results are shown in Table II below.
"AA" and "A" in the following criteria were regarded as practically acceptable.
(standard)
AA: Adhesive strength 0.65 kN/m or more A: Adhesive strength 0.5 kN/m or more and less than 0.65 kN/m B: Adhesive strength less than 0.5 kN/m
上記結果に示されるように、本発明の非感光性表面改質剤に含有される複素環化合物は、その構造中における窒素原子とフェノール性ヒドロキシ基が分子骨格の対角に存在し、分子骨格が垂直方向に配位していることが分かる。
そして、このような配向性の複素環化合物を含有した本発明の非感光性表面改質剤を用いることにより、比較例の表面改質剤を用いる場合に比べて、レジスト接着性及びプリプレグ接着性に優れることが認められる。 As shown in the above results, the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention has a nitrogen atom and a phenolic hydroxy group in its structure that are diagonally opposite to each other. It can be seen that is coordinated in the vertical direction.
By using the non-photosensitive surface modifier of the present invention containing such an oriented heterocyclic compound, the resist adhesion and prepreg adhesion are improved as compared with the case of using the surface modifier of the comparative example. It is recognized that it is superior to
そして、このような配向性の複素環化合物を含有した本発明の非感光性表面改質剤を用いることにより、比較例の表面改質剤を用いる場合に比べて、レジスト接着性及びプリプレグ接着性に優れることが認められる。 As shown in the above results, the heterocyclic compound contained in the non-photosensitive surface modifier of the present invention has a nitrogen atom and a phenolic hydroxy group in its structure that are diagonally opposite to each other. It can be seen that is coordinated in the vertical direction.
By using the non-photosensitive surface modifier of the present invention containing such an oriented heterocyclic compound, the resist adhesion and prepreg adhesion are improved as compared with the case of using the surface modifier of the comparative example. It is recognized that it is superior to
本発明は、金属層と樹脂層との間の密着性をより向上させることができる非感光性表面改質剤、積層体、プリント基板及び電子デバイスに利用することができる。
The present invention can be used for non-photosensitive surface modifiers, laminates, printed circuit boards, and electronic devices that can further improve the adhesion between a metal layer and a resin layer.
１ 絶縁層
２ 金属層
３ 表面改質層
４ レジスト層
５ 金属張積層板
６ 積層体
７ 金属配線パターン
１０ 金属層
２０ 樹脂層
３０ 表面改質層
Ａ 中心線 1 InsulatingLayer 2 Metal Layer 3 Surface Modified Layer 4 Resist Layer 5 Metal-clad Laminate 6 Laminate 7 Metal Wiring Pattern 10 Metal Layer 20 Resin Layer 30 Surface Modified Layer A Center Line
２ 金属層
３ 表面改質層
４ レジスト層
５ 金属張積層板
６ 積層体
７ 金属配線パターン
１０ 金属層
２０ 樹脂層
３０ 表面改質層
Ａ 中心線 1 Insulating
Claims (11)
- 金属層と樹脂層の間に表面改質層を形成する非感光性表面改質剤であって、
少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する非感光性表面改質剤。
Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基、ヘテロアリール基又はハロゲン原子を表す。
ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合は、それぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。］ A non-photosensitive surface modifier that forms a surface modification layer between the metal layer and the resin layer,
A non-photosensitive surface modifier containing at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
Each of n and m is an integer of 0 to 5, and n+m=an integer of 0 to 5 (however, an integer of 0 to 4 for general formula (1)). When having multiple substituents R 2 , each substituent R 2 may be the same or different. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may ] - 前記複素環化合物が、前記一般式（１）で表される構造を有する請求項１に記載の非感光性表面改質剤。 The non-photosensitive surface modifier according to claim 1, wherein the heterocyclic compound has a structure represented by the general formula (1).
- 前記複素環化合物が、下記一般式（５）で表される構造を有する複素環化合物である請求項２に記載の非感光性表面改質剤。
- 少なくとも水又はアルコール類を含有する請求項１から請求項３までのいずれか一項に記載の非感光性表面改質剤。 The non-photosensitive surface modifier according to any one of claims 1 to 3, which contains at least water or alcohols.
- 金属層上に表面改質層及び樹脂層を順次設けた積層体であって、
前記表面改質層が、少なくとも下記一般式（１）、（２）、（３）又は（４）で表される構造を有する複素環化合物を一種以上含有する積層体。
Ｒ２は、水素原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、カルボキシ基、エステル基、アミド基、ヘテロアリール基又はハロゲン原子を表す。
ｎ及びｍは、それぞれ０～５の整数で、ｎ＋ｍ＝０～５の整数（ただし、一般式（１）に関しては、０～４の整数）を表す。複数の置換基Ｒ２を有する場合は、各置換基Ｒ２は相互に同一であっても異なっていてもよい。また、複数のｎを有する場合は、それぞれのｎは相互に同一であっても異なっていてもよく、さらに、複数のｍを有する場合は、それぞれのｍは相互に同一であっても異なっていてもよい。］ A laminate in which a surface-modified layer and a resin layer are sequentially provided on a metal layer,
A laminate in which the surface-modified layer contains at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an ester group, an amide group, a heteroaryl group or a halogen atom.
Each of n and m is an integer of 0 to 5, and n+m=an integer of 0 to 5 (however, an integer of 0 to 4 for general formula (1)). When having multiple substituents R 2 , each substituent R 2 may be the same or different. In addition, when there are multiple n's, each n may be the same or different, and when there are multiple m's, each m may be the same or different. may ] - 前記複素環化合物が、前記一般式（１）で表される構造を有する複素環化合物である請求項５に記載の積層体。 The laminate according to claim 5, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1).
- 前記複素環化合物が、下記一般式（５）で表される構造を有する複素環化合物である請求項６に記載の積層体。
- 前記樹脂層が、アルカリ可溶性樹脂を含有する感光性樹脂組成物である請求項５から請求項７までのいずれか一項に記載の積層体。 The laminate according to any one of claims 5 to 7, wherein the resin layer is a photosensitive resin composition containing an alkali-soluble resin.
- 前記樹脂層が、少なくともエポキシ構造を有する樹脂を含有する熱硬化性樹脂組成物である請求項５から請求項７までのいずれか一項に記載の積層体。 The laminate according to any one of claims 5 to 7, wherein the resin layer is a thermosetting resin composition containing at least a resin having an epoxy structure.
- 請求項５から請求項９までのいずれか一項に記載の積層体を用いたプリント基板。 A printed circuit board using the laminate according to any one of claims 5 to 9.
- 請求項５から請求項９までのいずれか一項に記載の積層体を用いた電子デバイス。 An electronic device using the laminate according to any one of claims 5 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-183868 | 2021-11-11 | ||
| JP2021183868 | 2021-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023085246A1 true WO2023085246A1 (en) | 2023-05-19 |
Family
ID=86336023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/041485 WO2023085246A1 (en) | 2021-11-11 | 2022-11-08 | Nonphotosensitive surface modifying agent, laminate, printed circuit board, and electronic device |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TWI822452B (en) |
| WO (1) | WO2023085246A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04314895A (en) * | 1991-04-15 | 1992-11-06 | Nikko Kyodo Co Ltd | Liquid and method for surface treatment |
| JPH05281722A (en) * | 1992-03-31 | 1993-10-29 | Dainippon Toryo Co Ltd | Negative photosensitive electrodepositin coating resin composition, electrodeposition coating bath using the same and production of resist pattern |
| JPH0853427A (en) * | 1994-07-27 | 1996-02-27 | Ciba Geigy Ag | Trisaryl-s-triazine shifted to red side and composition stabilized therewith |
| JP2011515542A (en) * | 2008-03-21 | 2011-05-19 | エントン インコーポレイテッド | Promoting metal adhesion to laminates using a multifunctional molecular system |
| JP2017125226A (en) * | 2016-01-12 | 2017-07-20 | ナガセケムテックス株式会社 | Primer composition for electroless plating, primer component for electroless plating, and plated article |
| JP2018044241A (en) * | 2016-09-13 | 2018-03-22 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Block coating for selective metal coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112015000524B1 (en) * | 2012-07-09 | 2021-03-30 | Shikoku Chemicals Corporation | METHOD FOR FORMING A COPPER FILM AND METHOD FOR MANUFACTURING A WIRING PLATE |
-
2022
- 2022-11-08 WO PCT/JP2022/041485 patent/WO2023085246A1/en active Application Filing
- 2022-11-09 TW TW111142807A patent/TWI822452B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04314895A (en) * | 1991-04-15 | 1992-11-06 | Nikko Kyodo Co Ltd | Liquid and method for surface treatment |
| JPH05281722A (en) * | 1992-03-31 | 1993-10-29 | Dainippon Toryo Co Ltd | Negative photosensitive electrodepositin coating resin composition, electrodeposition coating bath using the same and production of resist pattern |
| JPH0853427A (en) * | 1994-07-27 | 1996-02-27 | Ciba Geigy Ag | Trisaryl-s-triazine shifted to red side and composition stabilized therewith |
| JP2011515542A (en) * | 2008-03-21 | 2011-05-19 | エントン インコーポレイテッド | Promoting metal adhesion to laminates using a multifunctional molecular system |
| JP2017125226A (en) * | 2016-01-12 | 2017-07-20 | ナガセケムテックス株式会社 | Primer composition for electroless plating, primer component for electroless plating, and plated article |
| JP2018044241A (en) * | 2016-09-13 | 2018-03-22 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Block coating for selective metal coating |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202335538A (en) | 2023-09-01 |
| TWI822452B (en) | 2023-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI503383B (en) | Composition for forming plating layer and method for producing laminate having metal film | |
| CN101351086B (en) | Inside imbedded type line structural technique | |
| TWI772364B (en) | Method for forming circuits using seed layer and etchant composition for selective etching of seed layer | |
| JP2002026475A (en) | Copper foil circuit with carrier foil, method of manufacturing printed wiring board, using the same, and printed wiring board | |
| US8465656B2 (en) | Method for manufacturing a printed circuit board and a printed circuit board obtained by the manufacturing method | |
| WO2023085246A1 (en) | Nonphotosensitive surface modifying agent, laminate, printed circuit board, and electronic device | |
| US8663484B2 (en) | Method for manufacturing a printed circuit board and a printed circuit board obtained by the manufacturing method | |
| WO2023199849A1 (en) | Non-photosensitive surface modifier, layered product, printed wiring board, and electronic device | |
| JP5010554B2 (en) | Method for forming conductive pattern | |
| KR20240055049A (en) | Non-photosensitive surface modifiers, laminates, printed boards and electronic devices | |
| CN105188267A (en) | Method for mirroring production of FPC (Flexible Printed Circuit) single panel | |
| TW201832627A (en) | Conductive film manufacturing method and conductive film | |
| JP2011166028A (en) | Method of manufacturing cof substrate | |
| TW202411365A (en) | Non-photosensitive surface modifiers, laminates, printed circuit boards and electronic devices | |
| TWI815535B (en) | Surface modifier, laminate, metal circuit pattern forming method, and printed circuit board manufacturing method | |
| CN102223764A (en) | Manufacturing method of flexible circuit boards | |
| WO2012133297A1 (en) | Laminate having metal film, manufacturing method therefor, laminate having patterned metal film, and manufacturing method therefor | |
| JP2007523255A (en) | Etched polycarbonate film | |
| JP2019159151A (en) | Method for forming wiring pattern, and printed circuit board, semiconductor package and electronic apparatus using the method | |
| JP3660733B2 (en) | Photosensitive film material for circuit board insulation, flexible printed wiring board using the same, and sequential multilayer board | |
| JP2009295872A (en) | Method for manufacturing printed circuit board, and printed circuit board | |
| JP2012207258A (en) | Composition for forming layered to be plated, and method for producing laminate having metal film | |
| TW200911057A (en) | Method for manufacturing electrical traces of printed circuit board | |
| KR20090076176A (en) | Flexible printed circuits board using nano-electron inc and manufacturing method the same | |
| KR101215604B1 (en) | Method for isolating of FPCB has been applied to etching techniques of PCB |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22892745 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2023559629 Country of ref document: JP |