JP2010103081A - Electroconductive fine particles, anisotropic electroconductive material and connecting structure - Google Patents
Electroconductive fine particles, anisotropic electroconductive material and connecting structure Download PDFInfo
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- JP2010103081A JP2010103081A JP2009079912A JP2009079912A JP2010103081A JP 2010103081 A JP2010103081 A JP 2010103081A JP 2009079912 A JP2009079912 A JP 2009079912A JP 2009079912 A JP2009079912 A JP 2009079912A JP 2010103081 A JP2010103081 A JP 2010103081A
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- JP
- Japan
- Prior art keywords
- fine particles
- conductive fine
- alkyl group
- resin
- nickel layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000010419 fine particle Substances 0.000 title claims abstract description 198
- 239000000463 material Substances 0.000 title abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 230
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 115
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 45
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 45
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 66
- 239000011347 resin Substances 0.000 claims description 66
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 239000004020 conductor Substances 0.000 claims description 23
- -1 phosphate ester Chemical class 0.000 claims description 18
- 150000001356 alkyl thiols Chemical class 0.000 claims description 16
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 82
- 239000000243 solution Substances 0.000 description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 41
- 238000000034 method Methods 0.000 description 40
- 239000002245 particle Substances 0.000 description 36
- 238000007747 plating Methods 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000007772 electroless plating Methods 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 239000012153 distilled water Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910000420 cerium oxide Inorganic materials 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IDJPKRIELSFBPE-UHFFFAOYSA-N 1-(decyldisulfanyl)decane Chemical compound CCCCCCCCCCSSCCCCCCCCCC IDJPKRIELSFBPE-UHFFFAOYSA-N 0.000 description 2
- IFGAFLQUAVLERP-UHFFFAOYSA-N 1-(heptyldisulfanyl)heptane Chemical compound CCCCCCCSSCCCCCCC IFGAFLQUAVLERP-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 2
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001785 cerium compounds Chemical class 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 2
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GAYUSSOCODCSNF-UHFFFAOYSA-N 1-(dodecyldisulfanyl)dodecane Chemical compound CCCCCCCCCCCCSSCCCCCCCCCCCC GAYUSSOCODCSNF-UHFFFAOYSA-N 0.000 description 1
- GUBWMRCVCQFLOJ-UHFFFAOYSA-N 1-(hexadecyldisulfanyl)hexadecane Chemical compound CCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCC GUBWMRCVCQFLOJ-UHFFFAOYSA-N 0.000 description 1
- GJPDBURPGLWRPW-UHFFFAOYSA-N 1-(hexyldisulfanyl)hexane Chemical compound CCCCCCSSCCCCCC GJPDBURPGLWRPW-UHFFFAOYSA-N 0.000 description 1
- AVWMIWJCGFMMNP-UHFFFAOYSA-N 1-(nonyldisulfanyl)nonane Chemical compound CCCCCCCCCSSCCCCCCCCC AVWMIWJCGFMMNP-UHFFFAOYSA-N 0.000 description 1
- AROCLDYPZXMJPW-UHFFFAOYSA-N 1-(octyldisulfanyl)octane Chemical compound CCCCCCCCSSCCCCCCCC AROCLDYPZXMJPW-UHFFFAOYSA-N 0.000 description 1
- ULLWKWAZWYSPDY-UHFFFAOYSA-N 1-(pentadecyldisulfanyl)pentadecane Chemical compound CCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCC ULLWKWAZWYSPDY-UHFFFAOYSA-N 0.000 description 1
- PVHFXVCJLSWJAO-UHFFFAOYSA-N 1-(tetradecyldisulfanyl)tetradecane Chemical compound CCCCCCCCCCCCCCSSCCCCCCCCCCCCCC PVHFXVCJLSWJAO-UHFFFAOYSA-N 0.000 description 1
- QYVIBJKOSSAQLE-UHFFFAOYSA-N 1-(tridecyldisulfanyl)tridecane Chemical compound CCCCCCCCCCCCCSSCCCCCCCCCCCCC QYVIBJKOSSAQLE-UHFFFAOYSA-N 0.000 description 1
- BMMUJKMHJWGHJA-UHFFFAOYSA-N 1-(undecyldisulfanyl)undecane Chemical compound CCCCCCCCCCCSSCCCCCCCCCCC BMMUJKMHJWGHJA-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical compound CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- LCNHRERMIXAWNV-UHFFFAOYSA-M [Na+].C(CCCCCC)OP([O-])(O)=O Chemical compound [Na+].C(CCCCCC)OP([O-])(O)=O LCNHRERMIXAWNV-UHFFFAOYSA-M 0.000 description 1
- HVOBIHRXEHOVCL-UHFFFAOYSA-L [Na+].C(CCCCCCCCCCCCCC)OP(=O)([O-])[O-].[Ca+2] Chemical compound [Na+].C(CCCCCCCCCCCCCC)OP(=O)([O-])[O-].[Ca+2] HVOBIHRXEHOVCL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GGKJPMAIXBETTD-UHFFFAOYSA-L heptyl phosphate Chemical compound CCCCCCCOP([O-])([O-])=O GGKJPMAIXBETTD-UHFFFAOYSA-L 0.000 description 1
- VRINOTYEGADLMW-UHFFFAOYSA-N heptyl(trimethoxy)silane Chemical compound CCCCCCC[Si](OC)(OC)OC VRINOTYEGADLMW-UHFFFAOYSA-N 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- PHNWGDTYCJFUGZ-UHFFFAOYSA-L hexyl phosphate Chemical compound CCCCCCOP([O-])([O-])=O PHNWGDTYCJFUGZ-UHFFFAOYSA-L 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect 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
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZVEZMVFBMOOHAT-UHFFFAOYSA-N nonane-1-thiol Chemical compound CCCCCCCCCS ZVEZMVFBMOOHAT-UHFFFAOYSA-N 0.000 description 1
- WYAKJXQRALMWPB-UHFFFAOYSA-N nonyl dihydrogen phosphate Chemical compound CCCCCCCCCOP(O)(O)=O WYAKJXQRALMWPB-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- HIEAVKFYHNFZNR-UHFFFAOYSA-N pentadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCOP(O)(O)=O HIEAVKFYHNFZNR-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- KLEHMHBLPUXXPU-UHFFFAOYSA-M sodium;decyl hydrogen phosphate Chemical compound [Na+].CCCCCCCCCCOP(O)([O-])=O KLEHMHBLPUXXPU-UHFFFAOYSA-M 0.000 description 1
- JDSVWTAJRNTSSL-UHFFFAOYSA-M sodium;dodecyl hydrogen phosphate Chemical compound [Na+].CCCCCCCCCCCCOP(O)([O-])=O JDSVWTAJRNTSSL-UHFFFAOYSA-M 0.000 description 1
- QDZFJQPFGZWVHR-UHFFFAOYSA-M sodium;hexyl hydrogen phosphate Chemical compound [Na+].CCCCCCOP(O)([O-])=O QDZFJQPFGZWVHR-UHFFFAOYSA-M 0.000 description 1
- DZNVQXUZTZXYPW-UHFFFAOYSA-M sodium;nonyl hydrogen phosphate Chemical compound [Na+].CCCCCCCCCOP(O)([O-])=O DZNVQXUZTZXYPW-UHFFFAOYSA-M 0.000 description 1
- KOJSOGZMZDBNPG-UHFFFAOYSA-M sodium;octyl hydrogen phosphate Chemical compound [Na+].CCCCCCCCOP(O)([O-])=O KOJSOGZMZDBNPG-UHFFFAOYSA-M 0.000 description 1
- ZGMLVUQCSRECAE-UHFFFAOYSA-M sodium;undecyl hydrogen phosphate Chemical compound [Na+].CCCCCCCCCCCOP(O)([O-])=O ZGMLVUQCSRECAE-UHFFFAOYSA-M 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- IPBROXKVGHZHJV-UHFFFAOYSA-N tridecane-1-thiol Chemical compound CCCCCCCCCCCCCS IPBROXKVGHZHJV-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 description 1
- SAWDTKLQESXBDN-UHFFFAOYSA-N triethoxy(heptyl)silane Chemical compound CCCCCCC[Si](OCC)(OCC)OCC SAWDTKLQESXBDN-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- FZXOVEZAKDRQJC-UHFFFAOYSA-N triethoxy(nonyl)silane Chemical compound CCCCCCCCC[Si](OCC)(OCC)OCC FZXOVEZAKDRQJC-UHFFFAOYSA-N 0.000 description 1
- ZJLGWINGXOQWDC-UHFFFAOYSA-N triethoxy(pentadecyl)silane Chemical compound CCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC ZJLGWINGXOQWDC-UHFFFAOYSA-N 0.000 description 1
- SVKDNKCAGJVMMY-UHFFFAOYSA-N triethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OCC)(OCC)OCC SVKDNKCAGJVMMY-UHFFFAOYSA-N 0.000 description 1
- BBWMWJONYVGXGQ-UHFFFAOYSA-N triethoxy(undecyl)silane Chemical compound CCCCCCCCCCC[Si](OCC)(OCC)OCC BBWMWJONYVGXGQ-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- LCXXOYOABWDYBF-UHFFFAOYSA-N trimethoxy(pentadecyl)silane Chemical compound CCCCCCCCCCCCCCC[Si](OC)(OC)OC LCXXOYOABWDYBF-UHFFFAOYSA-N 0.000 description 1
- AXNJHBYHBDPTQF-UHFFFAOYSA-N trimethoxy(tetradecyl)silane Chemical compound CCCCCCCCCCCCCC[Si](OC)(OC)OC AXNJHBYHBDPTQF-UHFFFAOYSA-N 0.000 description 1
- QSYYSIXGDAAPNN-UHFFFAOYSA-N trimethoxy(tridecyl)silane Chemical compound CCCCCCCCCCCCC[Si](OC)(OC)OC QSYYSIXGDAAPNN-UHFFFAOYSA-N 0.000 description 1
- LIJFLHYUSJKHKV-UHFFFAOYSA-N trimethoxy(undecyl)silane Chemical compound CCCCCCCCCCC[Si](OC)(OC)OC LIJFLHYUSJKHKV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CCIDWXHLGNEQSL-UHFFFAOYSA-N undecane-1-thiol Chemical compound CCCCCCCCCCCS CCIDWXHLGNEQSL-UHFFFAOYSA-N 0.000 description 1
- VAIOGRPEROWKJX-UHFFFAOYSA-N undecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCOP(O)(O)=O VAIOGRPEROWKJX-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は、信頼性が高い電気接続ができる導電性微粒子に関する。また、該導電性微粒子を含有する異方性導電材料、及び、該導電性微粒子又は該異方性導電材料によって接続された接続構造体に関する。 The present invention relates to conductive fine particles that can be electrically connected with high reliability. The present invention also relates to an anisotropic conductive material containing the conductive fine particles, and a connection structure connected by the conductive fine particles or the anisotropic conductive material.
絶縁性のバインダー樹脂に導電性微粒子が分散されている異方性導電材料は、電極接続材料として使用されている。異方性導電材料は、異方性導電フィルム、異方性導電シート、異方性導電接着剤等が挙げられる。例えば、異方性導電材料は、基板に形成されている電極を電気的に接続するために、基板や電子部品の電極間に挟み込んで使用される。特に、異方性導電材料は液晶ディスプレイ、パーソナルコンピュータ、携帯電話等の電子機器に広く用いられている。 An anisotropic conductive material in which conductive fine particles are dispersed in an insulating binder resin is used as an electrode connecting material. Examples of the anisotropic conductive material include an anisotropic conductive film, an anisotropic conductive sheet, and an anisotropic conductive adhesive. For example, an anisotropic conductive material is used by being sandwiched between electrodes of a substrate or an electronic component in order to electrically connect electrodes formed on the substrate. In particular, anisotropic conductive materials are widely used in electronic devices such as liquid crystal displays, personal computers, and mobile phones.
従来、導電性微粒子として、表面に金めっき層が形成された導電性微粒子が用いられている。特許文献１には、非金属材料の芯材粉体の表面に無電解めっき層が形成され、無電解めっき層として、最上層に位置する金めっき層と該層に隣接するニッケル層とを含む多層構造が形成された導電性無電解めっき粉体が開示されている。このような導電性無電解めっき粉体を用いれば、対向する電極間の導通が得られることが開示されている。 Conventionally, conductive fine particles having a gold plating layer formed on the surface have been used as the conductive fine particles. In Patent Document 1, an electroless plating layer is formed on the surface of a non-metallic material core material powder, and the electroless plating layer includes a gold plating layer positioned at the uppermost layer and a nickel layer adjacent to the gold plating layer. A conductive electroless plating powder having a multilayer structure is disclosed. It is disclosed that when such a conductive electroless plating powder is used, conduction between opposing electrodes can be obtained.
しかしながら、表面に金めっき層が形成された導電性微粒子が分散した異方性導電材料を用いて基板や電子部品の電極間を接続すると、導電性微粒子と電極との間に絶縁性のバインダー樹脂が残留するという問題があった。また、表面に金めっき層が形成された導電性微粒子は、電極の表面に形成された酸化被膜を突き破ることができず、電極間の接続抵抗値が高くなることがあるという問題があった。これらの問題は、金が比較的柔らかい金属であるためと考えられる。 However, when an anisotropic conductive material in which conductive fine particles having a gold plating layer formed on the surface are dispersed is used to connect between electrodes of a substrate or an electronic component, an insulating binder resin is formed between the conductive fine particles and the electrodes. There was a problem that remained. Further, the conductive fine particles having the gold plating layer formed on the surface cannot break through the oxide film formed on the surface of the electrode, and there is a problem that the connection resistance value between the electrodes may be increased. These problems are considered because gold is a relatively soft metal.
そこで、金よりも硬い金属で形成された導電層を有する導電性微粒子が検討されている。特許文献２には、芯材粉体の表面に無電解めっき法により、ニッケル被膜を形成した導電性無電解めっき粉体が開示されている。しかしながら、ニッケルは金より酸化されやすいため、このような導電性無電解めっき粉体は信頼性が高い電気接続ができないという問題があった。 Therefore, conductive fine particles having a conductive layer formed of a metal harder than gold have been studied. Patent Document 2 discloses a conductive electroless plating powder in which a nickel coating is formed on the surface of a core powder by an electroless plating method. However, since nickel is more easily oxidized than gold, such a conductive electroless plating powder has a problem that electrical connection with high reliability cannot be achieved.
本発明は、信頼性が高い電気接続ができる導電性微粒子を提供することを目的とする。また、本発明は、該導電性微粒子を含有する異方性導電材料、及び、該導電性微粒子又は該異方性導電材料によって接続された接続構造体を提供することを目的とする。 An object of this invention is to provide the electroconductive fine particles which can perform electrical connection with high reliability. Another object of the present invention is to provide an anisotropic conductive material containing the conductive fine particles, and a connection structure connected by the conductive fine particles or the anisotropic conductive material.
本発明は、基材微粒子の表面に、ニッケル層が形成されている導電性微粒子であって、上記ニッケル層のニッケル含有率が９６重量％以上であり、かつ、上記ニッケル層の表面に、セリウム、又は、チタンを含有する金属酸化物層が形成されている導電性微粒子である。
以下に本発明を詳述する。
The present invention relates to conductive fine particles in which a nickel layer is formed on the surface of a substrate fine particle, the nickel content of the nickel layer is 96% by weight or more, and cerium is formed on the surface of the nickel layer. Alternatively, conductive fine particles in which a metal oxide layer containing titanium is formed.
The present invention is described in detail below.
本発明の導電性微粒子は、基材微粒子の表面に、ニッケル層が形成されており、上記ニッケル層のニッケル含有率は９６重量％以上である。 In the conductive fine particles of the present invention, a nickel layer is formed on the surface of the substrate fine particles, and the nickel content of the nickel layer is 96% by weight or more.
上記基材微粒子は特に限定されず、例えば、樹脂微粒子、無機微粒子、有機無機ハイブリッド微粒子、金属微粒子等が挙げられる。
上記樹脂微粒子は特に限定されず、例えば、ポリオレフィン樹脂、アクリル樹脂、ポリアルキレンテレフタレート樹脂、ポリスルホン樹脂、ポリカーボネート樹脂、ポリアミド樹脂、フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂等で構成される樹脂微粒子が挙げられる。
上記ポリオレフィン樹脂は特に限定されず、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリイソブチレン樹脂、ポリブタジエン樹脂等が挙げられる。上記アクリル樹脂は特に限定されず、例えば、ポリメチルメタクリレート樹脂、ポリメチルアクリレート樹脂等が挙げられる。これらの樹脂は、単独で用いられてもよいし、２種以上が併用されてもよい。
The substrate fine particles are not particularly limited, and examples thereof include resin fine particles, inorganic fine particles, organic-inorganic hybrid fine particles, and metal fine particles.
The resin fine particles are not particularly limited, and include, for example, polyolefin resin, acrylic resin, polyalkylene terephthalate resin, polysulfone resin, polycarbonate resin, polyamide resin, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, and the like. Resin fine particles.
The polyolefin resin is not particularly limited, and examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, polyisobutylene resin, and polybutadiene resin. The acrylic resin is not particularly limited, and examples thereof include polymethyl methacrylate resin and polymethyl acrylate resin. These resins may be used alone or in combination of two or more.
上記無機微粒子は特に限定されず、例えば、シリカ、アルミナ等の金属酸化物で構成される微粒子が挙げられる。上記有機無機ハイブリッド微粒子は特に限定されず、例えば、オルガノシロキサン骨格の中にアクリルポリマーを含有するハイブリッド微粒子が挙げられる。上記金属微粒子は特に限定されず、例えば、銅を含有する金属微粒子等が挙げられる。 The inorganic fine particles are not particularly limited, and examples thereof include fine particles composed of metal oxides such as silica and alumina. The organic-inorganic hybrid fine particles are not particularly limited, and examples thereof include hybrid fine particles containing an acrylic polymer in an organosiloxane skeleton. The metal fine particles are not particularly limited, and examples thereof include metal fine particles containing copper.
上記樹脂微粒子の１０％Ｋ値の好ましい下限は１０００Ｎ／ｍｍ２、好ましい上限は１５０００Ｎ／ｍｍ２である。上記１０％Ｋ値が１０００Ｎ／ｍｍ２未満であると、樹脂微粒子を圧縮変形させると、樹脂微粒子が破壊されることがある。上記１０％Ｋ値が１５０００Ｎ／ｍｍ２を超えると、導電性微粒子が電極を傷つけることがある。上記１０％Ｋ値のより好ましい下限は２０００Ｎ／ｍｍ２、より好ましい上限は１００００Ｎ／ｍｍ２である。 A preferred lower limit of the 10% K value of the resin fine particles 1000 N / mm 2, the upper limit is preferably 15000 N / mm 2. If the 10% K value is less than 1000 N / mm 2 , the resin fine particles may be destroyed when the resin fine particles are compressed and deformed. When the 10% K value exceeds 15000 N / mm 2 , the conductive fine particles may damage the electrode. A more preferred lower limit of the 10% K value 2000N / mm 2, and more preferable upper limit is 10000 N / mm 2.
なお、上記１０％Ｋ値は、微小圧縮試験器（例えば、島津製作所社製「ＰＣＴ−２００」）を用い、樹脂微粒子を直径５０μｍのダイアモンド製円柱の平滑圧子端面で、圧縮速度２．６ｍＮ／秒、最大試験荷重１０ｇの条件下で圧縮した場合の圧縮変位（ｍｍ）を測定し、下記式により求めることができる。
Ｋ値（Ｎ／ｍｍ２）＝（３／√２）・Ｆ・Ｓ−３／２・Ｒ−１／２
Ｆ：樹脂微粒子の１０％圧縮変形における荷重値（Ｎ）
Ｓ：樹脂微粒子の１０％圧縮変形における圧縮変位（ｍｍ）
Ｒ：樹脂微粒子の半径（ｍｍ）
The 10% K value is obtained by using a micro compression tester (for example, “PCT-200” manufactured by Shimadzu Corporation), and using a smooth indenter end face of a diamond cylinder having a diameter of 50 μm and a compression speed of 2.6 mN / The compression displacement (mm) when compressed under conditions of seconds and a maximum test load of 10 g can be measured and determined by the following equation.
K value (N / mm 2) = ( 3 / √2) · F · S -3/2 · R -1/2
F: Load value at 10% compression deformation of resin fine particles (N)
S: Compression displacement (mm) in 10% compression deformation of resin fine particles
R: radius of resin fine particles (mm)
上記基材微粒子の平均粒子径は特に限定されないが、好ましい下限は０．５μｍ、好ましい上限は１００μｍである。上記基材微粒子の平均粒子径が０．５μｍ未満であると、基材微粒子が凝集しやすいため、凝集した基材微粒子の表面にニッケル層を形成した導電性微粒子は、隣接する電極間を短絡させることがある。上記基材微粒子の平均粒子径が１００μｍを超えると、基材微粒子の表面からニッケル層が剥がれやすくなるため、接続信頼性が低下することがある。上記基材微粒子の平均粒子径のより好ましい下限は１μｍ、より好ましい上限は２０μｍである。
なお、上記基材微粒子の平均粒子径は、光学顕微鏡又は電子顕微鏡を用いて無作為に選んだ５０個の基材微粒子の粒子径を測定し、測定した粒子径を算術平均することにより求めることができる。
The average particle diameter of the substrate fine particles is not particularly limited, but a preferable lower limit is 0.5 μm and a preferable upper limit is 100 μm. When the average particle size of the base material particles is less than 0.5 μm, the base material particles are likely to aggregate. Therefore, the conductive fine particles in which the nickel layer is formed on the surface of the aggregated base material particles are short-circuited between adjacent electrodes. There are things to do. When the average particle diameter of the substrate fine particles exceeds 100 μm, the nickel layer is easily peeled off from the surface of the substrate fine particles, so that connection reliability may be lowered. The more preferable lower limit of the average particle diameter of the substrate fine particles is 1 μm, and the more preferable upper limit is 20 μm.
The average particle size of the above-mentioned substrate fine particles is obtained by measuring the particle size of 50 randomly selected substrate fine particles using an optical microscope or an electron microscope and arithmetically averaging the measured particle sizes. Can do.
上記基材微粒子の平均粒子径の変動係数は特に限定されないが、１０％以下であることが好ましい。上記変動係数が１０％を超えると、導電性微粒子の接続信頼性が低下することがある。なお、上記変動係数とは、粒子径分布から得られる標準偏差を平均粒子径で除して得られる値を百分率（％）で示した数値である。 The coefficient of variation of the average particle diameter of the substrate fine particles is not particularly limited, but is preferably 10% or less. If the coefficient of variation exceeds 10%, the connection reliability of the conductive fine particles may be lowered. The coefficient of variation is a numerical value obtained by dividing the standard deviation obtained from the particle size distribution by the average particle size and expressed as a percentage (%).
上記基材微粒子の形状は、対向する電極の間隔を維持できる形状であれば特に限定されないが、真球形状であることが好ましい。また、上記基材微粒子の表面は平滑であってもよいし、突起を有していてもよい。 The shape of the substrate fine particles is not particularly limited as long as the distance between the opposing electrodes can be maintained, but a true spherical shape is preferable. Further, the surface of the substrate fine particles may be smooth or may have a protrusion.
上記ニッケル層のニッケル含有率は９６重量％以上である。上記ニッケル含有率が９６重量％未満であると、導電性微粒子の接続抵抗値が高くなるため、信頼性が高い電気接続ができない。また、上記ニッケル層が酸化されやすくなる。上記ニッケル含有率は９７重量％以上であることが好ましく、９９重量％以上であることがより好ましい。なお、上記ニッケル層のニッケル含有率とは、ニッケル層に含有される元素の合計重量に占めるニッケルの重量の割合を百分率（％）で示した数値である。 The nickel content of the nickel layer is 96% by weight or more. When the nickel content is less than 96% by weight, the connection resistance value of the conductive fine particles is increased, so that highly reliable electrical connection cannot be achieved. Further, the nickel layer is easily oxidized. The nickel content is preferably 97% by weight or more, and more preferably 99% by weight or more. In addition, the nickel content rate of the said nickel layer is the numerical value which showed the ratio of the weight of nickel to the total weight of the element contained in a nickel layer in percentage (%).
上記ニッケル層は、ニッケル以外の元素を含有してもよい。上記ニッケル以外の元素は特に限定されず、例えば、リン、ホウ素、コバルト、タングステン等が挙げられる。上記ニッケル層のニッケル以外の元素の含有率は４重量％以下であれば、特に限定されないが、上記ニッケル以外の元素の含有率は３重量％以下であることが好ましく、１重量％以下であることがより好ましい。
なお、上記ニッケル層のニッケル含有率は、高周波誘導結合プラズマ発光分光分析装置（堀場製作所社製「ＩＣＰ−ＡＥＳ」）、蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ−８００ＨＳ」）等を用いて測定することができる。
The nickel layer may contain an element other than nickel. The elements other than nickel are not particularly limited, and examples thereof include phosphorus, boron, cobalt, tungsten, and the like. The content of elements other than nickel in the nickel layer is not particularly limited as long as it is 4% by weight or less, but the content of elements other than nickel is preferably 3% by weight or less, and is preferably 1% by weight or less. It is more preferable.
The nickel content of the nickel layer is determined using a high frequency inductively coupled plasma emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.), a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu), or the like. Can be measured.
上記ニッケル層は、上記基材微粒子の表面に直接形成されていてもよい。また、上記ニッケル層は、上記ニッケル層と上記基材微粒子との間に、下地金属層が形成されていてもよい。
上記下地金属層を構成する金属は特に限定されず、例えば、金、銀、銅、白金、亜鉛、鉄、錫、鉛、アルミニウム、コバルト、インジウム、クロム、チタン、アンチモン、ビスマス、ゲルマニウム、カドミウム等が挙げられる。
The nickel layer may be directly formed on the surface of the substrate fine particles. In the nickel layer, a base metal layer may be formed between the nickel layer and the substrate fine particles.
The metal constituting the base metal layer is not particularly limited. For example, gold, silver, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, chromium, titanium, antimony, bismuth, germanium, cadmium, etc. Is mentioned.
上記ニッケル層の厚さは特に限定されないが、好ましい下限は０．００５μｍ、好ましい上限は３μｍである。上記ニッケル層の厚さが０．００５μｍ未満であると、導電性微粒子の接続抵抗値が高くなることがある。上記ニッケル層の厚さが３μｍを超えると、導電性微粒子の柔軟性が損なわれることがある。上記ニッケル層の厚さのより好ましい下限は０．０８μｍ、より好ましい上限は０．３μｍである。
なお、上記ニッケル層の厚さは、無作為に選んだ１０個の導電性微粒子の断面を走査型電子顕微鏡（ＳＥＭ）により観察して厚さを測定し、測定値を算術平均した厚さである。
Although the thickness of the said nickel layer is not specifically limited, A preferable minimum is 0.005 micrometer and a preferable upper limit is 3 micrometers. When the thickness of the nickel layer is less than 0.005 μm, the connection resistance value of the conductive fine particles may increase. When the thickness of the nickel layer exceeds 3 μm, the flexibility of the conductive fine particles may be impaired. The minimum with more preferable thickness of the said nickel layer is 0.08 micrometer, and a more preferable upper limit is 0.3 micrometer.
The thickness of the nickel layer is a thickness obtained by observing a section of 10 randomly selected conductive fine particles with a scanning electron microscope (SEM) and measuring the thickness and arithmetically averaging the measured values. is there.
本発明の導電性微粒子は、上記ニッケル層の表面に、セリウム、又は、チタンを含有する金属酸化物層が形成されている。上記ニッケル層の表面に、セリウム、又は、チタンを含有する金属酸化物層が形成されているため、上記ニッケル層が直接酸素と接触しない。その結果、上記ニッケル層の酸化が防止できる。なかでも、上記ニッケル層の表面に、セリウムを含有する金属酸化物層が形成されていることが好ましい。上記セリウムを含有する金属酸化物層は自己修復機能を有するため、上記ニッケル層に亀裂が発生しても、上記ニッケル層の内部の酸化を防止する効果に優れる。
なお、上記金属酸化物層は、少なくとも酸化セリウム、又は、酸化チタンを含有すればよいが、実質的に、酸化セリウム、又は、酸化チタンで構成されていることが好ましい。
In the conductive fine particles of the present invention, a metal oxide layer containing cerium or titanium is formed on the surface of the nickel layer. Since the metal oxide layer containing cerium or titanium is formed on the surface of the nickel layer, the nickel layer is not in direct contact with oxygen. As a result, oxidation of the nickel layer can be prevented. In particular, a metal oxide layer containing cerium is preferably formed on the surface of the nickel layer. Since the metal oxide layer containing cerium has a self-healing function, even if cracks occur in the nickel layer, it is excellent in the effect of preventing oxidation inside the nickel layer.
In addition, although the said metal oxide layer should just contain a cerium oxide or a titanium oxide at least, it is preferable that it is substantially comprised with the cerium oxide or the titanium oxide.
上記セリウム、又は、チタンを含有する金属酸化物層の厚さは特に限定されないが、好ましい下限は０．００５μｍ、好ましい上限は０．０５μｍである。上記金属酸化物層の厚さが０．００５μｍ未満であると、上記ニッケル層の酸化が防止できないことがある。上記金属酸化物層の厚さが０．０５μｍを超えると、導電性微粒子の接続抵抗値が高くなることがある。上記金属酸化物層の厚さのより好ましい下限は０．０１μｍ、より好ましい上限は０．０３μｍである。
なお、上記金属酸化物層の厚さは、無作為に選んだ１０個の導電性微粒子の断面を走査型電子顕微鏡（ＳＥＭ）により観察して厚さを測定し、測定値を算術平均した厚さである。
The thickness of the metal oxide layer containing cerium or titanium is not particularly limited, but a preferable lower limit is 0.005 μm and a preferable upper limit is 0.05 μm. When the thickness of the metal oxide layer is less than 0.005 μm, oxidation of the nickel layer may not be prevented. When the thickness of the metal oxide layer exceeds 0.05 μm, the connection resistance value of the conductive fine particles may increase. The more preferable lower limit of the thickness of the metal oxide layer is 0.01 μm, and the more preferable upper limit is 0.03 μm.
The thickness of the metal oxide layer is a thickness obtained by observing a section of 10 randomly selected conductive fine particles with a scanning electron microscope (SEM) and measuring the thickness and arithmetically averaging the measured values. That's it.
上記ニッケル層の表面に、セリウムを含有する金属酸化物層を形成する方法は特に限定されないが、ニッケル層が形成された基材微粒子を、セリウム化合物が溶解している水溶液に添加する方法等が挙げられる。また、上記ニッケル層の表面に、チタンを含有する金属酸化物層を形成する方法は特に限定されないが、ニッケル層が形成された基材微粒子を、チタン化合物が溶解している水溶液に添加する方法等が挙げられる。 The method of forming the metal oxide layer containing cerium on the surface of the nickel layer is not particularly limited, but there is a method of adding the substrate fine particles on which the nickel layer is formed to an aqueous solution in which the cerium compound is dissolved. Can be mentioned. The method of forming the titanium-containing metal oxide layer on the surface of the nickel layer is not particularly limited, but the method of adding the substrate fine particles on which the nickel layer is formed to the aqueous solution in which the titanium compound is dissolved. Etc.
上記セリウム化合物は特に限定されないが、硫酸セリウム、塩化セリウム、硝酸セリウム、ステアリン酸セリウム等が挙げられる。上記チタン化合物は特に限定されないが、シュウ酸チタンカリウム、硫酸チタン、塩化チタン等が挙げられる。 The cerium compound is not particularly limited, and examples thereof include cerium sulfate, cerium chloride, cerium nitrate, and cerium stearate. The titanium compound is not particularly limited, and examples thereof include potassium potassium oxalate, titanium sulfate, and titanium chloride.
本発明の導電性微粒子は、水に対する表面接触角が９０°以上、かつ、体積抵抗率が０．００３０Ω・ｃｍ以下であることが好ましい。水に対する表面接触角が９０°以上となるように表面処理を施すことにより、ニッケル層の酸化をより効果的に防止することができる。これは、水に対する表面接触角を一定以上とすることにより、酸化の原因となる水分の接触を最低限に抑えることができるためと考えられる。しかしながら、表面接触角を調整するために表面処理を施こす場合、導電接続性を損なうこともある。水に対する表面接触角が９０°以上となると同時に、体積抵抗率が０．００３０Ω・ｃｍ以下となるような表面処理を施すことにより、酸化の抑制と導電接続性とを両立して、信頼性が高い電気接続を行うことができる。 The conductive fine particles of the present invention preferably have a surface contact angle with water of 90 ° or more and a volume resistivity of 0.0030 Ω · cm or less. By performing the surface treatment so that the surface contact angle with respect to water is 90 ° or more, oxidation of the nickel layer can be more effectively prevented. This is considered to be because the contact of moisture that causes oxidation can be minimized by setting the surface contact angle to water to a certain level or more. However, when surface treatment is performed to adjust the surface contact angle, the conductive connectivity may be impaired. The surface contact angle to water is 90 ° or more, and at the same time, the surface resistivity is 0.0030 Ω · cm or less, so that both the suppression of oxidation and the conductive connectivity can be achieved with high reliability. High electrical connection can be made.
水に対する表面接触角が９０°未満であると、ニッケル層が酸化しやすくなり、信頼性が高い電気接続を行うことができないことがある。水に対する表面接触角のより好ましい下限は１１０°であり、更に好ましい下限は１１０°である水に対する表面接触角の上限は特にないが、実質的には１６０°程度が上限である。 When the surface contact angle with respect to water is less than 90 °, the nickel layer is likely to be oxidized, and electrical connection with high reliability may not be performed. The more preferable lower limit of the surface contact angle with respect to water is 110 °, and the more preferable lower limit is 110 °. There is no particular upper limit of the surface contact angle with respect to water, but substantially 160 ° is the upper limit.
導電性微粒子の水に対する表面接触角は、例えば、全自動接触角測定装置（データフィジックス社製「ＯＣＡ３５」）を用いて測定することができる。導電性微粒子１ｇをスライドガラス上に置き、ニードルを導電性微粒子表面に近づけ、ニードルを用いて純水３μＬを導電性微粒子表面に付着させる。純水が付着した導電性微粒子を撮影した画像を解析し、表面接触角を測定できる。 The surface contact angle of the conductive fine particles with respect to water can be measured using, for example, a fully automatic contact angle measuring device (“OCA35” manufactured by Data Physics Co., Ltd.). 1 g of conductive fine particles are placed on a slide glass, the needle is brought close to the surface of the conductive fine particles, and 3 μL of pure water is attached to the surface of the conductive fine particles using the needle. The surface contact angle can be measured by analyzing an image obtained by photographing conductive fine particles to which pure water is adhered.
体積抵抗率が０．００３０Ω・ｃｍを超えると、信頼性の高い電気接続を行うことができないことがある。体積抵抗率のより好ましい上限は０．００２５Ω・ｃｍである。体積抵抗率の下限は特にないが、実質的には０．００１０Ω・ｃｍ程度が下限である。 When the volume resistivity exceeds 0.0030 Ω · cm, a highly reliable electrical connection may not be performed. A more preferable upper limit of the volume resistivity is 0.0025 Ω · cm. There is no particular lower limit for the volume resistivity, but the lower limit is substantially about 0.0010 Ω · cm.
本明細書において体積抵抗率は、三菱化学社製「粉体抵抗率測定システム」を用いて測定できる。なお、体積抵抗率とは、導電性微粒子２．５ｇに２０ｋＮの荷重を与えた際の体積抵抗率を意味する。 In the present specification, the volume resistivity can be measured using a “powder resistivity measurement system” manufactured by Mitsubishi Chemical Corporation. The volume resistivity means the volume resistivity when a load of 20 kN is applied to 2.5 g of conductive fine particles.
本発明の導電性微粒子の水に対する表面接触角を９０°以上、かつ、体積抵抗率が０．００３０Ω・ｃｍ以下とするためには、上記金属酸化物層の表面に表面処理を施す必要がある。
上記表面処理は特に限定されないが、例えば、上記金属酸化物層の表面に炭素数が６〜２２のアルキル基を有する化合物を反応させて結合させる方法が挙げられる。炭素数が６〜２２のアルキル基を有する化合物が結合した金属酸化物層は、疎水性となって水に対する表面接触角が９０°以上となる一方、体積抵抗率はそれほど低下せず、０．００３０Ω・ｃｍ以下にすることができる。
In order to set the surface contact angle of the conductive fine particles of the present invention to water to 90 ° or more and the volume resistivity to 0.0030 Ω · cm or less, it is necessary to subject the surface of the metal oxide layer to surface treatment. .
Although the said surface treatment is not specifically limited, For example, the method of making the surface of the said metal oxide layer react and couple | bond with the compound which has a C6-C22 alkyl group is mentioned. The metal oxide layer to which the compound having an alkyl group having 6 to 22 carbon atoms is bonded becomes hydrophobic and the surface contact angle with respect to water is 90 ° or more, while the volume resistivity does not decrease so much. It can be set to 0030 Ω · cm or less.
上記炭素数が６〜２２のアルキル基を有する化合物のアルキル基の炭素数の下限は６、上限は２２である。上記アルキル基の炭素数が６未満であると、得られる導電性微粒子の表面接触角を９０°以上とすることができず、ニッケル層が酸化しやすくなり、信頼性が高い電気接続を行うことができないことがある。上記アルキル基の炭素数が２２を超えると、得られる導電性微粒子の導電率が低下して、信頼性の高い電気接続を行うことができないことがある。上記アルキル基の炭素数の好ましい上限は１６である。
上記アルキル基は直鎖構造のアルキル基であってもよいし、分岐構造のアルキル基であってもよいが、直鎖構造のアルキル基であることが好ましい。
The lower limit of the carbon number of the alkyl group of the compound having an alkyl group having 6 to 22 carbon atoms is 6, and the upper limit is 22. When the alkyl group has less than 6 carbon atoms, the surface contact angle of the obtained conductive fine particles cannot be 90 ° or more, the nickel layer is easily oxidized, and highly reliable electrical connection is performed. May not be possible. When the alkyl group has more than 22 carbon atoms, the conductivity of the obtained conductive fine particles may be reduced, and reliable electrical connection may not be performed. The upper limit with preferable carbon number of the said alkyl group is 16.
The alkyl group may be a linear alkyl group or a branched alkyl group, but is preferably a linear alkyl group.
上記炭素数が６〜２２のアルキル基を有する化合物は特に限定されないが、炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩、炭素数が６〜２２のアルキル基を有するアルコキシシラン、炭素数が６〜２２のアルキル基を有するアルキルチオール及び炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドからなる群より選択される少なくとも１種が好適である。 Although the said compound which has a C6-C22 alkyl group is not specifically limited, The phosphate ester which has a C6-C22 alkyl group, or its salt, The alkoxysilane which has a C6-C22 alkyl group At least one selected from the group consisting of an alkylthiol having an alkyl group having 6 to 22 carbon atoms and a dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms is preferable.
上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩は、例えば、リン酸ヘキシルエステル、リン酸ヘプチルエステル、リン酸モノオクチルエステル、リン酸モノノニルエステル、リン酸モノデシルエステル、リン酸モノウンデシルエステル、リン酸モノドデシルエステル、リン酸モノトリデシルエステル、リン酸モノテトラデシルエステル、リン酸モノペンタデシルエステル、リン酸モノヘキシルエステルモノナトリウム塩、リン酸モノヘプチルエステルモノナトリウム塩、リン酸モノオクチルエステルモノナトリウム塩、リン酸モノノニルエステルモノナトリウム塩、リン酸モノデシルエステルモノナトリウム塩、リン酸モノウンデシルエステルモノナトリウム塩、リン酸モノドデシルエステルモノナトリウム塩、リン酸モノトリデシルエステルモノナトリウム塩、リン酸モノテトラデシルエステルモノナトリウム塩、リン酸モノペンタデシルエステルモノナトリウム塩等が挙げられる。 Examples of the phosphoric acid ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof include hexyl phosphate, heptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, Monoundecyl phosphate, monododecyl phosphate, monotridecyl phosphate, monotetradecyl phosphate, monopentadecyl phosphate, monohexyl phosphate monosodium salt, monoheptyl phosphate monosodium Salt, monooctyl phosphate monosodium salt, monononyl phosphate monosodium salt, monodecyl phosphate monosodium salt, monoundecyl phosphate monosodium salt, monododecyl phosphate monosodium salt, phosphorus Mono tridecyl ester monosodium salt, phosphate acid mono tetradecyl ester monosodium salt, monocalcium phosphate pentadecyl ester monosodium salt.
上記金属酸化物層の表面に、上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩を反応させる方法は特に限定されないが、例えば、上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩の水溶液を付着させる方法等が挙げられる。上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩の水溶液を付着させることにより、上記金属酸化物層の表面の金属酸化物と、上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩とが反応し、上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩が結合される。
上記リン酸エステル又はその塩の水溶液のリン酸エステルの濃度は特に限定されないが、リン酸エステルの濃度の好ましい下限は０．５重量％、好ましい上限は３重量％である。
なお、上記リン酸エステル水溶液は、テトラヒドロフランや、メタノール、エタノール、プロパノール等のアルコール等の有機溶剤を含有してもよい。
The method of reacting the phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof on the surface of the metal oxide layer is not particularly limited. For example, the base material on which the metal oxide layer is formed Examples thereof include a method in which an aqueous solution of a phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof is attached to fine particles. The surface of the metal oxide layer is oxidized by attaching an aqueous solution of a phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof to the substrate fine particles on which the metal oxide layer is formed. A phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, and a phosphate ester having an alkyl group having 6 to 22 carbon atoms on the surface of the metal oxide layer, or The salt is bound.
The concentration of the phosphate ester in the aqueous solution of the phosphate ester or a salt thereof is not particularly limited, but the preferred lower limit of the phosphate ester concentration is 0.5% by weight, and the preferred upper limit is 3% by weight.
In addition, the said phosphate ester aqueous solution may contain organic solvents, such as alcohol, such as tetrahydrofuran and methanol, ethanol, and propanol.
上記炭素数が６〜２２のアルキル基を有するアルコキシシランは、例えば、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、ヘプチルトリメトキシシラン、ヘプチルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、ノニルトリメトキシシラン、ノニルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシラン、ウンデシルトリメトキシシラン、ウンデシルトリエトキシシラン、ドデシルトリメトキシシラン、ドデシルトリエトキシシラン、トリデシルトリメトキシシラン、トリデシルトリエトキシシラン、テトラデシルトリメトキシシラン、テトラデシルトリエトキシシラン、ペンタデシルトリメトキシシラン、ペンタデシルトリエトキシシラン等が挙げられる。 Examples of the alkoxysilane having an alkyl group having 6 to 22 carbon atoms include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltri. Methoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxy Examples include silane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, and pentadecyltriethoxysilane.
上記金属酸化物層の表面を、上記炭素数が６〜２２のアルキル基を有するアルコキシシランで被覆する方法は特に限定されないが、上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するアルコキシシランの水溶液を付着させる方法等が挙げられる。上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するアルコキシシランの水溶液を付着させることにより、上記金属酸化物層の表面が、上記炭素数が６〜２２のアルキル基を有するアルコキシシランで被覆される。
上記アルコキシシランの水溶液のアルコキシシランの濃度は特に限定されないが、アルコキシシランの濃度の好ましい下限は０．５重量％、好ましい上限は３重量％である。
なお、上記炭素数が６〜２２のアルキル基を有するアルコキシシラン水溶液は、メタノール、エタノール、プロパノール等のアルコール等の有機溶剤を含有してもよい。
The method for coating the surface of the metal oxide layer with the alkoxysilane having an alkyl group having 6 to 22 carbon atoms is not particularly limited, but the substrate fine particles on which the metal oxide layer is formed have the carbon number. And a method of attaching an aqueous solution of an alkoxysilane having an alkyl group of 6-22. By attaching an aqueous solution of an alkoxysilane having an alkyl group having 6 to 22 carbon atoms to the substrate fine particles on which the metal oxide layer is formed, the surface of the metal oxide layer has 6 carbon atoms. It is coated with an alkoxysilane having ˜22 alkyl groups.
The concentration of the alkoxysilane in the alkoxysilane aqueous solution is not particularly limited, but the preferred lower limit of the alkoxysilane concentration is 0.5% by weight, and the preferred upper limit is 3% by weight.
In addition, the alkoxysilane aqueous solution which has the said C6-C22 alkyl group may contain organic solvents, such as alcohol, such as methanol, ethanol, and propanol.
上記炭素数が６〜２２のアルキル基を有するアルキルチオールは、例えば、ヘキシルチオール、ヘプチルチオール、オクチルチオール、ノニルチオール、デシルチオール、ウンデシルチオール、ドデシルチオール、トリデシルチオール、テトラデシルチオール、ペンタデシルチオール、ヘキサデシルチオール等が挙げられる。上記アルキルチオールは、アルキル鎖の末端にチオール基が存在することが好ましい。 Examples of the alkyl thiol having an alkyl group having 6 to 22 carbon atoms include hexyl thiol, heptyl thiol, octyl thiol, nonyl thiol, decyl thiol, undecyl thiol, dodecyl thiol, tridecyl thiol, tetradecyl thiol, pentadecyl Examples include thiol and hexadecyl thiol. The alkyl thiol preferably has a thiol group at the end of the alkyl chain.
上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するアルキルチオールを反応させる方法は特に限定されないが、上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するアルキルチオールが溶解している溶液に付着させる方法等が挙げられる。上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するアルキルチオールが溶解している溶液に付着させることにより、上記金属酸化物層の表面の金属酸化物と、上記炭素数が６〜２２のアルキル基を有するアルキルチオールとが反応し、上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するアルキルチオールが結合される。
上記アルキルチオールが溶解している溶液の上記アルキルチオールの濃度は特に限定されないが、アルキルチオールの濃度の好ましい下限は０．５重量％、好ましい上限は３重量％である。
なお、上記炭素数が６〜２２のアルキル基を有するアルキルチオールが溶解している溶液は、アルキルチオールが溶解すれば特に限定されず、メタノール、エタノール、プロパノール等のアルコール等の有機溶剤を含有してもよい。
The method of reacting the alkyl thiol having an alkyl group having 6 to 22 carbon atoms on the surface of the metal oxide layer is not particularly limited, but the base particles on which the metal oxide layer is formed have the above carbon number. Examples include a method of adhering to a solution in which an alkylthiol having 6 to 22 alkyl groups is dissolved. By attaching the alkyl thiol having an alkyl group having 6 to 22 carbon atoms to the substrate fine particles on which the metal oxide layer is formed, the metal oxide on the surface of the metal oxide layer is adhered. And an alkyl thiol having an alkyl group having 6 to 22 carbon atoms react with each other, and the alkyl thiol having an alkyl group having 6 to 22 carbon atoms is bonded to the surface of the metal oxide layer.
The concentration of the alkylthiol in the solution in which the alkylthiol is dissolved is not particularly limited, but the preferred lower limit of the alkylthiol concentration is 0.5% by weight, and the preferred upper limit is 3% by weight.
The solution in which the alkylthiol having an alkyl group having 6 to 22 carbon atoms is dissolved is not particularly limited as long as the alkylthiol dissolves, and contains an organic solvent such as alcohol such as methanol, ethanol, and propanol. May be.
上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドは、例えば、ジヘキシルジスルフィド、ジヘプチルジスルフィド、ジオクチルジスルフィド、ジノニルジスルフィド、ジデシルジスルフィド、ジウンデシルジスルフィド、ジドデシルジスルフィド、ジトリデシルジスルフィド、ジテトラデシルジスルフィド、ジペンタデシルジスルフィド、ジヘキサデシルジスルフィド等が挙げられる。 Examples of the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms include dihexyl disulfide, diheptyl disulfide, dioctyl disulfide, dinonyl disulfide, didecyl disulfide, diundecyl disulfide, didodecyl disulfide, ditridecyl disulfide, ditetradecyl disulfide. Examples include decyl disulfide, dipentadecyl disulfide, and dihexadecyl disulfide.
上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドを反応させる方法は特に限定されないが、上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドが溶解している溶液に付着させる方法等が挙げられる。上記金属酸化物層が形成された基材微粒子に、上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドが溶解している溶液を付着させることにより、上記金属酸化物層の表面の金属酸化物と、上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドとが反応し、上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドが結合される。
上記ジアルキルジスルフィドが溶解している溶液の上記ジアルキルジスルフィドの濃度は特に限定されないが、ジアルキルジスルフィドの濃度の好ましい下限は０．５重量％、好ましい上限は３重量％である。
なお、上記ジアルキルジスルフィドが溶解している溶液は、ジアルキルジスルフィドが溶解すれば特に限定されず、メタノール、エタノール、プロパノール等のアルコール等の有機溶剤を含有してもよい。
The method for reacting the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms on the surface of the metal oxide layer is not particularly limited, but the fine particles on the substrate on which the metal oxide layer is formed have the carbon number. Examples thereof include a method of adhering to a solution in which a dialkyl disulfide having 6 to 22 alkyl groups is dissolved. The surface of the metal oxide layer is oxidized by attaching a solution in which the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms is dissolved to the substrate fine particles on which the metal oxide layer is formed. And the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms react with each other, and the dialkyl disulfide having an alkyl group having 6 to 22 carbon atoms is bonded to the surface of the metal oxide layer.
The concentration of the dialkyl disulfide in the solution in which the dialkyl disulfide is dissolved is not particularly limited, but the preferred lower limit of the dialkyl disulfide concentration is 0.5% by weight, and the preferred upper limit is 3% by weight.
The solution in which the dialkyl disulfide is dissolved is not particularly limited as long as the dialkyl disulfide is dissolved, and may contain an organic solvent such as alcohol such as methanol, ethanol, and propanol.
上記表面処理の方法のなかでも、上記ニッケル層又は上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩を反応させる方法、上記ニッケル層又は上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するアルキルチオールを反応させる方法、及び、上記ニッケル層又は上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するジアルキルジスルフィドを反応させる方法が好ましく、上記ニッケル層又は上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩を反応させる方法、及び、上記ニッケル層又は上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するアルキルチオールを反応させる方法がより好ましく、上記ニッケル層又は上記金属酸化物層の表面に上記炭素数が６〜２２のアルキル基を有するリン酸エステル又はその塩を反応させる方法が更に好ましい。なお、上記表面接触角及び体積抵抗率は、上記炭素数が６〜２２のアルキル基を有する化合物の炭素数を変更したり、上記炭素数が６〜２２のアルキル基を有する化合物を反応させる時間、温度等を制御したりすることによって調整することができる。 Among the surface treatment methods, the nickel layer or the metal oxide layer is reacted with the phosphoric acid ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof, the nickel layer or the metal. A method of reacting an alkylthiol having an alkyl group having 6 to 22 carbon atoms on the surface of the oxide layer, and an alkyl group having 6 to 22 carbon atoms on the surface of the nickel layer or the metal oxide layer. A method of reacting a dialkyl disulfide having a reaction is preferable, a method of reacting a phosphate ester having an alkyl group having 6 to 22 carbon atoms or a salt thereof on the surface of the nickel layer or the metal oxide layer, and the nickel layer Or the method of making the surface of the said metal oxide layer react the said alkylthiol which has the said C6-C22 alkyl group is more preferable. How the number of carbon atoms on the surface of the nickel layer or the metal oxide layer reacting phosphoric acid ester or a salt thereof having an alkyl group of 6 to 22 is more preferred. In addition, the said surface contact angle and volume resistivity are the time which changes the carbon number of the compound which has the said C6-C22 alkyl group, or the compound which has the said C6-C22 alkyl group reacts. It can be adjusted by controlling the temperature or the like.
本発明の導電性微粒子の製造方法は特に限定されず、例えば、以下の方法により製造できる。 The manufacturing method of the electroconductive fine particles of this invention is not specifically limited, For example, it can manufacture with the following method.
基材微粒子の表面に、ニッケル含有率が９６重量％以上となるように、ニッケル層を形成させる。基材微粒子の表面に、ニッケル層を形成させる方法は特に限定されず、例えば、電解めっき法、無電解めっき法等の方法が挙げられる。
電解めっき法を用いて基材微粒子の表面に、ニッケル層を形成すると、ニッケル含有率が高いニッケル層が形成できる。しかし、電解めっき法を用いて、平均粒子径が１００μｍ未満の基材微粒子の表面に、ニッケル層を形成させると、基材微粒子が凝集してしまうことがあった。
A nickel layer is formed on the surface of the substrate fine particles so that the nickel content is 96% by weight or more. The method for forming the nickel layer on the surface of the substrate fine particles is not particularly limited, and examples thereof include methods such as an electrolytic plating method and an electroless plating method.
When a nickel layer is formed on the surface of the substrate fine particles using the electrolytic plating method, a nickel layer having a high nickel content can be formed. However, when the nickel layer is formed on the surface of the substrate fine particles having an average particle diameter of less than 100 μm using the electrolytic plating method, the substrate fine particles sometimes aggregate.
また、従来の無電解めっき法を用いて、基材微粒子の表面に、ニッケル層を形成すると、無電解めっき浴に含まれる還元剤由来のリンやホウ素等が、ニッケル層に含まれてしまうことがあった。リンやホウ素がニッケル層に含まれてしまうと、導電性微粒子の接続抵抗値が高くなってしまう。
従来の無電解めっき法では、基材微粒子が分散している懸濁液に、還元剤を含有する無電解ニッケルめっき液を滴下していたため、懸濁液中の還元剤濃度が高くなる。還元剤由来のリンやホウ素等がニッケル層に含まれるため、ニッケル層のニッケル含有率が低くなることがあった。また、このような無電解めっき法では、懸濁液のｐＨや、液温を調整しても、ニッケル層のニッケル含有率を高くすることは困難であった。
したがって、本発明では、ニッケル含有率が高いニッケル層を形成するために、無電解めっき浴中の還元剤の濃度を低く保ちながら、前期めっき工程と、後期めっき工程とを行うことが好ましい。このような工程で無電解めっきを行うことにより、ニッケル含有率が高いニッケル層を得ることができる。
In addition, when a nickel layer is formed on the surface of the substrate fine particles using a conventional electroless plating method, phosphorus or boron derived from a reducing agent contained in the electroless plating bath may be included in the nickel layer. was there. If phosphorus or boron is contained in the nickel layer, the connection resistance value of the conductive fine particles is increased.
In the conventional electroless plating method, since the electroless nickel plating solution containing the reducing agent is dropped into the suspension in which the base particles are dispersed, the reducing agent concentration in the suspension is increased. Since the nickel layer contains phosphorus, boron, and the like derived from the reducing agent, the nickel content of the nickel layer may be low. In addition, in such an electroless plating method, it is difficult to increase the nickel content of the nickel layer even if the pH of the suspension or the liquid temperature is adjusted.
Therefore, in the present invention, in order to form a nickel layer having a high nickel content, it is preferable to perform the first plating step and the second plating step while keeping the concentration of the reducing agent in the electroless plating bath low. By performing electroless plating in such a process, a nickel layer having a high nickel content can be obtained.
本発明では、無電解めっき法において、一般にエッチング工程、触媒化工程を行った後、無電解めっき工程を行うことが好ましい。
上記エッチング工程は、クロム酸、硫酸−クロム酸混液、過マンガン酸溶液等の酸化剤や、塩酸、硫酸等の強酸や、水酸化ナトリウム、水酸化カリウム等の強アルカリの水溶液等を用いて基材微粒子の表面に微小な凹凸を形成させ、ニッケル層の密着をよくするための工程である。
In the present invention, in the electroless plating method, it is generally preferable to perform an electroless plating step after performing an etching step and a catalytic step.
The etching process is based on an oxidizing agent such as chromic acid, sulfuric acid-chromic acid mixture, permanganic acid solution, strong acid such as hydrochloric acid or sulfuric acid, or strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide. This is a process for forming minute irregularities on the surface of the material fine particles and improving the adhesion of the nickel layer.
上記触媒化工程は、基材微粒子の表面に無電解めっきの起点となる触媒を付与する工程である。上記触媒化工程では、例えば、センシタイジング工程と、アクチベイジング工程とが行われる。上記センシタイジング工程として、エッチングされた基材微粒子を二塩化錫溶液に浸漬させることにより、基材微粒子の表面にＳｎ２＋イオンが吸着される。上記アクチベイジング工程として、Ｓｎ２＋イオンが吸着した基材微粒子を、二塩化パラジウム溶液に浸漬させることにより、基材微粒子の表面にパラジウム触媒が付与される。なお、上記アクチベイジング工程では、基材微粒子の表面で、Ｓｎ２＋＋Ｐｄ２＋→Ｓｎ４＋＋Ｐｄ０で示される反応が行われる。 The catalyzing step is a step of imparting a catalyst serving as a starting point of electroless plating to the surface of the substrate fine particles. In the catalyzing step, for example, a sensitizing step and an activating step are performed. As the sensitizing step, Sn 2+ ions are adsorbed on the surface of the substrate fine particles by immersing the etched substrate fine particles in a tin dichloride solution. As the above-mentioned activating step, the base material fine particles adsorbed with Sn 2+ ions are immersed in a palladium dichloride solution, whereby a palladium catalyst is imparted to the surface of the base material fine particles. In the activating process, a reaction represented by Sn 2+ + Pd 2+ → Sn 4+ + Pd 0 is performed on the surface of the base particle.
上記無電解めっき工程は、パラジウム触媒が付与された基材微粒子を還元剤の存在下で、無電解めっき浴中に浸漬し、付与されたパラジウム触媒を起点として基材微粒子の表面にめっき金属を析出させる工程である。上記無電解めっき工程では、前期めっき工程と、後期めっき工程とを有することが好ましい。
例えば、上記無電解めっき工程において、前期めっき工程の反応が停止した後、ニッケル層が形成された基材微粒子を洗浄する。洗浄された基材微粒子を還元剤が含まれないイオン交換水等に分散させ、後期めっき工程を行なうことが好ましい。このようなめっき工程を有することで、ニッケル層に含まれるリンやホウ素等の含有率を低減できる。
The electroless plating step involves immersing the substrate fine particles provided with a palladium catalyst in an electroless plating bath in the presence of a reducing agent, and depositing a plating metal on the surface of the substrate fine particles using the provided palladium catalyst as a starting point. It is the process of making it precipitate. In the electroless plating process, it is preferable to have an early plating process and a late plating process.
For example, in the electroless plating step, after the reaction in the previous plating step is stopped, the substrate fine particles on which the nickel layer is formed are washed. It is preferable to disperse the cleaned substrate fine particles in ion-exchanged water or the like that does not contain a reducing agent, and perform the late plating step. By having such a plating step, the content of phosphorus, boron, etc. contained in the nickel layer can be reduced.
本発明の導電性微粒子をバインダー樹脂に分散させることにより異方性導電材料を製造することができる。本発明の導電性微粒子と、バインダー樹脂とを含有する異方性導電材料もまた、本発明の１つである。 An anisotropic conductive material can be produced by dispersing the conductive fine particles of the present invention in a binder resin. An anisotropic conductive material containing the conductive fine particles of the present invention and a binder resin is also one aspect of the present invention.
本発明の異方性導電材料として、例えば、異方性導電ペースト、異方性導電インク、異方性導電接着剤、異方性導電フィルム、異方性導電シート等が挙げられる。 Examples of the anisotropic conductive material of the present invention include anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, anisotropic conductive film, and anisotropic conductive sheet.
上記バインダー樹脂は特に限定されないが、絶縁性の樹脂が用いられ、例えば、ビニル樹脂、熱可塑性樹脂、硬化性樹脂、熱可塑性ブロック共重合体、エラストマー等が挙げられる。
上記ビニル樹脂は特に限定されないが、例えば、酢酸ビニル樹脂、アクリル樹脂、スチレン樹脂等が挙げられる。
上記熱可塑性樹脂は特に限定されないが、例えば、ポリオレフィン樹脂、エチレン−酢酸ビニル共重合体、ポリアミド樹脂等が挙げられる。
上記硬化性樹脂は特に限定されないが、例えば、エポキシ樹脂、ウレタン樹脂、ポリイミド樹脂、不飽和ポリエステル樹脂等が挙げられる。なお、上記硬化性樹脂は、常温硬化型樹脂、熱硬化型樹脂、光硬化型樹脂、湿気硬化型樹脂であってもよい。上記硬化性樹脂は硬化剤と併用してもよい。
上記熱可塑性ブロック共重合体は特に限定されないが、例えば、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−ブタジエン−スチレンブロック共重合体の水素添加物、スチレン−イソプレン−スチレンブロック共重合体の水素添加物等が挙げられる。
上記エラストマーは特に限定されないが、例えば、スチレン−ブタジエン共重合ゴム、アクリロニトリル−スチレンブロック共重合ゴム等が挙げられる。
これらの樹脂は、単独で用いられてもよいし、２種以上が併用されてもよい。
The binder resin is not particularly limited, but an insulating resin is used, and examples thereof include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, and an elastomer.
Although the said vinyl resin is not specifically limited, For example, a vinyl acetate resin, an acrylic resin, a styrene resin etc. are mentioned.
Although the said thermoplastic resin is not specifically limited, For example, polyolefin resin, ethylene-vinyl acetate copolymer, a polyamide resin etc. are mentioned.
Although the said curable resin is not specifically limited, For example, an epoxy resin, a urethane resin, a polyimide resin, an unsaturated polyester resin etc. are mentioned. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent.
The thermoplastic block copolymer is not particularly limited. For example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated product of styrene-butadiene-styrene block copolymer, styrene -Hydrogenated product of isoprene-styrene block copolymer.
The elastomer is not particularly limited, and examples thereof include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
These resins may be used alone or in combination of two or more.
本発明の異方性導電材料は、本発明の導電性微粒子、及び、上記バインダー樹脂の他に、本発明の課題達成を阻害しない範囲で、例えば、増量剤、可塑剤、粘接着性向上剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、着色剤、難燃剤、有機溶媒等を含有してもよい。 In addition to the conductive fine particles of the present invention and the above-mentioned binder resin, the anisotropic conductive material of the present invention is, for example, an extender, a plasticizer, and improved adhesiveness within a range that does not hinder the achievement of the present invention. Agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants, flame retardants, organic solvents, and the like.
本発明の異方性導電材料の製造方法は特に限定されず、例えば、上記バインダー樹脂に本発明の導電性微粒子を添加し、均一に混合して分散させ、例えば、異方性導電ペースト、異方性導電インク、異方性導電接着剤等を製造する方法が挙げられる。また、上記バインダー樹脂に本発明の導電性微粒子を添加し、均一に分散させるか、又は、加熱溶解させて、離型紙や離型フィルム等の離型材の離型処理面に所定のフィルム厚さとなるように塗工し、例えば、異方性導電フィルム、異方性導電シート等を製造する方法も挙げられる。
また、上記バインダー樹脂と、本発明の導電性微粒子とを混合することなく、別々に用いて異方性導電材料としてもよい。
The method for producing the anisotropic conductive material of the present invention is not particularly limited. For example, the conductive fine particles of the present invention are added to the binder resin, and the mixture is uniformly mixed and dispersed. Examples thereof include a method for producing an anisotropic conductive ink, an anisotropic conductive adhesive, and the like. Further, the conductive fine particles of the present invention are added to the binder resin and uniformly dispersed or dissolved by heating, and a predetermined film thickness is applied to a release treatment surface of a release material such as release paper or release film. For example, a method for producing an anisotropic conductive film, an anisotropic conductive sheet or the like by coating may be used.
Moreover, it is good also as an anisotropic conductive material by using separately the said binder resin and the electroconductive fine particles of this invention, without mixing.
本発明の導電性微粒子、又は、本発明の異方性導電材料によって接続されている接続構造体もまた、本発明の１つである。
本発明の接続構造体は、一対の回路基板間に、本発明の導電性微粒子又は本発明の異方性導電材料を充填することにより、一対の回路基板間を電気接続させた接続構造体である。
A connection structure connected by the conductive fine particles of the present invention or the anisotropic conductive material of the present invention is also one aspect of the present invention.
The connection structure of the present invention is a connection structure in which a pair of circuit boards are electrically connected by filling the conductive fine particles of the present invention or the anisotropic conductive material of the present invention between a pair of circuit boards. is there.
本発明によれば、信頼性が高い電気接続ができる導電性微粒子を提供することができる。また、本発明によれば、該導電性微粒子を含有する異方性導電材料、及び、該導電性微粒子又は該異方性導電材料によって接続された接続構造体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the electroconductive fine particles which can make highly reliable electrical connection can be provided. Further, according to the present invention, it is possible to provide an anisotropic conductive material containing the conductive fine particles, and a connection structure connected by the conductive fine particles or the anisotropic conductive material.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
（１）樹脂微粒子の作製
ポリビニルアルコールを３重量％含む水溶液８００重量部に、ジビニルベンゼン７０重量部、トリメチロールプロパントリメタクリレート３０重量部、過酸化ベンゾイル２重量部を加え、混合物を攪拌した。窒素気流下にて、混合物を撹拌しながら８０℃で、１５時間重合し、樹脂微粒子を得た。
得られた樹脂微粒子を蒸留水及びメタノールで洗浄した後、分級操作を行った。樹脂微粒子の平均粒子径は４．１μｍ、変動係数は５．０％であった。
Example 1
(1) Preparation of resin fine particles 70 parts by weight of divinylbenzene, 30 parts by weight of trimethylolpropane trimethacrylate and 2 parts by weight of benzoyl peroxide were added to 800 parts by weight of an aqueous solution containing 3% by weight of polyvinyl alcohol, and the mixture was stirred. Under a nitrogen stream, the mixture was polymerized at 80 ° C. with stirring for 15 hours to obtain resin fine particles.
The obtained resin fine particles were washed with distilled water and methanol, and then classified. The average particle size of the resin fine particles was 4.1 μm, and the coefficient of variation was 5.0%.
得られた樹脂微粒子１０ｇをエッチング処理し水洗した。パラジウムイオンを吸着させた樹脂微粒子を０．５重量％のジメチルアミンボラン水溶液に添加し、パラジウムが付与された樹脂微粒子を得た。 10 g of the obtained resin fine particles were etched and washed with water. Resin fine particles adsorbed with palladium ions were added to a 0.5% by weight dimethylamine borane aqueous solution to obtain resin fine particles to which palladium was imparted.
（２）ニッケル層の形成
パラジウムが付与された樹脂微粒子１０ｇを、イオン交換水１２００ｍＬに分散させ、めっき安定剤４ｍＬを添加し、懸濁液Ａを作製した。次いで、硫酸ニッケル４５０ｇ／Ｌと、次亜リン酸ナトリウム１５０ｇ／Ｌと、クエン酸ナトリウム１１６ｇ／Ｌと、めっき安定剤６ｍＬとの混合溶液１２０ｍＬをアンモニアでｐＨ８．５に調整し、前期めっき液を作製した。懸濁液Ａに、８１ｍＬ／分の添加速度で定量ポンプを通して、前期めっき液を添加した。その後、水溶液のｐＨが安定するまで攪拌し、水素の発泡が停止するまで、前期めっき工程を行った。前期めっき工程が終了した後、めっき液をろ過し、粒子を蒸留水及びメタノールで洗浄した。洗浄した粒子を、イオン交換水１２００ｍＬに分散させ、懸濁液Ｂを作製した。
(2) Formation of nickel layer 10 g of resin fine particles provided with palladium were dispersed in 1200 mL of ion-exchanged water, and 4 mL of a plating stabilizer was added to prepare a suspension A. Next, 120 mL of a mixed solution of 450 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 116 g / L of sodium citrate, and 6 mL of a plating stabilizer was adjusted to pH 8.5 with ammonia. Produced. The plating solution was added to the suspension A through a metering pump at an addition rate of 81 mL / min. Thereafter, stirring was performed until the pH of the aqueous solution was stabilized, and the previous plating step was performed until hydrogen foaming stopped. After the previous plating process was completed, the plating solution was filtered, and the particles were washed with distilled water and methanol. The washed particles were dispersed in 1200 mL of ion exchange water to prepare a suspension B.
次いで、硫酸ニッケル４５０ｇ／Ｌと、次亜リン酸ナトリウム１５０ｇ／Ｌと、クエン酸ナトリウム１１６ｇ／Ｌと、めっき安定剤３５ｍＬとの混合溶液６５０ｍＬをアンモニアでｐＨ９．５に調整し、後期めっき液を作製した。懸濁液Ｂに、２７ｍＬ／分の添加速度で定量ポンプを通して、後期めっき液を添加した。その後、ｐＨが安定するまで攪拌し、水素の発泡が停止するまで、後期めっき工程を行った。
次いで、めっき液をろ過し、粒子を蒸留水及びメタノールで洗浄した後、８０℃の真空乾燥機で乾燥させ、ニッケル層が形成された樹脂微粒子を得た。
なお、蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ−８００ＨＳ」）により測定すると、ニッケル層のニッケル含有率は９７重量％であった。
Next, 650 mL of a mixed solution of 450 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 116 g / L of sodium citrate, and 35 mL of a plating stabilizer is adjusted to pH 9.5 with ammonia. Produced. Late plating solution was added to suspension B through a metering pump at an addition rate of 27 mL / min. Then, it stirred until pH was stabilized and the latter plating process was performed until hydrogen foaming stopped.
Next, the plating solution was filtered, and the particles were washed with distilled water and methanol and then dried with a vacuum dryer at 80 ° C. to obtain resin fine particles on which a nickel layer was formed.
In addition, the nickel content of the nickel layer was 97% by weight as measured by a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu Corporation).
（３）酸化セリウム層の形成
ニッケル層が形成された樹脂微粒子１０ｇを、１重量％の硫酸セリウム水溶液１Ｌに添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。硫酸セリウム水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化セリウム層が形成された導電性微粒子を作製した。
なお、エネルギー分散型Ｘ線分光器により測定すると、ニッケル層の表面に酸化セリウム層が形成されていることが確認された。また、得られた導電性微粒子のニッケル層の厚さは、０．１μｍ、酸化セリウム層の厚さは、０．００５μｍであった。
(3) Formation of cerium oxide layer 10 g of resin fine particles on which a nickel layer was formed were added to 1 L of a 1% by weight cerium sulfate aqueous solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous cerium sulfate solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles on which a cerium oxide layer was formed.
In addition, when measured with an energy dispersive X-ray spectrometer, it was confirmed that a cerium oxide layer was formed on the surface of the nickel layer. Moreover, the thickness of the nickel layer of the obtained conductive fine particles was 0.1 μm, and the thickness of the cerium oxide layer was 0.005 μm.
（実施例２）
実施例１と同様にして得られたニッケル層が形成された樹脂微粒子１０ｇを、１重量％のシュウ酸チタンカリウム水溶液１Ｌに添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。シュウ酸チタンカリウム水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化チタン層が形成された導電性微粒子を作製した。
なお、エネルギー分散型Ｘ線分光器により測定すると、ニッケル層の表面に酸化チタン層が形成されていることが確認された。また、得られた導電性微粒子のニッケル層の厚さは、０．１μｍ、酸化チタン層の厚さは、０．００５μｍであった。
(Example 2)
10 g of resin fine particles formed with a nickel layer obtained in the same manner as in Example 1 were added to 1 L of a 1% by weight aqueous solution of potassium potassium oxalate, and stirred for 1 hour while maintaining the liquid temperature at 50 ° C. . After filtering the aqueous potassium potassium oxalate solution and washing the particles with distilled water, the particles were dried with a vacuum dryer at 80 ° C. to produce conductive fine particles on which a titanium oxide layer was formed.
In addition, when measured with the energy dispersive X-ray spectrometer, it was confirmed that a titanium oxide layer was formed on the surface of the nickel layer. Moreover, the thickness of the nickel layer of the obtained conductive fine particles was 0.1 μm, and the thickness of the titanium oxide layer was 0.005 μm.
（実施例３）
ニッケル層の形成において、前期めっき液のｐＨを８．０に変更し、後期めっき液のｐＨを９．０に変更したこと以外は、実施例１と同様に導電性微粒子を作製した。
なお、蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ−８００ＨＳ」）により測定すると、ニッケル層のニッケル含有率は９６重量％であった。また、ニッケル層の厚さは、０．１μｍ、酸化セリウム層の厚さは、０．００５μｍであった。
(Example 3)
In the formation of the nickel layer, conductive fine particles were produced in the same manner as in Example 1 except that the pH of the first plating solution was changed to 8.0 and the pH of the latter plating solution was changed to 9.0.
In addition, the nickel content of the nickel layer was 96% by weight as measured by a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu Corporation). Moreover, the thickness of the nickel layer was 0.1 μm, and the thickness of the cerium oxide layer was 0.005 μm.
（実施例４）
ニッケル層の形成において、前期めっき液のｐＨを８．０に変更し、後期めっき液のｐＨを９．０に変更したこと以外は、実施例２と同様に導電性微粒子を作製した。
なお、蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ−８００ＨＳ」）により測定すると、ニッケル層のニッケル含有率は９６重量％であった。また、ニッケル層の厚さは、０．１μｍ、酸化チタン層の厚さは、０．００５μｍであった。
Example 4
In the formation of the nickel layer, conductive fine particles were prepared in the same manner as in Example 2 except that the pH of the first plating solution was changed to 8.0 and the pH of the latter plating solution was changed to 9.0.
In addition, the nickel content of the nickel layer was 96% by weight as measured by a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu Corporation). Moreover, the thickness of the nickel layer was 0.1 μm, and the thickness of the titanium oxide layer was 0.005 μm.
（実施例５）
リン酸モノドデシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例１と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化セリウム層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ドデシル基が形成されていることが確認された。
(Example 5)
1 g of phosphoric acid monododecyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 1 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the cerium oxide layer.
In addition, when analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that dodecyl groups were formed on the surface of the conductive fine particles.
（実施例６）
リン酸モノドデシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例２と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化チタン層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ドデシル基が形成されていることが確認された。
(Example 6)
1 g of phosphoric acid monododecyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 2 was added to an aqueous tetrahydrofuran solution, and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the titanium oxide layer.
In addition, when analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that dodecyl groups were formed on the surface of the conductive fine particles.
（実施例７）
リン酸モノへキシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例１と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化セリウム層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ヘキシル基が形成されていることが確認された。
(Example 7)
1 g of monohexyl phosphate was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 1 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the cerium oxide layer.
When analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that hexyl groups were formed on the surface of the conductive fine particles.
（実施例８）
リン酸モノヘキシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例２と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化チタン層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ヘキシル基が形成されていることが確認された。
(Example 8)
1 g of phosphoric acid monohexyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 2 was added to an aqueous tetrahydrofuran solution, and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water, and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the titanium oxide layer.
When analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that hexyl groups were formed on the surface of the conductive fine particles.
（実施例９）
リン酸モノヘキサデシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例１と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化セリウム層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ヘキサデシル基が形成されていることが確認された。
Example 9
1 g of phosphoric acid monohexadecyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50 wt%: 50 wt%). 10 g of conductive fine particles obtained in the same manner as in Example 1 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the cerium oxide layer.
When analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that hexadecyl groups were formed on the surface of the conductive fine particles.
（実施例１０）
リン酸モノヘキサデシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例２と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化チタン層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ヘキサデシル基が形成されていることが確認された。
(Example 10)
1 g of phosphoric acid monohexadecyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50 wt%: 50 wt%). 10 g of conductive fine particles obtained in the same manner as in Example 2 was added to an aqueous tetrahydrofuran solution, and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the titanium oxide layer.
When analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that hexadecyl groups were formed on the surface of the conductive fine particles.
（実施例１１）
リン酸モノドデシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例３と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化セリウム層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ドデシル基が形成されていることが確認された。
(Example 11)
1 g of phosphoric acid monododecyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 3 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the cerium oxide layer.
In addition, when analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that dodecyl groups were formed on the surface of the conductive fine particles.
（実施例１２）
リン酸モノドデシルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例４と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化チタン層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ドデシル基が形成されていることが確認された。
Example 12
1 g of phosphoric acid monododecyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 4 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the titanium oxide layer.
In addition, when analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that dodecyl groups were formed on the surface of the conductive fine particles.
（実施例１３）
リン酸モノブチルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例３と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化セリウム層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ブチル基が形成されていることが確認された。
(Example 13)
1 g of phosphoric acid monobutyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 3 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the cerium oxide layer.
In addition, when analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that a butyl group was formed on the surface of the conductive fine particles.
（実施例１４）
リン酸モノブチルエステル１ｇを、テトラヒドロフラン水溶液（水：テトラヒドロフラン＝５０重量％：５０重量％）１Ｌに溶解させた。実施例４と同様にして得られた導電性微粒子１０ｇを、テトラヒドロフラン水溶液に添加し、水溶液の液温を５０℃に保ちながら、１時間攪拌した。テトラヒドロフラン水溶液をろ過し、粒子を蒸留水で洗浄した後、８０℃の真空乾燥機で乾燥させ、酸化チタン層の表面にアルキル基を有する導電性微粒子を作製した。
なお、飛行時間型二次イオン質量分析装置（ＴＯＦ−ＳＩＭＳ）により分析すると、導電性微粒子の表面に、ブチル基が形成されていることが確認された。
(Example 14)
1 g of phosphoric acid monobutyl ester was dissolved in 1 L of an aqueous tetrahydrofuran solution (water: tetrahydrofuran = 50% by weight: 50% by weight). 10 g of conductive fine particles obtained in the same manner as in Example 4 was added to an aqueous tetrahydrofuran solution and stirred for 1 hour while maintaining the liquid temperature of the aqueous solution at 50 ° C. The aqueous tetrahydrofuran solution was filtered, and the particles were washed with distilled water, and then dried with a vacuum dryer at 80 ° C. to produce conductive fine particles having an alkyl group on the surface of the titanium oxide layer.
In addition, when analyzed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), it was confirmed that a butyl group was formed on the surface of the conductive fine particles.
（比較例１）
（１）樹脂微粒子の作製
ポリビニルアルコールを３重量％含む水溶液８００重量部に、ジビニルベンゼン７０重量部、トリメチロールプロパントリメタクリレート３０重量部、過酸化ベンゾイル２重量部を加え、混合物を攪拌した。窒素気流下にて、混合物を撹拌しながら８０℃で、１５時間重合し、樹脂微粒子を得た。
得られた樹脂微粒子を蒸留水及びメタノールで洗浄した後、分級操作を行った。樹脂微粒子の平均粒子径は４．１μｍ、変動係数は５．０％であった。
(Comparative Example 1)
(1) Preparation of resin fine particles 70 parts by weight of divinylbenzene, 30 parts by weight of trimethylolpropane trimethacrylate and 2 parts by weight of benzoyl peroxide were added to 800 parts by weight of an aqueous solution containing 3% by weight of polyvinyl alcohol, and the mixture was stirred. Under a nitrogen stream, the mixture was polymerized at 80 ° C. with stirring for 15 hours to obtain resin fine particles.
The obtained resin fine particles were washed with distilled water and methanol, and then classified. The average particle size of the resin fine particles was 4.1 μm, and the coefficient of variation was 5.0%.
得られた樹脂微粒子１０ｇをエッチング処理し水洗した。パラジウムイオンを吸着させた樹脂微粒子を０．５重量％のジメチルアミンボラン水溶液に添加し、パラジウムが付与された樹脂微粒子を得た。 10 g of the obtained resin fine particles were etched and washed with water. Resin fine particles adsorbed with palladium ions were added to a 0.5% by weight dimethylamine borane aqueous solution to obtain resin fine particles to which palladium was imparted.
（２）ニッケル層の形成
パラジウムが付与された樹脂微粒子１０ｇを、イオン交換水１２００ｍＬに分散させ、めっき安定剤４ｍＬを添加し、水溶液を調整した。この水溶液に硫酸ニッケル４５０ｇ／Ｌと、次亜リン酸ナトリウム１５０ｇ／Ｌと、クエン酸ナトリウム１１６ｇ／Ｌと、めっき安定剤６ｍＬとの混合溶液１２０ｍＬを８１ｍＬ／分の添加速度で定量ポンプを通して添加した。その後、水溶液のｐＨが安定するまで攪拌し、水素の発泡が停止するまで、前期めっき工程を行った。
(2) Formation of nickel layer 10 g of resin fine particles provided with palladium were dispersed in 1200 mL of ion-exchanged water, and 4 mL of a plating stabilizer was added to prepare an aqueous solution. To this aqueous solution, 120 mL of a mixed solution of nickel sulfate 450 g / L, sodium hypophosphite 150 g / L, sodium citrate 116 g / L, and plating stabilizer 6 mL was added at a rate of 81 mL / min through a metering pump. . Thereafter, stirring was performed until the pH of the aqueous solution was stabilized, and the previous plating step was performed until hydrogen foaming stopped.
次いで、前期めっき工程が終了した水溶液に、硫酸ニッケル４５０ｇ／Ｌと、次亜リン酸ナトリウム１５０ｇ／Ｌと、クエン酸ナトリウム１１６ｇ／Ｌと、めっき安定剤３５ｍＬとの混合溶液６５０ｍＬを２７ｍＬ／分の添加速度で定量ポンプを通して添加した。その後、ｐＨが安定するまで攪拌し、水素の発泡が停止するまで、後期めっき工程を行った。
次いで、めっき液をろ過し、粒子を蒸留水及びメタノールで洗浄した後、８０℃の真空乾燥機で乾燥させ、ニッケル層が形成された樹脂微粒子を得た。
なお、蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ−８００ＨＳ」）により測定すると、ニッケル層のニッケル含有率は９４重量％であった。また、ニッケル層の厚さは、０．１μｍであった。
Next, 650 mL of a mixed solution of 450 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 116 g / L of sodium citrate, and 35 mL of a plating stabilizer was added to the aqueous solution after the previous plating step was 27 mL / min. It was added through a metering pump at an addition rate. Then, it stirred until pH was stabilized and the latter plating process was performed until hydrogen foaming stopped.
Next, the plating solution was filtered, and the particles were washed with distilled water and methanol and then dried with a vacuum dryer at 80 ° C. to obtain resin fine particles on which a nickel layer was formed.
In addition, the nickel content of the nickel layer was 94% by weight as measured by a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu Corporation). The thickness of the nickel layer was 0.1 μm.
（比較例２）
比較例１で得られたニッケル層が形成された樹脂微粒子を使用したこと以外は、実施例１と同様に、導電性微粒子を作製した。
(Comparative Example 2)
Conductive fine particles were produced in the same manner as in Example 1, except that the resin fine particles formed with the nickel layer obtained in Comparative Example 1 were used.
（比較例３）
比較例１で得られたニッケル層が形成された樹脂微粒子を使用したこと以外は、実施例２と同様に、導電性微粒子を作製した。
(Comparative Example 3)
Conductive fine particles were produced in the same manner as in Example 2, except that the resin fine particles formed with the nickel layer obtained in Comparative Example 1 were used.
（比較例４）
実施例１で得られたニッケル層が形成された樹脂微粒子を導電性微粒子として使用した。
(Comparative Example 4)
The resin fine particles formed with the nickel layer obtained in Example 1 were used as conductive fine particles.
＜評価＞
実施例１〜１４及び比較例１〜４で得られた導電性微粒子について以下の評価を行った。結果を表１に示した。
<Evaluation>
The following evaluation was performed about the electroconductive fine particles obtained in Examples 1-14 and Comparative Examples 1-4. The results are shown in Table 1.
（１）水に対する表面接触角の測定
導電性微粒子の水に対する表面接触角は、全自動接触角測定装置（データフィジックス社製「ＯＣＡ３５」）を用いて測定した。即ち、得られた導電性微粒子１ｇをスライドガラス上に置き、ニードルを導電性微粒子表面に近づけ、ニードルを用いて純水３μＬを導電性微粒子表面に付着させた。純水が付着した導電性微粒子を撮影した画像を解析し、表面接触角を測定した。
(1) Measurement of surface contact angle to water The surface contact angle of conductive fine particles to water was measured using a fully automatic contact angle measuring device (“OCA35” manufactured by Data Physics Co., Ltd.). That is, 1 g of the obtained conductive fine particles were placed on a slide glass, the needle was brought close to the surface of the conductive fine particle, and 3 μL of pure water was attached to the surface of the conductive fine particle using the needle. An image obtained by photographing the conductive fine particles to which pure water adhered was analyzed, and the surface contact angle was measured.
（２）体積抵抗率の測定
導電性微粒子の体積抵抗率は、三菱化学社製「粉体抵抗率測定システム」を用い、導電性微粒子２．５ｇに２０ｋＮの荷重を与えた条件下で測定した。
(2) Measurement of volume resistivity The volume resistivity of the conductive fine particles was measured using a “powder resistivity measurement system” manufactured by Mitsubishi Chemical Corporation under a condition in which a load of 20 kN was applied to 2.5 g of the conductive fine particles. .
（３）異方性導電フィルムの作製
バインダー樹脂としてエポキシ樹脂（油化シェルエポキシ社製「エピコート８２８」）１００重量部、トリスジメチルアミノエチルフェノール２重量部、及び、トルエン１００重量部を、遊星式攪拌機を用いて充分に混合し、混合物を得た。得られた混合物を、離型フィルム上に乾燥後の厚さが１０μｍとなるように塗布し、トルエンを揮発させて接着性フィルム１を得た。
次いで、バインダー樹脂としてエポキシ樹脂（油化シェルエポキシ社製「エピコート８２８」）１００重量部、トリスジメチルアミノエチルフェノール２重量部、及び、トルエン１００重量部に、導電性微粒子を添加し、遊星式攪拌機を用いて充分に混合し、混合物を得た。得られた混合物を、離型フィルム上に乾燥後の厚さが７μｍとなるように塗布し、トルエンを揮発させて導電性微粒子を含有する接着性フィルム２を得た。なお、接着性フィルム２における導電性微粒子の含有量は５万個／ｃｍ２となるように調整した。
得られた接着性フィルム１と接着性フィルム２とを常温でラミネートし、２層構造を有する厚さ１７μｍの異方性導電フィルムを得た。
(3) Production of anisotropic conductive film 100 parts by weight of epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.), 2 parts by weight of trisdimethylaminoethylphenol, and 100 parts by weight of toluene as a binder resin The mixture was sufficiently mixed using a stirrer to obtain a mixture. The obtained mixture was applied onto a release film so that the thickness after drying was 10 μm, and toluene was volatilized to obtain an adhesive film 1.
Next, conductive fine particles were added to 100 parts by weight of an epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.), 2 parts by weight of trisdimethylaminoethylphenol, and 100 parts by weight of toluene as a binder resin, and a planetary stirrer Was mixed well to obtain a mixture. The obtained mixture was applied onto a release film so that the thickness after drying was 7 μm, and toluene was volatilized to obtain an adhesive film 2 containing conductive fine particles. In addition, the content of the conductive fine particles in the adhesive film 2 was adjusted to be 50,000 / cm 2 .
The obtained adhesive film 1 and adhesive film 2 were laminated at room temperature to obtain a 17 μm thick anisotropic conductive film having a two-layer structure.
（４）接続構造体の作製
得られた異方性導電フィルムを５ｍｍ×５ｍｍの大きさに切断した。切断した異方性導電フィルムを、一方に抵抗測定用の引き回し線を有するアルミニウム電極（高さ０．２μｍ、Ｌ／Ｓ＝２０μｍ／２０μｍ）が形成されたガラス基板のアルミニウム電極側のほぼ中央に貼り付けた。次いで、同じアルミニウム電極が形成されたガラス基板を、電極同士が重なるように位置合わせをしてから貼り合わせた。このガラス基板の積層体を、１０Ｎ、１８０℃の圧着条件で熱圧着し、接続構造体を得た。
(4) Preparation of connection structure The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. At the center of the glass substrate on which the aluminum electrode (height 0.2 μm, L / S = 20 μm / 20 μm) having a resistance measurement lead wire formed on one side is formed on the cut anisotropic conductive film. Pasted. Next, the glass substrates on which the same aluminum electrodes were formed were bonded together after being aligned so that the electrodes overlap each other. The laminated body of the glass substrates was thermocompression bonded under pressure bonding conditions of 10N and 180 ° C. to obtain a connection structure.
（５）接続抵抗値の測定
得られた接続構造体の対向する電極間の接続抵抗値を４端子法により測定した。また、ＰＣＴ試験後の接続構造体の接続抵抗値を同様に測定した。なお、ＰＣＴ試験とは、得られた接続構造体を８５℃、相対湿度８５％の恒温恒湿器内に１００時間保管する加速試験を意味する。
(5) Measurement of connection resistance value The connection resistance value between the opposing electrodes of the obtained connection structure was measured by a four-terminal method. Moreover, the connection resistance value of the connection structure after a PCT test was measured similarly. The PCT test means an accelerated test in which the obtained connection structure is stored in a constant temperature and humidity chamber at 85 ° C. and a relative humidity of 85% for 100 hours.
本発明によれば、信頼性が高い電気接続ができる導電性微粒子を提供することができる。また、本発明によれば、該導電性微粒子を含有する異方性導電材料、及び、該導電性微粒子又は該異方性導電材料によって接続された接続構造体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the electroconductive fine particles which can make highly reliable electrical connection can be provided. Further, according to the present invention, it is possible to provide an anisotropic conductive material containing the conductive fine particles, and a connection structure connected by the conductive fine particles or the anisotropic conductive material.
Claims (8)
前記ニッケル層のニッケル含有率が９６重量％以上であり、かつ、前記ニッケル層の表面に、セリウム、又は、チタンを含有する金属酸化物層が形成されている
ことを特徴とする導電性微粒子。 Conductive fine particles having a nickel layer formed on the surface of the substrate fine particles,
Conductive fine particles, wherein the nickel layer has a nickel content of 96% by weight or more, and a metal oxide layer containing cerium or titanium is formed on the surface of the nickel layer.
A connection structure which is connected using the anisotropic conductive material according to claim 6.
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