CN118202008A - Non-photosensitive surface modifier, laminate, printed circuit board, and electronic device - Google Patents
Non-photosensitive surface modifier, laminate, printed circuit board, and electronic device Download PDFInfo
- Publication number
- CN118202008A CN118202008A CN202280073097.1A CN202280073097A CN118202008A CN 118202008 A CN118202008 A CN 118202008A CN 202280073097 A CN202280073097 A CN 202280073097A CN 118202008 A CN118202008 A CN 118202008A
- Authority
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- China
- Prior art keywords
- layer
- group
- resin
- general formula
- heterocyclic compound
- Prior art date
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- Pending
Links
- 239000003607 modifier Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 116
- 239000002184 metal Substances 0.000 claims abstract description 116
- 229920005989 resin Polymers 0.000 claims abstract description 85
- 239000011347 resin Substances 0.000 claims abstract description 85
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 54
- 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 abstract description 16
- 230000004048 modification Effects 0.000 abstract description 16
- 239000010410 layer Substances 0.000 description 212
- 238000000034 method Methods 0.000 description 30
- 238000005406 washing Methods 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 230000003993 interaction Effects 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 nitrogen-containing compound Chemical class 0.000 description 5
- 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
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004643 cyanate ester Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000835 fiber Substances 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
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- 238000003775 Density Functional Theory Methods 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 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
- 238000005457 optimization Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000005554 pickling Methods 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 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
- 150000001298 alcohols Chemical class 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
- 238000013459 approach Methods 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
- 239000002585 base Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 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
- 150000002739 metals Chemical class 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
- 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
- 229920000573 polyethylene 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
- 239000005033 polyvinylidene 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
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 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
- 238000011105 stabilization Methods 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
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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- 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
- B32B2363/00—Epoxy resins
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier in which a surface modification layer is formed between a metal layer and a resin layer, and at least one heterocyclic compound having a structure represented by general formula (1), (2), (3) or (4) is contained. [ R 1 ] represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent. R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group, a heteroaryl group, or a halogen atom. n and m each represent an integer of 0 to 5, and n+m=an integer of 0 to 5 (wherein, in the general formula (1), the integer is 0 to 4).
Description
Technical Field
The present invention relates to a non-photosensitive surface modifier, a laminate, a printed circuit board, and an electronic device, and more particularly, to a non-photosensitive surface modifier or the like capable of further improving adhesion between a metal layer and a resin layer.
Background
In recent years, with the progress of data society, a printed wiring board (also referred to as "printed circuit board") having high density and high definition is demanded.
In the process of manufacturing a printed wiring board, a resin material such as a resist, a plating resist, a solder resist, a presoaking agent, or the like is bonded to the surface of a metal layer or a metal wiring. In the manufacturing process of the printed wiring board and the manufactured product, high adhesion is required between the metal layer and the resin layer.
Therefore, in order to improve the adhesion between the metal layer and the resin layer, the following methods are known: a method of forming an adhesion-improving film on the surface of a metal layer, the method being to improve adhesion to a resin layer (for example, refer to patent document 1); a method of improving adhesion by containing a sulfur-containing compound and a nitrogen-containing compound in a photosensitive resin (for example, refer to patent document 2).
However, in 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 been obtained yet. In particular, in recent years, high-density mounting technology of 5G and semiconductor packages for mobile communication has been advanced, and demands for low roughening of a metal layer and miniaturization of metal wiring of a printed wiring board have been increased, and accordingly, adhesion between the metal layer and a resin layer has been required to be higher than ever.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-203073
Patent document 2: japanese patent laid-open No. 2020-34933
Disclosure of Invention
The present invention has been made in view of the above-described problems and circumstances, and an object of the present invention is to provide a non-photosensitive surface modifier capable of further improving adhesion between a metal layer and a resin layer, and a laminate, a printed wiring board, and an electronic device using the non-photosensitive surface modifier.
The present inventors have studied for solving the above problems and have found that, in the course of a study for the reasons of the above problems, the adhesion between a metal layer and a resin layer can be further improved by containing a heterocyclic compound having a specific structure as a non-photosensitive surface modifier for forming a surface modification layer between the metal layer and the resin layer, and have completed the present invention.
That is, the above-described problems of the present invention are solved by the following method.
A non-photosensitive surface modifier is a non-photosensitive surface modifier in which a surface modifying layer is formed between a metal layer and a resin layer,
At least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4).
[ Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent.
R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group, a heteroaryl group, or a halogen atom.
N and m each represent an integer of 0 to 5, and n+m=an integer of 0 to 5 (wherein, in the general formula (1), an integer of 0 to 4). In the case of having a plurality of substituents R 2, the substituents R 2 may be the same or different from each other. In the case of a plurality of n, n may be the same or different from each other, and in the case of a plurality of m, m may be the same or different from each other. ]
2. The non-photosensitive surface modifier according to item 1, wherein the heterocyclic compound has a structure represented by the general formula (1).
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).
General formula (5)
[ Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent. ]
4. The non-photosensitive surface modifier according to any one of items 1 to 3, wherein the non-photosensitive surface modifier contains at least water or an alcohol.
5. A laminate comprising a surface-modified layer and a resin layer sequentially provided on a metal layer,
The surface-modified layer contains at least one or more heterocyclic compounds having a structure represented by the following general formula (1), (2), (3) or (4).
[ Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent.
R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group, a heteroaryl group, or a halogen atom.
N and m each represent an integer of 0 to 5, and n+m=an integer of 0 to 5 (wherein, in the general formula (1), an integer of 0 to 4). In the case of having a plurality of substituents R 2, the substituents R 2 may be the same or different from each other. In the case of a plurality of n, n may be the same or different from each other, and in the case of a plurality of m, m may be the same or different from each other. ]
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. The laminate according to item 6, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (5).
General formula (5)
[ Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent. ]
8. The laminate according to any one of claim 5 to 7, wherein the resin layer is a photosensitive resin composition containing an alkali-soluble resin.
9. The laminate according to any one of claim 5 to 7, wherein the resin layer is a thermosetting resin composition containing at least a resin having an epoxy structure.
10. A printed wiring board using the laminate according to any one of items 5 to 9.
11. An electronic device using the laminate according to any one of items 5 to 9.
According to the method of the present invention, a non-photosensitive surface modifier capable of further improving adhesion between a metal layer and a resin layer, and a laminate, a printed wiring board, and an electronic device using the non-photosensitive surface modifier can be provided.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
The non-photosensitive surface modifier of the present invention contains at least one or more heterocyclic compounds having a structure represented by the above general formula (1), (2), (3) or (4), and therefore, a nitrogen atom (N atom) present in the structure of the heterocyclic compound interacts with a metal, and a phenolic hydroxyl group interacts with a resin. Therefore, the surface-modified layer formed of such a non-photosensitive surface-modifying agent is present between the metal layer and the resin layer, and the adhesion between the metal layer and the resin layer is improved by the surface-modified layer having the above-mentioned interaction.
The phenolic hydroxyl group can be hydrogen-bonded to a polar group present in the resin or covalently bonded to a polymerizable resin represented by an epoxy group, and can be bonded under an interaction force stronger than pi-pi interaction or van der Waals force.
In particular, it is presumed that, since the nitrogen atom and the phenolic hydroxyl group in the structure of the above-mentioned heterocyclic compound exist in the diagonal direction of the molecular skeleton, as shown in fig. 1, the molecular skeleton of the above-mentioned heterocyclic compound (for example, the example compound (1-1) of fig. 1) coordinates in the vertical direction (the thickness direction of the surface modification layer 30), the nitrogen atom (N) interacts with the metal of the metal layer 10, the phenolic hydroxyl group (OH) can approach the resin layer 20, and a stronger interaction can be obtained.
The atoms shown in fig. 1 represent the same atoms as in fig. 2.
Drawings
FIG. 1 is a schematic view showing the coordination state of a nitrogen atom and a phenolic hydroxyl group present in the structure of a heterocyclic compound of the present invention
FIG. 2 is a view for explaining the orientation of the heterocyclic compound of the present invention
FIG. 3 is a view showing a step of forming a metal wiring pattern (metal-clad laminate)
FIG. 4 is a view showing a step of forming a metal wiring pattern (formation of a surface-modified layer)
FIG. 5 is a view showing a step of forming a metal wiring pattern (formation of a resist layer)
FIG. 6 is a diagram showing a step of forming a metal wiring pattern (patterning of a resist layer)
FIG. 7 is a view showing a step of forming a metal wiring pattern (etching of a surface-modified layer and a metal layer)
FIG. 8 is a view showing a step of forming a metal wiring pattern (resist layer separation)
Detailed Description
The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier in which a surface modification layer is formed between a metal layer and a resin layer, and at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4) is contained.
This feature is common to or corresponds to each of the following embodiments.
In an embodiment of the present invention, the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (1), and in particular, the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (5) from the viewpoint of improving adhesion between a metal layer and a resin layer.
In addition, from the viewpoint of solubility, it is preferable to contain at least water or alcohol.
The laminate of the present invention is a laminate comprising a metal layer and a surface-modifying layer and a resin layer sequentially provided on the metal layer,
The surface-modified layer contains at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4). This can provide a laminate with improved adhesion between the metal layer and the resin layer.
The resin layer is preferably a photosensitive resin composition containing an alkali-soluble resin or a thermosetting resin composition containing at least a resin having an epoxy structure, from the viewpoint of improving adhesion due to interaction with a phenolic hydroxyl group contained in the heterocyclic compound.
In addition, the laminate of the present invention can be applied to a printed circuit board or an electronic device.
The present application and its constituent elements, and modes for carrying out the present application will be described below. In the present application, the numerical range described with reference to "means that the numerical values described before and after" are included as the lower limit value and the upper limit value.
[ Non-photosensitive surface modifier ]
The non-photosensitive surface modifier of the present invention is a non-photosensitive surface modifier in which a surface modification layer is formed between a metal layer and a resin layer, and at least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4) is contained.
In the above general formula (1), R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, particularly preferably represents an aryl group, and may have a substituent.
Examples of the substituent include a hydroxyl group and an amide group.
In the general formulae (1) to (4), R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group, a halogen atom or a heteroaryl group, and particularly preferably represents an alkyl group.
In the general formulae (1) to (4), n and m each represent an integer of 0 to 5, and n+m=an integer of 0 to 5 (wherein, in the general formula (1), the integer of 0 to 4).
In the general formulae, when a plurality of substituents R 2 are present, the substituents R 2 may be the same or different from each other. In the case of a plurality of n, n may be the same or different from each other, and in the case of a plurality of m, m may be the same or different from each other.
In view of improving adhesion between the metal layer and the resin layer by interaction between the metal layer and the surface-modified layer and between the surface-modified layer and the resin layer, the heterocyclic compound of the present invention is preferably a heterocyclic compound having a structure represented by the general formula (1) among the heterocyclic compounds having structures represented by the general formulae (1) to (4).
In addition, from the viewpoint of improving adhesion between the metal layer and the resin layer, the heterocyclic compound of the present invention is preferably a heterocyclic compound having a structure represented by the following general formula (5).
General formula (5)
In the above general formula (5), R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, particularly preferably represents an aryl group, and may have a substituent.
Examples of the substituent include a hydroxyl group and an amide group.
The following examples of the heterocyclic compounds having the structures represented by the general formulae (1) to (5) are given, but the heterocyclic compounds of the present invention are not limited thereto.
The heterocyclic compound contained in the non-photosensitive surface modifier of the present invention may be one or two or more.
From the viewpoint of solubility, the non-photosensitive surface modifier of the present invention preferably contains at least water or an alcohol as a solvent. Examples of the alcohol include methanol, ethanol, and 2-propanol. Two or more kinds of water or alcohols may be used in the solvent at the same time.
Specifically, the mass ratio (mass%) of water to alcohol is preferably set to 100:0 to 50:50, more preferably 100:0 to 75: 25.
From the viewpoint of film formability, the aromatic heterocyclic compound is preferably contained in the range of 0.00001 (0.1 ppm) to 0.1 (1000 ppm) by mass, particularly preferably in the range of 0.00001 (0.1 ppm) to 0.01 (100 ppm) by mass, relative to the entire non-photosensitive surface modifier.
The non-photosensitive surface modifier of the present invention may contain other components than the above, but may be composed of a non-polymerizable material without containing a polymer, a polymerizable monomer or an oligomer, that is, without containing a resin.
Examples of the other components include surfactants, preservatives, stabilizers, acids, bases, and pH adjusters.
[ Laminate ]
The laminate of the present invention is a laminate comprising a metal layer and a surface-modified layer and a resin layer sequentially provided on the metal layer, wherein the surface-modified layer contains at least one heterocyclic compound having a structure represented by the general formula (1), (2), (3) or (4).
The heterocyclic compounds having the structures represented by the general formulae (1) to (4) are described above, and therefore, the description thereof is omitted.
In addition, from the viewpoint of improving adhesion between the metal layer and the resin layer by interaction between the metal layer and the surface-modified layer and between the surface-modified layer and the resin layer, among the heterocyclic compounds having structures represented by the general formulae (1) to (4), the heterocyclic compound of the present invention is preferably one having a structure represented by the general formula (1).
In particular, from the viewpoint of improving adhesion between the metal layer and the resin layer, the heterocyclic compound is preferably a heterocyclic compound having a structure represented by the general formula (5).
In the laminate of the present invention, the heterocyclic ring of the heterocyclic compound is preferably oriented in a direction substantially perpendicular to the metal layer, and the phenolic hydroxyl group of the heterocyclic compound is preferably oriented in a direction substantially perpendicular to the resin layer, from the viewpoint that the phenolic hydroxyl group can be brought closer to the resin layer and stronger interaction can be obtained, and adhesion can be improved.
Regarding the orientation of the heterocyclic compound, for example, a quantum chemical calculation software Gaussian16 (manufactured by Gaussian), and a structure optimization using B3LYP (Density-generalized function) in DFT calculation are used.
For copper, the calculation was performed using SDD (Stuttgart/DRESDEN ECP) as the basis function, and the other elements were 6-31G (d). Then, a Grid scan module of software MATERIAL SCIENCE Suite, manufactured by schrodinger, was used to set the position where copper ions were re-stabilized in the space around the ligand as the initial configuration.
Regarding the optimal structure obtained by the above calculation, for example, the example compound (1-1) is described as an example, and as shown in fig. 2, it is preferable that the interaction site between the compound (example compound (1-1)) and copper (Cu) is taken as an axial direction, and when a center line a perpendicular to the axial direction is drawn at the center position of the compound, the interaction site with copper (Cu) and the phenolic hydroxyl group (OH) are oriented on opposite sides with respect to the center line a.
Specifically, when the optimal structure calculated in Winmostar is presented, at least one angle represented by copper atom (Cu) -nitrogen atom (N) -oxygen atom (O) -is preferably 140 ° or more (see fig. 2).
For example, the angle of copper atom-nitrogen atom-oxygen atom was 169 ° in example compound (1-1), 168 ° in example compound (2-2), and 71 ° in example compound (3-8).
By such coordination, the nitrogen atom (N) and the phenolic hydroxyl group (OH) in the structure of the heterocyclic compound exist at the opposite angles of the molecular skeleton, and therefore the nitrogen atom (N) exists in the direction perpendicular to the metal layer 10, and the phenolic hydroxyl group (OH) can be brought closer to the resin layer 20, thereby obtaining stronger interaction (refer to fig. 1).
The laminate of the present invention can be applied to, for example, a printed circuit board (printed wiring board) or an electronic device.
The printed circuit board may be formed by a method of forming a metal wiring pattern by photolithography, as will be described later.
Examples of the electronic device include a smart phone, a tablet terminal, a personal computer, a server, a router, a communication base station, a display device, and a home appliance.
The structure of the laminate of the present invention will be described below.
The laminate of the present invention is a laminate comprising a metal layer and a surface-modified layer and a resin layer laminated in this order. That is, the metal layer is adjacent to the surface modification layer, and the surface modification layer is adjacent to the resin layer.
< Metal layer >)
The metal layer is a layer containing a metal as a main component. The main component herein means a component containing 50 mass% or more.
Examples of the metal used for the metal layer include metals such as gold, silver, platinum, zinc, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, indium, aluminum, lead, and molybdenum, and alloys thereof. Among these, copper or a copper alloy is preferable as a main component from the viewpoint of workability and conductivity.
The metal layer may be formed by a metal foil, plating, or vacuum film forming method.
The thickness of the metal layer is not particularly limited as long as it is, for example, a thickness corresponding to the thickness of the metal wiring pattern or the like to be formed.
In the formation of the metal wiring pattern, a metal-clad laminate having a metal layer formed on an insulating layer is used, and therefore, 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 which is generally used as an insulating layer can be used.
The laminate having the insulating layer described above corresponds to the laminate 6 in fig. 5 showing a resist layer forming process described later, as shown in the figure.
< Surface modification layer >)
The surface-modified layer can be formed by coating the surface of the metal layer with the non-photosensitive surface modifier of the present invention and drying the same.
The thickness of the surface-modified layer is not particularly limited, but is preferably in the range of 0.1 to 20nm from the viewpoint of the effect of the present invention.
< Resin layer >)
The resin layer used in the present invention is not particularly limited, and examples thereof include thermoplastic resins such AS acrylonitrile/styrene copolymer resin (AS resin), acrylonitrile/butadiene/styrene copolymer resin (ABS resin), fluorine resin, polyamide, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, cyclic polyolefin resin, liquid crystal polymer, thermosetting resins such AS epoxy resin, phenolic resin, polyimide, polyurethane, bismaleimide-triazine resin, modified polyphenylene ether, cyanate ester, and the like, or ultraviolet curable resins such AS ultraviolet curable epoxy resin, ultraviolet curable acrylic resin, and the like. These resins may be modified with functional groups or reinforced with glass fibers, aramid fibers, other fibers, and the like.
In the laminate of the present invention, when a printed wiring board is laminated (when a printed wiring board laminate is used), a commercially available resin film or prepreg (sheet-like fiber containing a liquid resin) can be used as the resin layer, and a fluororesin, a cyclic polyolefin resin, a liquid crystal polymer, an epoxy resin, a phenol resin, a polyimide, a bismaleimide-triazine resin, a modified polyphenylene ether, or a resin containing a cyanate ester is preferably used.
In the case of forming wiring of a printed wiring board (in the case of forming a metal wiring pattern), a commercially available liquid resist or dry film resist may be used as the resin layer, and an ultraviolet curable epoxy resin, an ultraviolet curable acrylic resin, or a polyimide containing an alkali-soluble resin is 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, and preferably includes a step of forming a surface-modified layer between a metal layer and a resist using the non-photosensitive surface modifier according to the present invention.
Method for forming metal wiring pattern
Specifically, the metal wiring pattern is formed by the following steps (a) to (F). Step (A): acid washing the metal-clad laminate having the metal layer formed on the insulating layer
Step (B): a step of forming a surface-modified layer on the metal layer of the metal-clad laminate using the non-photosensitive surface modifier of the present invention
Step (C): a step (D) of forming a resist layer containing a photosensitive resin on the surface-modified layer: patterning the resist layer by exposure and development
Step (E): etching the surface-modified layer and the metal layer through the resist layer
Step (F): a step of peeling the resist layer from the metal-clad laminate
Each step will be described with reference to fig. 3 to 8.
In step (a), the metal-clad laminate 5 (see fig. 3) having the metal layer 2 formed on the insulating layer 1 is pickled. This can remove dirt, antioxidants, oxide films, and the like adhering to the metal surface, which inhibit interaction between the non-photosensitive surface modifier and the metal layer. The pickling solution is not particularly limited, and conventionally known pickling solutions can be used. In addition, water washing may be performed after the acid washing.
The insulating layer 1 is an insulating layer as a base material of the metal wiring pattern. The insulating layer 1 may be a prepreg made of an insulating material such as resin and impregnated with a resin into a base material such as paper or glass.
The metal layer 2 is the same as the metal layer of the laminate.
In the 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 coated on the metal layer 2 to form a surface modified layer 3. The thickness of the surface-modified layer 3 is not particularly limited, but is preferably in the range of 0.1 to 20nm from the viewpoint of the effect of the present invention.
The metal-clad laminate 5 on which the surface-modified layer 3 is formed is preferably washed with water between the step (B) and the subsequent step (C). This results in insufficient interaction with the metal layer, and can remove the excess non-photosensitive surface modifier.
In step (C), a resist layer 4 containing a photosensitive resin is formed on the surface-modified layer 3 (see fig. 5). The laminate 6 in this state includes the metal layer 2, the surface modification layer 3, and the resist layer 4, and 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, similar to the resist layer of the laminate, and may be formed by bonding a dry film resist or applying a liquid resist material.
In step (D), the resist layer 4 is patterned by exposure and development (see fig. 6). Specifically, the resist layer 4 is exposed using a photomask capable of exposing the resist layer 4 in an arbitrary pattern, and then unnecessary portions of the resist layer 4 are dissolved and removed using a developer, thereby patterning. Preferably, the development is followed by water washing.
The exposure conditions and development conditions are not particularly limited, and conventionally known conditions can be used.
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 modified layer 3 and the metal layer 2, from which the resist layer 4 is removed, are dissolved by wet etching using an etching liquid, whereby the surface modified layer 3 and the metal layer 2 are patterned.
The etching conditions are not particularly limited, and conventionally known conditions can be used.
In step (F), the resist layer 4 is peeled off from the metal-clad laminate 5 (see fig. 8). At this time, the surface modification layer 3 is easily peeled off from the resist layer 4 due to the effect of the present invention, and therefore the surface modification layer 3 is easily left on the metal layer 2 of the metal-clad laminate 5, but the surface modification layer 3 may be left on the metal layer 2 or may be peeled off together with the resist layer 4.
The method for stripping the resist layer 4 is not particularly limited, and stripping is preferably performed using a stripping liquid. The stripping liquid is not particularly limited, and conventionally known stripping liquids can be used.
Through the above steps, the metal wiring pattern 7 can be formed.
In the method for forming a metal wiring pattern, a metal wiring pattern having a high density and a high definition can be formed, and therefore, a printed wiring board (printed wiring board) of the present invention having a high density and a high definition can be manufactured by mounting electronic components as needed on the metal wiring pattern.
Method for forming printed circuit board laminate
The method for forming a laminate (printed wiring board laminate) of the present invention is a method for forming a resin layer on a metal layer, and includes a step of forming a surface-modified layer between the metal layer and the resin layer using the non-photosensitive surface-modifying agent of the present invention.
The metal layer may be entirely or patterned, and a known method such as hot pressing may be used as a lamination method.
As the resin layer, a commercially available resin film or prepreg (sheet-like fiber obtained by impregnating a liquid resin) may be used, and a resin layer containing a fluororesin, a cyclic polyolefin resin, a liquid crystal polymer, an epoxy resin, a phenolic resin, a polyimide, a bismaleimide-triazine resin, a modified polyphenylene ether, or a resin containing a cyanate ester may be preferably used, and the bonding surface of the resin layer may be subjected to a surface treatment such as corona treatment or plasma treatment before lamination.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, the operation was performed at room temperature (25 ℃ C.) unless otherwise specified. Unless otherwise indicated, "%" and "parts" mean "% by mass" and "parts by mass", respectively.
The compounds used in the examples are shown below.
Example 1
The orientation of each of the compounds described in tables I and II below was evaluated.
Specifically, using quantum chemical computing software Gaussian16 (manufactured by Gaussian), B3LYP (Density-generalized function) was used for structural optimization in DFT calculation. For copper, the calculation was performed using SDD (Stuttgart/DRESDEN ECP) as the basis function, and the other elements were 6-31G (d).
The position of the copper ion re-stabilization in the space around the ligand was set as the initial configuration using the Grid scan module of software MATERIAL SCIENCE Suite by Schrodinger corporation. When Winmostar indicates the above calculated optimum structure, the orientation of the angle represented by the copper atom (Cu) -nitrogen atom (N) -oxygen atom (O) was selected according to the following standard evaluation.
(Reference)
AA: angle of copper atom-nitrogen atom-oxygen atom: 140 DEG or more
A: the angle of copper atom-nitrogen atom-oxygen atom is 0 DEG or more and less than 140 DEG
B: the compound has no phenolic hydroxyl group in the structure.
Example 2
Preparation of non-photosensitive surface modifier
To a solvent composed of 20 mass% of ethanol and 80 mass% of ion-exchanged water, the following compounds in table I were added so as to be 20 mass ppm, to prepare non-photosensitive surface modifiers 1 to 8 and 12 to 15, respectively. The non-photosensitive surface modifiers 10 and 11 were prepared in the same manner as in table I below except that the ratio of ethanol to ion-exchanged water was changed to table I below and the concentration of the compound (1-1) was changed to table I below.
< Formation of Metal Wiring Pattern (laminate) 1 >
The following steps (a) to (F) are performed to form the metal wiring pattern 1.
(Process (A))
A copper-clad laminate (Megtron R-5785 manufactured by Panasonic Co., ltd.) having a metal layer formed on an insulating layer was acid-washed with an acid washing solution (CP-30 manufactured by Sanwa chemical Co., ltd.) and a spray washing apparatus, followed by water washing.
(Process (B))
The non-photosensitive surface modifier 1 prepared as described above was coated on the metal layer of the copper-clad laminate after acid washing and water washing using a coating apparatus of a spray system, and then water washed. After washing with water, the water was drained off with a PVA roll, and dried with an air knife at 80℃to form a surface-modified layer having a thickness of 5 nm.
(Process (C))
A dry film resist (AK-4034, manufactured by Asahi Kabushiki Kaisha) was laminated as a resin layer on the surface-modified layer by a hot roll laminator at a roll temperature of 105℃under an air pressure of 0.35MPa and a lamination speed of 1.5m/min to form a resist layer. The dry film resist (AK-4034 manufactured by asahi chemical industry Co., ltd.) used had a support made of polyethylene terephthalate film on one surface and a protective layer made of polyethylene film on the other surface. Lamination is performed by bonding the surface having the protective layer to the metal layer via the surface modification layer while peeling the protective layer.
(Process (D)
The resist layer was exposed to light by a parallel light exposure machine (HMW-801 manufactured by OAK Co.) using a chrome glass mask. The exposure conditions used were recommended conditions for dry film resist, namely 60mj/cm 2.
The support is peeled off from the exposed resist layer. Then, the unexposed portion of the resist layer was removed by dissolution at 30℃using a developer made of an aqueous solution of 1% by mass sodium carbonate (Na 2CO3) and an alkaline developer, followed by washing with water and development.
The resist layer is patterned by the above operation.
(Process (E))
The surface-modified layer and the metal layer were etched by dipping using an etchant composed of an aqueous solution of 2 mass% hydrochloric acid (HCl) and 2 mass% ferric chloride (FeCl 3) at a temperature of 30 ℃ for a dipping time (1 minute).
(Process (F))
The resist was peeled from the copper-clad laminate at a temperature of 50℃using a peeling liquid composed of a3 mass% aqueous solution of sodium hydroxide (NaOH).
< Formation of Metal Wiring patterns 2-15 >
In the formation of the metal wiring pattern 1, metal wiring patterns 2 to 15 were similarly formed 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.
[ Evaluation ]
Resist adhesion >
Each of the metal wiring patterns formed as described above was observed with a microscope, and the resist adhesiveness (thin line formation) was evaluated according to the following criteria. The results of the evaluation are shown in Table I below. The references "AAA", "AA" and "A" below are practically no problems.
(Reference)
AAA: the residual ratio of the metal wiring is more than 99%.
AA: the metal wiring has a residual ratio of 97% or more and less than 99%.
A: the residual ratio of the metal wiring is 95% or more and less than 97%.
B: the residual ratio of the metal wiring is less than 95%.
TABLE I
Example 3
Preparation of non-photosensitive surface modifier
Non-photosensitive surface modifiers 1 to 15 were prepared in the same manner as in example 2.
< Formation of printed Circuit Board laminate (laminate) 1 >
The following steps (I) to (III) were performed to form the printed wiring board laminate 1.
(Process (I))
A copper-clad laminate (R-1766 manufactured by Panasonic Co., ltd.) having a metal layer formed on an insulating layer was acid-washed with an acid washing solution (CP-30 manufactured by Sanwa chemical Co., ltd.) and a spray washing apparatus, followed by water washing.
(Process (II))
The non-photosensitive surface modifier 1 prepared as described above was coated on the metal layer of the copper-clad laminate after acid washing and water washing using a coating apparatus of a spray system, and then water washed. After washing with water, the water was drained off with a PVA roll, and dried with an air knife at 80℃to form a surface modifier layer having a thickness of 5 nm.
(Process (III))
A prepreg (R-1661) (epoxy resin, manufactured by Panasonic corporation) was laminated and adhered to the surface modifier layer, and the laminate was heated from room temperature (25 ℃) to 120 ℃ at a temperature rise rate of 10 ℃/min at a pressure of 3.0MPa for 30 minutes, and heated to 190 ℃ at a temperature rise rate of 10 ℃/min for 2 hours, whereby lamination adhesion was performed, to produce a printed wiring board laminate 1.
< Production of printed Circuit Board laminate 2-15 >)
Printed circuit board laminates 2 to 15 were produced in the same manner as in the production of the printed circuit board laminate 1 described above, except that the non-photosensitive surface modifier 1 was changed to each of the non-photosensitive surface modifiers 2 to 15 shown in table II below.
[ Evaluation ]
< Evaluation of prepreg adhesion >
Each of the printed wiring board laminates prepared above was cut into a 10mm wide strip shape, and the peel strength was measured at 90 degrees using a Tensilon (Orientech company), and the prepreg adhesiveness was evaluated according to the following criteria. The results of the evaluation are shown in Table II below.
The references "AA" and "a" described below are practically no problem.
(Reference)
AA: the bonding strength is more than 0.65kN/m
A: the bonding strength is more than 0.5kN/m and less than 0.65kN/m
B: the bonding strength is less than 0.5kN/m
TABLE I
As is clear from the above results, in the heterocyclic compound containing the non-photosensitive surface modifier of the present invention, the nitrogen atom and the phenolic hydroxyl group in the structure are present at the opposite corners of the molecular skeleton, and the molecular skeleton coordinates in the vertical direction.
Further, by using the non-photosensitive surface modifier of the present invention containing the heterocyclic compound having such an orientation, it was confirmed that the resist adhesion and the prepreg adhesion were excellent, as compared with the case of using the surface modifier of the comparative example.
Industrial applicability
The present invention can be used for a non-photosensitive surface modifier, a laminate, a printed wiring board, and an electronic device, which can further improve adhesion between a metal layer and a resin layer.
Symbol description
1. Insulating layer
2. Metal layer
3. Surface modification layer
4. Resist layer
5. Metal-clad laminate
6. Laminate body
7. Metal wiring pattern
10. Metal layer
20. Resin layer
30. Surface modification layer
A centerline
Claims (11)
1. A non-photosensitive surface modifier is a non-photosensitive surface modifier in which a surface modifying layer is formed between a metal layer and a resin layer,
At least one heterocyclic compound having a structure represented by the following general formula (1), (2), (3) or (4),
Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent,
R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group, a heteroaryl group or a halogen atom,
N and m each represent an integer of 0 to 5, n+m=an integer of 0 to 5 (wherein, in the general formula (1), the integer of 0 to 4), when a plurality of substituents R 2 are provided, the substituents R 2 may be the same or different from each other, when a plurality of n are provided, the n may be the same or different from each other, and when a plurality of m are provided, the m may be the same or different from each other.
2. The non-photosensitive surface modifier according to claim 1, wherein the heterocyclic compound has a structure represented by the general formula (1).
3. The non-photosensitive surface modifier according to claim 2, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5),
General formula (5)
Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent.
4. The non-photosensitive surface modifier according to any one of claims 1 to 3, wherein the non-photosensitive surface modifier contains at least water or an alcohol.
5. A laminate comprising a metal layer and a surface-modifying layer and a resin layer sequentially provided on the metal layer,
The surface-modified layer contains at least one or more heterocyclic compounds having a structure represented by the following general formula (1), (2), (3) or (4),
Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent,
R 2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an ester group, an amide group, a heteroaryl group or a halogen atom,
N and m each represent an integer of 0 to 5, n+m=an integer of 0 to 5 (wherein, in the general formula (1), the integer of 0 to 4), when a plurality of substituents R 2 are provided, the substituents R 2 may be the same or different from each other, when a plurality of n are provided, the n may be the same or different from each other, and when a plurality of m are provided, the m may be the same or different from each other.
6. The laminate according to claim 5, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the general formula (1).
7. The laminate according to claim 6, wherein the heterocyclic compound is a heterocyclic compound having a structure represented by the following general formula (5),
General formula (5)
Wherein R 1 represents a hydrogen atom, an aryl group or a heteroaryl group, and may have a substituent.
8. 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.
9. 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.
10. A printed circuit board using the laminate according to any one of claims 5 to 9.
11. An electronic device using the laminate according to any one of claims 5 to 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021183868 | 2021-11-11 | ||
| JP2021-183868 | 2021-11-11 | ||
| PCT/JP2022/041485 WO2023085246A1 (en) | 2021-11-11 | 2022-11-08 | Nonphotosensitive surface modifying agent, laminate, printed circuit board, and electronic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118202008A true CN118202008A (en) | 2024-06-14 |
Family
ID=86336023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280073097.1A Pending CN118202008A (en) | 2021-11-11 | 2022-11-08 | Non-photosensitive surface modifier, laminate, printed circuit board, and electronic device |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20240055049A (en) |
| CN (1) | CN118202008A (en) |
| TW (1) | TWI822452B (en) |
| WO (1) | WO2023085246A1 (en) |
Family Cites Families (9)
| 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 |
| US5556973A (en) * | 1994-07-27 | 1996-09-17 | Ciba-Geigy Corporation | Red-shifted tris-aryl-s-triazines and compositions stabilized therewith |
| US20120168075A1 (en) * | 2008-03-21 | 2012-07-05 | Enthone Inc. | Adhesion promotion of metal to laminate with multi-functional molecular system |
| US10405422B2 (en) * | 2012-07-09 | 2019-09-03 | Shikoku Chemicals Corporation | Copper film-forming agent and method for forming copper film |
| 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 |
| JP6232605B2 (en) | 2016-05-10 | 2017-11-22 | メック株式会社 | Film-forming composition, method for producing surface-treated metal member, and method for producing metal-resin composite |
| US9797043B1 (en) * | 2016-09-13 | 2017-10-24 | Rohm And Haas Electronic Materials Llc | Shielding coating for selective metallization |
| JP6612485B1 (en) | 2018-03-27 | 2019-11-27 | 東京応化工業株式会社 | Method for producing plated shaped object |
-
2022
- 2022-11-08 WO PCT/JP2022/041485 patent/WO2023085246A1/en active Application Filing
- 2022-11-08 CN CN202280073097.1A patent/CN118202008A/en active Pending
- 2022-11-08 KR KR1020247010870A patent/KR20240055049A/en unknown
- 2022-11-09 TW TW111142807A patent/TWI822452B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023085246A1 (en) | 2023-05-19 |
| KR20240055049A (en) | 2024-04-26 |
| TW202335538A (en) | 2023-09-01 |
| TWI822452B (en) | 2023-11-11 |
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