CN116841120A - Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof - Google Patents
Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116841120A CN116841120A CN202310598138.5A CN202310598138A CN116841120A CN 116841120 A CN116841120 A CN 116841120A CN 202310598138 A CN202310598138 A CN 202310598138A CN 116841120 A CN116841120 A CN 116841120A
- Authority
- CN
- China
- Prior art keywords
- silver
- groups
- particles
- component
- composition
- 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.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 76
- 239000004332 silver Substances 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000001259 photo etching Methods 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 91
- 239000000178 monomer Substances 0.000 claims abstract description 44
- -1 photoinitiator Substances 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 10
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- GCOWTRMQPXDRQQ-UHFFFAOYSA-N [Mg].[Cu].[Zn] Chemical compound [Mg].[Cu].[Zn] GCOWTRMQPXDRQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000002923 metal particle Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 5
- WXENESFPQCWDHY-UHFFFAOYSA-M silver;2-ethylhexanoate Chemical compound [Ag+].CCCCC(CC)C([O-])=O WXENESFPQCWDHY-UHFFFAOYSA-M 0.000 claims description 5
- PLGAYGHFBSTWCA-UHFFFAOYSA-N 10-phenylsulfanylacridin-9-one Chemical compound C1(=CC=CC=C1)SN1C=2C=CC=CC2C(C2=CC=CC=C12)=O PLGAYGHFBSTWCA-UHFFFAOYSA-N 0.000 claims description 4
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 4
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 claims description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 claims description 3
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 3
- HOTUFGDVXNSGLQ-UHFFFAOYSA-N CN(C)C1=CC=C(C=CC2=N[S+](C=CC(C=C3)=CC=C3N(C)C)C=C2)C=C1 Chemical compound CN(C)C1=CC=C(C=CC2=N[S+](C=CC(C=C3)=CC=C3N(C)C)C=C2)C=C1 HOTUFGDVXNSGLQ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- FXYGHKTWVGLQJG-UHFFFAOYSA-N [Sb].[Cu].[Sn] Chemical compound [Sb].[Cu].[Sn] FXYGHKTWVGLQJG-UHFFFAOYSA-N 0.000 claims description 3
- 229940072056 alginate Drugs 0.000 claims description 3
- 229920000615 alginic acid Polymers 0.000 claims description 3
- 235000010443 alginic acid Nutrition 0.000 claims description 3
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003211 polymerization photoinitiator Substances 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 3
- TYTYIUANSACAEM-UHFFFAOYSA-M silver;2,4,6-trinitrophenolate Chemical compound [Ag+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O TYTYIUANSACAEM-UHFFFAOYSA-M 0.000 claims description 3
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 claims description 3
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 claims description 3
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 25
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 2
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- MNMVKGDEKPPREK-UHFFFAOYSA-N trimethyl(prop-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=C MNMVKGDEKPPREK-UHFFFAOYSA-N 0.000 description 2
- PJAKWOZHTFWTNF-UHFFFAOYSA-N (2-nonylphenyl) prop-2-enoate Chemical class CCCCCCCCCC1=CC=CC=C1OC(=O)C=C PJAKWOZHTFWTNF-UHFFFAOYSA-N 0.000 description 1
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- KCKJMQMEWMHVCH-UHFFFAOYSA-N 1-butoxy-2-[2-(2-hydroxyethoxy)ethoxy]ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCOC(O)COCCOCCO KCKJMQMEWMHVCH-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- IVZMCRURFJCDCS-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCCCCCO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCCCCCO IVZMCRURFJCDCS-UHFFFAOYSA-N 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XEOUTFBSZIJVCK-UHFFFAOYSA-N prop-2-enyl 2-cyclohexylpropanoate Chemical compound C=CCOC(=O)C(C)C1CCCCC1 XEOUTFBSZIJVCK-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- OTYBJBJYBGWBHB-UHFFFAOYSA-N trimethylsilyl prop-2-enoate Chemical compound C[Si](C)(C)OC(=O)C=C OTYBJBJYBGWBHB-UHFFFAOYSA-N 0.000 description 1
- 238000000233 ultraviolet lithography Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of photosensitive silver paste, and discloses a composition for preparing ultraviolet sensitive photoetching silver paste, the ultraviolet sensitive photoetching silver paste, a preparation method and application thereof. The composition comprises a component A and a component B, wherein the component A comprises conductive particles and an inorganic binder which is optionally contained; the component B contains photopolymerization resin, photosensitive monomer, photoinitiator, photosensitizer, additive and optionally organic silver salt and organic solvent. When the ultraviolet sensitive photoetching silver paste prepared by the composition provided by the invention is used for preparing the microelectrode wire, the upper layer and the lower layer can be both solidified, the undercut and the edge curling phenomena are avoided, and a stable high-resolution line width of not more than 30 mu m is formed; meanwhile, the prepared microelectrode wire has higher conductivity and stronger adhesive force with the substrate.
Description
Technical Field
The invention relates to the technical field of photosensitive silver paste, in particular to a composition for preparing ultraviolet sensitive photoetching silver paste, the ultraviolet sensitive photoetching silver paste, a preparation method and application thereof.
Background
Current electronic systems are continually pursuing advanced performance goals of miniaturization, versatility, high density, high transmission speeds, and high reliability. This requires that the electrode wiring inside the electronic component be high-density interconnected, the electrodes must be made finer, and good electrical performance still be maintained. At the same time, the high density interconnection of electrode wiring also facilitates the integration of complex process monitoring in smart devices and related subsystems (e.g., digital signal processors, motherboards, microcontrollers, etc.).
A conventional method of forming a desired electrode pattern on the surface of a substrate is a screen printing conductive silver paste method. Screen printing is a stencil printing method in which conductive silver paste is applied to the surface of a substrate through a fine mesh screen with a doctor blade. Although screen printing has the advantages of simplicity, rapidity, mass production and low cost; however, when the screen holes become finer, problems of uneven printing paste and burrs at the edges of the electrode lines are easily caused, so that the reliability of the circuit becomes poor. The minimum line width resolution currently achievable for screen printing is about 40 μm (Hyun WJ, lim S, ahn B Y, et al screen Printing of Highly Loaded Silver Inks on Plastic Substrates Using Silicon stencils acs appl. Screen printing has difficulty in forming a line system having a specific line width below 40 μm while forming a high-density pattern.
And the photoetching conductive silver paste rule can remove the limitation of the line width resolution ratio and meet the requirement of smaller-size patterns. The method of lithographically conducting silver paste is by depositing a paste on a substrate (e.g., al 2 O 3 A substrate), drying the substrate under predetermined conditions, and exposing the silver paste film using a UV exposure apparatus having a photomask, followed by proper developmentA method of solution developing to remove uncured portions of the silver paste film masked by the photomask and firing the remaining cured layer at a predetermined temperature to form a patterned electrode.
CN108182985A, JP2002311581A, US20200278609A1 and KR1020140094030a disclose a method of forming a fine electrode wiring pattern by photolithographic exposure using a photosensitive conductive silver paste. However, when the above-mentioned prior art photosensitive silver paste is used to manufacture electrode patterns having a line diameter of not more than 30 μm, the electrode lines thus manufactured often have insufficient photosensitive curing of the underlying silver paste, resulting in undercut phenomenon in which the underlying line width is narrower than the overlying line width.
The undercut phenomenon may cause a decrease in the adhesive strength of the electrode on the substrate, thereby making the electrode wire easily detached from the substrate, resulting in a short circuit and a decrease in resolution. In addition, the undercut phenomenon may cause an edge curl phenomenon of the upper edge portion of the electrode wire after firing, which may cause an electronic breakdown of a local current.
Disclosure of Invention
The invention aims to overcome the defect of lower electrode wiring resolution caused by undercut and edge curl in the existing photosensitive photoetching silver paste when an electrode line is prepared.
In order to achieve the above object, a first aspect of the present invention provides a composition for preparing an ultraviolet-sensitive optical silver paste, the composition comprising a component a and a component B,
the component A contains conductive particles and an inorganic binder which is optionally contained; the conductive particles contain particles I and particles II; the particles I are selected from at least 2 of flake silver powder, spherical silver powder and nano silver powder, the volume average particle size of the flake silver powder and the spherical silver powder is 0.6-10 mu m, and the volume average particle size of the nano silver powder is 50-500nm; the particles II are selected from at least one of metal simple substance particles and alloy particles, the volume average particle diameter of the particles II is 1-10 mu m, and the melting point is 100-650 ℃;
the component B contains photopolymerization resin, photosensitive monomer, photoinitiator, photosensitizer, additive and optionally organic silver salt and organic solvent; the additive comprises a dispersing agent, an antioxidant, a plasticizer, a leveling agent and a silane coupling agent;
The composition comprises, based on the total weight of the composition, 50-80wt% of conductive particles, 0-8wt% of inorganic binder, 5-20wt% of photopolymerized resin, 0-10wt% of organic silver salt, 5-15wt% of photosensitive monomer, 0.01-7wt% of photoinitiator, 0.01-3wt% of photosensitizer, 0-15wt% of organic solvent, 0.01-5wt% of additive, and
the content of the component A is 50-80wt%; the content of the component B is 20-50wt%.
Preferably, the particle I is a mixture with a content weight ratio of 1:0.5-1.5:0.5 to 1.5, the spherical silver powder and the nano silver powder.
Preferably, the content weight ratio of the particles I to the particles II is 10-15:1.
preferably, the inorganic binder is selected from B 2 O 3 、PbO-B 2 O 3 -SiO 2 ZnO-based glass frit and Bi 2 O 3 -B 2 O 3 -SiO 2 At least one of the ZnO glass powders.
Preferably, the metal element in the metal element particles is selected from at least one of indium, tin, bismuth, cadmium, lead and antimony.
Preferably, the alloy in the alloy particles is selected from at least one of a bismuth-tin alloy, a lead-tin alloy, a tin-antimony-copper alloy, and a zinc-magnesium-copper alloy.
Preferably, the particle II is a mixture with a content weight ratio of 1:0.1-1:0.4-1.6:0.1 to 1.5 of bismuth powder, tin powder, antimony powder and zinc-magnesium-copper alloy powder.
Preferably, the photopolymerizable resin is selected from at least one of an acrylic monomer homopolymer and an acrylic monomer copolymer.
According to a preferred embodiment, the acrylic monomer copolymer has a number average molecular weight of 5000 to 100000g/mol and an acid value of 50 to 300mgKOH/g.
According to another preferred embodiment, the acrylic monomer copolymer contains at least one of structural unit a and structural unit B; and the structural unit A is an acrylic structural unit containing an epoxy group, and the structural unit B is an acrylic structural unit containing a siloxane group.
According to a particularly preferred embodiment, the content of structural units A is from 10 to 50% by weight and the content of structural units B is from 5 to 50% by weight.
Preferably, the photosensitive monomer is selected from at least one of acrylate monomers with a molecular weight of 360-600 g/mol.
Further preferably, the photosensitive monomer is selected from at least one of decaethoxylated bisphenol a diacrylate, tetraethoxylated bisphenol a diacrylate, diethoxylated bisphenol a dimethacrylate and bisphenol a dimethacrylate.
Preferably, the photoinitiator is selected from at least one of radical polymerization photoinitiators.
More preferably, the photoinitiator is selected from at least one of phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 4-azidobenzo-hemiketone, N-phenylthioacridone, and benzothiazole disulfide.
Preferably, the photosensitizer is selected from at least one of N-phenylethanolamine, 2, 4-diethylthioxanthone, isopropylthioxanthone, 2, 3-bis (4-dimethylaminobenzoyl) cyclopentane, 2, 6-bis (4-dimethylaminobenzoyl) bis (dimethylamino) benzophenone, 4-bis (dimethylamino) dimethyl ketone, 2, 6-bis-p-dimethylaminobenzylidene indenone, 2- (p-dimethylaminophenyl vinyl) isothiazole, 1, 3-bis (4-dimethylaminophenyl vinyl) isothiazole, and 1, 3-bis (4-methylaminobenzyl) acetone.
Preferably, the organic silver salt is at least one selected from the group consisting of silver acetate, silver propionate, silver butyrate, silver oxalate, silver benzoate, silver 2-ethylhexanoate, silver picrate and silver alginate.
Preferably, the organic solvent is selected from at least one of terpineol, diethylene glycol butyl ether acetate, N-dimethylacetamide, N-methylformamide, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, dimethyl sulfoxide, ethoxy-2-propanol, ethylene glycol mono-N-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether acetate.
In a second aspect the present invention provides a method of preparing an ultraviolet sensitive lithographic silver paste using a composition as described in the first aspect, comprising: in a yellow light clean room with the pressure of 0.10-0.15 MPa:
(1) First mixing the components in the component A to obtain a mixture I; and
performing second mixing on each component in the component B to obtain a mixture II;
(2) And sequentially carrying out third mixing and fourth mixing on the mixture I and the mixture II.
Preferably, the conditions of the first mixing at least satisfy: the stirring is carried out under the stirring condition, the stirring rotating speed is 100-300rpm, the temperature is 20-60 ℃, and the time is 30-100min.
Preferably, the conditions of the second mixing at least satisfy: the stirring is carried out under the stirring condition, the stirring rotating speed is 200-500rpm, the temperature is 40-70 ℃, and the time is 30-100min.
According to a preferred embodiment, the conditions of the third mixing at least satisfy: the process is carried out in a gravity mixer at a rotation speed of 20-60rpm and a temperature of 50-70 ℃ for 50-90min.
According to another preferred embodiment, the fourth mixing conditions at least satisfy: the process is carried out in a mixer, the roll gap of the mixer is 20-50 mu m, the roll temperature is 50-60 ℃ and the time is 3-5h.
A third aspect of the present invention provides an ultraviolet-sensitive optical silver paste prepared by the method described in the foregoing second aspect.
A fourth aspect of the present invention provides a use of the ultraviolet-sensitive lithographic silver paste described in the foregoing third aspect for the preparation of a microelectrode.
Compared with the prior art, the invention has at least the following advantages:
(1) The ultraviolet photosensitive silver paste prepared by the composition provided by the invention can realize the preparation of conductive silver wires with the width not more than 30 mu m and electrode patterns with the wiring interval not more than 30 mu m.
(2) When the ultraviolet sensitive photoetching silver paste prepared by the composition provided by the invention is used for preparing the microelectrode wire, the upper layer and the lower layer can be both solidified, the undercut and the edge curling phenomena are avoided, and a stable high-resolution line width of not more than 30 mu m is formed; at the same time, the prepared microelectrode wire has the length of up to 2X 10 -4 High conductivity of omega cm, and strong adhesion between the substrate and the substrate.
(3) The method for preparing the ultraviolet photosensitive silver paste has better environmental friendliness, can reduce the material cost and is used for mass production in a more economic way.
Drawings
FIG. 1 is a preferred process flow for preparing a microelectrode provided by the present invention;
Fig. 2 is an SEM image of microelectrode wires prepared by ultraviolet-sensitive photoetching silver paste prepared in example 1;
fig. 3 is an SEM image of a cross section of a microelectrode prepared by using the ultraviolet-sensitive photolithography silver paste prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventors of the present invention have conducted intensive studies on photosensitive silver paste for preparing microelectrodes, and found that most of the photosensitive silver paste has undercut and edge curl phenomena. Generally, ultraviolet light cannot completely penetrate to the bottom of a silver paste line to induce high molecular polymerization, and unpolymerized parts at the bottom are easily dissolved by a developing solution, so that the silver line after development is in a shape with a wide upper layer and a narrow lower layer, and even is layered up and down, namely an undercut phenomenon. When the undercut phenomenon occurs, the effective contact area of the bottom is reduced, so that the bonding strength of the photosensitive silver paste and the substrate is weakened, and the electrode pattern is easily peeled off from the substrate; and the undercut phenomenon may also cause edge curl to occur at the upper edge portion after the electrode is fired. These phenomena all result in lower resolution of the electrode wiring pattern.
The inventors of the present invention have found out through extensive research that the shape and particle size of the conductive particles, the photopolymerizable resin, the photosensitive monomer, the photoinitiator, etc. are important factors affecting the wire resolution of the microelectrode. Meanwhile, the inventor also researches on the problem of the wiring reliability of the microelectrode, and based on the problem, the technical scheme of the invention is completed.
As previously described, a first aspect of the present invention provides a composition for preparing an ultraviolet-sensitive optical silver paste, the composition comprising a component A and a component B,
the component A contains conductive particles and an inorganic binder which is optionally contained; the conductive particles contain particles I and particles II; the particles I are selected from at least 2 of flake silver powder, spherical silver powder and nano silver powder, the volume average particle size of the flake silver powder and the spherical silver powder is 0.6-10 mu m, and the volume average particle size of the nano silver powder is 50-500nm; the particles II are selected from at least one of metal simple substance particles and alloy particles, the volume average particle diameter of the particles II is 1-10 mu m, and the melting point is 100-650 ℃;
the component B contains photopolymerization resin, photosensitive monomer, photoinitiator, photosensitizer, additive and optionally organic silver salt and organic solvent; the additive comprises a dispersing agent, an antioxidant, a plasticizer, a leveling agent and a silane coupling agent;
The composition comprises, based on the total weight of the composition, 50-80wt% of conductive particles, 0-8wt% of inorganic binder, 5-20wt% of photopolymerized resin, 0-10wt% of organic silver salt, 5-15wt% of photosensitive monomer, 0.01-7wt% of photoinitiator, 0.01-3wt% of photosensitizer, 0-15wt% of organic solvent, 0.01-5wt% of additive, and
the content of the component A is 50-80wt%; the content of the component B is 20-50wt%.
Preferably, the conductive particles are present in an amount of 60 to 70wt%, the inorganic binder is present in an amount of 4 to 6wt%, the photopolymerizable resin is present in an amount of 10 to 15wt%, the organic silver salt is present in an amount of 3 to 6wt%, the photosensitive monomer is present in an amount of 5 to 10wt%, the photoinitiator is present in an amount of 0.01 to 3wt%, the photosensitizer is present in an amount of 0.01 to 1wt%, the organic solvent is present in an amount of 5 to 10wt%, the additive is present in an amount of 0.01 to 3wt%, based on the total weight of the composition
The content of the component A is 60-75wt%; the content of the component B is 25-40wt%.
The inventors of the present invention have found through studies that when the particle I uses only one of the flake silver powder, the spherical silver powder and the nano silver powder, a balance cannot be achieved between avoiding the undercut phenomenon and enhancing the conductivity. When at least 2 of the particles are adopted, the ultraviolet light transmittance can be enhanced, and meanwhile, the contact probability of the particles I is improved, so that the resistivity value and the disconnection probability of the prepared microelectrode wire are reduced. In addition, the nano silver powder can adjust the viscosity of photosensitive silver paste while increasing the ultraviolet light transmittance, so that the printing quality is improved.
Preferably, the volume average particle diameter of the flake silver powder and the spherical silver powder is 1 to 2 μm, and the volume average particle diameter of the nano silver powder is 50 to 200nm.
Preferably, the particles II have a volume average particle diameter of 1 to 3. Mu.m.
The inventor of the invention discovers that the particles II are melted in the drying/sintering process of the photosensitive silver paste, so that the conductive particles are connected with each other, which is beneficial to reducing the disconnection probability of the prepared microelectrode wires and improving the conductivity of the microelectrode wires.
Preferably, the particle I is a mixture with a content weight ratio of 1:0.5-1.5:0.5 to 1.5, the spherical silver powder and the nano silver powder. The inventors of the present invention have found that a photosensitive silver paste prepared using the composition of the preferred case can obtain a microelectrode with higher resolution.
Preferably, the content weight ratio of the particles I to the particles II is 10-15:1.
preferably, the volume average particle diameter of the inorganic binder is 0.5 to 3 μm.
Preferably, the inorganic binder is selected from B 2 O 3 、PbO-B 2 O 3 -SiO 2 ZnO-based glass frit and Bi 2 O 3 -B 2 O 3 -SiO 2 At least one of the ZnO glass powders. Illustratively, the PbO-B 2 O 3 -SiO 2 the-ZnO glass powder may be PbO-B with glass transition temperature of 450 DEG C 2 O 3 -SiO 2 -ZnO-based glass frit; the Bi is 2 O 3 -B 2 O 3 -SiO 2 The ZnO-based glass frit may be Bi having a glass transition temperature of 500 DEG C 2 O 3 -B 2 O 3 -SiO 2 -ZnO-based glass frit.
Preferably, the metal element in the metal element particles is selected from at least one of indium, tin, bismuth, cadmium, lead and antimony.
Preferably, the alloy in the alloy particles is selected from at least one of a bismuth-tin alloy, a lead-tin alloy, a tin-antimony-copper alloy, and a zinc-magnesium-copper alloy.
Preferably, the particle II is a mixture with a content weight ratio of 1:0.1-1:0.4-1.6:0.1 to 1.5 of bismuth powder, tin powder, antimony powder and zinc-magnesium-copper alloy powder. The inventor of the present invention found that the photosensitive silver paste prepared by using the composition under the preferred condition can obtain microelectrodes with better electric conductivity.
Preferably, the photopolymerizable resin is selected from at least one of an acrylic monomer homopolymer and an acrylic monomer copolymer.
Preferably, the acrylic monomer is selected from at least one of methacrylate, methyl methacrylate, ethyl methacrylate, allyl methacrylate, oxypropyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate, N-butyl acrylate, isobutyl acrylate, isopropyl acrylate, allyl acrylate, glycidyl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, N-ethoxymethacrylate, butoxytriethylene glycol acrylate, dicyclopentenyl acrylate, dicyclopentadiene acrylate, 2-propenyl cyclohexylpropionate, 1, 4-butanediol diacrylate, 1, 3-butanediol diacrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacetate, dipentaerythritol hexaacrylate, bisphenol a glycerol diacrylate, bisphenol a methoxylated cyclohexyl diacrylate, bisphenol a diacrylate, acryloxytrimethylsilane and allyloxymethylsilane.
The acrylic monomer homopolymer and the acrylic monomer copolymer have certain viscosity and film forming property, and are favorable for adhering photosensitive silver paste on a substrate. Which contains a large number of carboxyl and hydroxyl groups in addition to the unsaturated c=c double bonds capable of participating in photoinitiated radical polymerization. The carboxyl groups enable the unexposed portions of the photosensitive silver paste to be removed by an alkaline developer (e.g., na 2 CO 3 Developer) is subjected to acid-base neutralization reaction to be etched away. The hydroxyl group can generate van der Waals force with the substrate, so that the adhesion strength of the prepared microelectrode wire and the substrate is enhanced.
According to a preferred embodiment, the acrylic monomer copolymer has a number average molecular weight of 5000 to 100000g/mol and an acid value of 50 to 300mgKOH/g.
More preferably, the acrylic monomer copolymer has a number average molecular weight of 30000 to 60000g/mol and an acid value of 100 to 200mgKOH/g. The inventors of the present invention have found that a photosensitive silver paste prepared using the composition of the preferred case can obtain a microelectrode with higher resolution.
Preferably, the glass transition temperature of the acrylic monomer copolymer is 0 to 150 ℃, preferably 50 to 100 ℃.
According to another preferred embodiment, the acrylic monomer copolymer contains at least one of structural unit a and structural unit B; and the structural unit A is an acrylic structural unit containing an epoxy group, and the structural unit B is an acrylic structural unit containing a siloxane group. The inventor of the present invention found that the photosensitive silver paste prepared by using the composition under the preferred condition can obtain microelectrodes with better adhesive force.
According to a particularly preferred embodiment, the content of structural units A is from 10 to 50% by weight and the content of structural units B is from 5 to 50% by weight.
Preferably, the photosensitive monomer is selected from at least one of acrylate monomers with a molecular weight of 360-600 g/mol.
In the invention, the photosensitive monomer initiates the C=C double bond fracture on the monomer to carry out polymerization reaction through the photoinitiator, so that the photopolymerization resin and the photosensitive monomer become a three-dimensional network structure with larger molecular weight, and are insoluble in the developing solution.
Preferably, the photoactive monomer is selected from at least one of ethoxylated trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, stearyl stearate, tetrahydrofurfuryl alcohol propylene ester, dodecyl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonylphenol acrylate, dipentaerythritol monohydroxypentaacrylate, 1, 6-hexanediol triacrylate, tripropylene glycol diacrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, tetraethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacetate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated neopentyl glycol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and pentaerythritol triacrylate.
Further preferably, the photosensitive monomer is selected from at least one of decaethoxylated bisphenol a diacrylate, tetraethoxylated bisphenol a diacrylate, diethoxylated bisphenol a dimethacrylate and bisphenol a dimethacrylate. The inventors of the present invention found that a photosensitive silver paste prepared using the composition in this preferred case can obtain a microelectrode having a higher resolution.
Preferably, the photoinitiator is selected from at least one of radical polymerization photoinitiators.
Further preferably, the photoinitiator is selected from at least one of 1-p-methylthiophenyl-2-methyl-2-morpholino-1-propanone, 2, 3-octanedione, 1- [4- (phenylthio) phenyl ] -1, 2-octanedione- (O-benzoyloxime) ], (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime), methyl O-benzoylbenzoate, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dichlorobenzophenone, 4-methylbenzophenone, dibenzylkenone, fluorenone, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylpropione, 4-azidobenzketone, N-phenylthioacridone and benzothiazole.
More preferably, the photoinitiator is selected from at least one of phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 4-azidobenzo-hemiketone, N-phenylthioacridone, and benzothiazole disulfide. The inventors of the present invention found that the photosensitive silver paste prepared using the composition in the preferred case has higher curing efficiency.
The inventors of the present invention have studied and found that when only a photoinitiator is contained in the composition, sufficient radical-initiated polymerization reaction cannot be obtained, and therefore, the present invention is aided by the addition of a specific amount of a photosensitizer. When ultraviolet light irradiates, the photosensitizer absorbs light with a specific wavelength, the electron absorption energy in the molecule transits from a ground state to an excited state, and when the excited state returns to the ground state, the energy is released to assist the photoinitiator to form active free radicals.
Preferably, the photosensitizer is selected from at least one of N-phenylethanolamine, 2, 4-diethylthioxanthone, isopropylthioxanthone, 2, 3-bis (4-dimethylaminobenzoyl) cyclopentane, 2, 6-bis (4-dimethylaminobenzoyl) bis (dimethylamino) benzophenone, 4-bis (dimethylamino) dimethyl ketone, 2, 6-bis-p-dimethylaminobenzylidene indenone, 2- (p-dimethylaminophenyl vinyl) isothiazole, 1, 3-bis (4-dimethylaminophenyl vinyl) isothiazole, and 1, 3-bis (4-methylaminobenzyl) acetone.
The inventors of the present invention found that the organic silver salt was insoluble in the developer solution and its thermal decomposition temperature was 150-300 c, which is comparable to the temperature of the drying/sintering process. The organic silver salt is thermally decomposed during the drying/sintering process to produce silver particles, which are conducive to connecting other conductive particles to form a complete conductive circuit. In addition, the organic silver salt is thermally decomposed to generate carbon free radicals, and the carbon free radicals can react with the polymer or the groups on the surface of the substrate to strengthen the molecular curing degree and the adhesion strength of the microelectrode wires and the substrate.
Preferably, the organic silver salt is at least one selected from the group consisting of silver acetate, silver propionate, silver butyrate, silver oxalate, silver benzoate, silver 2-ethylhexanoate, silver picrate and silver alginate. More preferably, the organic silver salt is selected from at least one of silver acetate, silver oxalate and silver 2-ethylhexanoate.
The inventor of the invention discovers that organic silver salt and organic solvent can form stable compound molecules to be fused in photosensitive silver slurry, and the compound molecules can not transmit ultraviolet light through the lower layer of the photosensitive silver slurry like solid silver during exposure, so that the curing rate of the lower layer of the photopolymerization resin and photosensitive monomer is increased.
Preferably, the organic solvent is selected from at least one of terpineol, diethylene glycol butyl ether acetate, N-dimethylacetamide, N-methylformamide, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, dimethyl sulfoxide, ethoxy-2-propanol, ethylene glycol mono-N-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether acetate.
Preferably, the dispersing agent is selected from at least one of alkylphenol ethoxylates. More preferably, the dispersant is at least one selected from the group consisting of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and dinonylphenol polyoxyethylene ether.
Preferably, the antioxidant is at least one selected from the group consisting of 2,2' -methylenebis- (4-methyl-6-tert-butylphenol), butylated hydroxyanisole and 2, 5-di-tert-butylhydroquinone.
Preferably, the plasticizer is at least one selected from diethyl phthalate, dibutyl phthalate, dioctyl phthalate and polyethylene glycol.
Preferably, the leveling agent is selected from at least one of fluorine modified acrylates. Illustratively, the fluorine modified acrylate may be a fluorine modified acrylate leveling agent LD-1087, a fluorine modified acrylate leveling agent RF-7377, or the like.
Preferably, the silane coupling agent is selected from at least one of n-octadecyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, and phenyltriethoxysilane.
As previously described, a second aspect of the present invention provides a method of preparing an ultraviolet-sensitive optical silver paste using the composition described in the first aspect, comprising: in a yellow light clean room with the pressure of 0.10-0.15 MPa:
(1) First mixing the components in the component A to obtain a mixture I; and
performing second mixing on each component in the component B to obtain a mixture II;
(2) And sequentially carrying out third mixing and fourth mixing on the mixture I and the mixture II.
Preferably, the conditions of the first mixing at least satisfy: the stirring is carried out under the stirring condition, the stirring rotating speed is 100-300rpm, the temperature is 20-60 ℃, and the time is 30-100min.
Preferably, the conditions of the second mixing at least satisfy: the stirring is carried out under the stirring condition, the stirring rotating speed is 200-500rpm, the temperature is 40-70 ℃, and the time is 30-100min.
According to a preferred embodiment, the conditions of the third mixing at least satisfy: the process is carried out in a gravity mixer at a rotation speed of 20-60rpm and a temperature of 50-70 ℃ for 50-90min.
According to another preferred embodiment, the fourth mixing conditions at least satisfy: the process is carried out in a mixer, the roll gap of the mixer is 20-50 mu m, the roll temperature is 50-60 ℃ and the time is 3-5h.
As described above, the third aspect of the present invention provides an ultraviolet-sensitive optical silver paste prepared by the method described in the second aspect.
As described above, a fourth aspect of the present invention provides a use of the ultraviolet-sensitive lithographic silver paste described in the foregoing third aspect for preparing a microelectrode.
The invention will be described in detail below by way of examples.
In the examples below, all the raw materials used are commercially available, unless otherwise specified.
In the examples below, room temperature represents 25.+ -. 2 ℃ unless otherwise specified.
The microelectrode of the present invention is preferably carried out according to the process flow shown in fig. 1, in particular as follows:
coating photosensitive silver paste on a substrate through screen printing, and drying the substrate coated with the photosensitive silver paste; then placing a mask on the upper part of the silver paste film, and performing ultraviolet exposure; developing by a developing device and a developing solution; finally, drying/sintering is carried out to obtain the microelectrode.
In the invention, the preparation method of the resin II 1-allyl acrylate-dicyclopentadiene acrylate copolymer is as follows:
0.5mol (analytically pure, aladedin reagent), 0.3mol (analytically pure, alfa Aesar reagent) of dicyclopentadiene acrylate, 6mmol (analytically pure, aladedin reagent) of benzyl alcohol and 60mL (used after anhydrous anaerobic treatment distillation with sodium metal particles) of tetrahydrofuran are weighed out.
The allyl acrylate, dicyclopentadiene acrylate, benzyl alcohol and tetrahydrofuran are added into a reaction vessel, the temperature is raised to 50 ℃ from room temperature under the protection of nitrogen, and after magnetic stirring is carried out for 20min, 4.4mL (aladin reagent) of P4-tertiary butyl phosphazene base (P4-t-Bu) is added into the reaction vessel in a dropwise manner, and the polymerization reaction is carried out under the condition of 50 ℃ by continuous stirring. Polymerization was monitored using a Rheonics SRV-3k (Lei Ao Nix, switzerland) online viscometer. When the viscosity of the reaction solution was monitored to reach 55.+ -. 5Pa.s, 10mmol of methanol was injected into the reaction solution to quench the polymerization reaction. And (3) carrying out pressurized distillation on the obtained reaction solution to remove small molecular compounds such as tetrahydrofuran, methanol and the like, and finally obtaining the viscous flow allyl acrylate-dicyclopentadiene acrylate copolymer.
The preparation of the resin II 2-allyl acrylate-dicyclopentadiene acrylate copolymer is similar to that of resin I, except that: the amount of allyl acrylate was 0.4mol, dicyclopentadiene acrylate was 0.6mol, benzyl alcohol was 8mmol, tetrahydrofuran was 80mL (sodium metal particles were used after anhydrous anaerobic treatment distillation), and P4-t-butylphosphazene base (P4-t-Bu) was 5.9mL, with the remaining conditions being the same.
The preparation method of the resin III-allyl acrylate-bisphenol A diacrylate copolymer comprises the following steps:
allyl acrylate 0.5mol, bisphenol A diacrylate 0.4mol (analytically pure, alfa Aesar), benzyl alcohol 6mmol and tetrahydrofuran 60mL (used after anhydrous anaerobic treatment distillation with sodium metal particles) were weighed.
Adding the allyl acrylate, bisphenol A diacrylate, benzyl alcohol and tetrahydrofuran into a reaction vessel, heating to 50 ℃ from room temperature under the protection of nitrogen, stirring for 20min, then dropwise adding 4.4mL of P4-tert-butyl phosphazene base (P4-t-Bu) into the reaction vessel, continuously stirring at 50 ℃ and continuously stirring at 50 ℃ to perform polymerization reaction. Polymerization was monitored using a Rheonics SRV-3k (Lei Ao Nix, switzerland) online viscometer. When the viscosity of the reaction solution was monitored to reach 55.+ -. 5Pa.s, 9mmol of methanol was injected into the reaction solution to quench the polymerization reaction. And (3) carrying out pressurized distillation on the obtained reaction solution to remove small molecular compounds such as tetrahydrofuran, methanol and the like, and finally obtaining the viscous flow allyl acrylate-bisphenol A diacrylate copolymer.
The preparation method of the resin IV-allyl acrylate-allyloxy trimethylsilane copolymer is as follows:
Allyl acrylate 0.5mol, allyloxy trimethylsilane 0.4mol (analytically pure, alfa Aesar), benzyl alcohol 6mmol and tetrahydrofuran 60mL (used after anhydrous anaerobic treatment distillation with sodium metal particles) were weighed.
Adding the allyl acrylate, allyloxy trimethyl silane, benzyl alcohol and tetrahydrofuran into a reaction container, heating to 50 ℃ from room temperature under the protection of nitrogen, stirring for 20min, dropwise adding 4.4mL of P4-tert-butyl phosphazene base (P4-t-Bu) into the reaction container, continuously stirring at 50 ℃ and continuously stirring at 50 ℃ to perform polymerization reaction. Polymerization was monitored using a Rheonics SRV-3k (Lei Ao Nix, switzerland) online viscometer. When the viscosity of the reaction solution was monitored to reach 55.+ -. 5Pa.s, 9mmol of methanol was injected into the reaction solution to quench the polymerization reaction. And (3) carrying out pressurized distillation on the obtained reacted solution to remove small molecular compounds such as tetrahydrofuran, methanol and the like, and finally obtaining the viscous flow allyl acrylate-allyloxy trimethyl silane copolymer.
The ultraviolet sensitive photo silver paste in the subsequent examples of the present invention was carried out in a yellow light clean room (class B) under normal pressure.
Raw materials:
Conductive particles:
particle I1: flake silver powder having a volume average particle diameter of 1 μm, available from Ames Goldsmith;
particle I2-1: spherical silver powder having a volume average particle diameter of 1 μm, available from Ames Goldsmith;
particles I2-2: spherical silver powder having a volume average particle diameter of 12 μm, available from Ames Goldsmith;
particle I3: the volume average particle diameter of the nano silver powder is 100nm, and the nano silver powder is purchased from Zhejiang Huawei materials science and technology Co., ltd;
particle II1: tin powder, having a volume average particle diameter of 1 μm and a melting point of 231 ℃, available from Belmont corporation;
particle II2: bismuth powder having a volume average particle diameter of 1 μm and a melting point of 271 ℃ and available from Belmont corporation;
particle II3: antimony powder having a volume average particle diameter of 1 μm and a melting point of 630 ℃ and available from Aba Ding Huaxue company;
particle II4: zinc magnesium copper alloy powder with volume average particle diameter of 1 μm and melting point of 342 ℃ and purchased from American Elements company;
an inorganic binder: b (B) 2 O 3 Powder with a volume average particle diameter of 1 μm, purchased from Shenzhen complex technology Co., ltd;
photopolymerized resin:
resin I: polyacrylate, number average molecular weight 40000g/mol, available from Sigma-Aldrich company;
resin II1: allyl acrylate-dicyclopentadiene acrylate copolymer with a number average molecular weight of 30000g/mol and an acid value of 100mgKOH/g;
Resin II2: allyl acrylate-dicyclopentadiene acrylate copolymer with a number average molecular weight of 65000g/mol and an acid value of 230mgKOH/g;
resin III: an allyl acrylate-bisphenol A diacrylate copolymer having a number average molecular weight of 35000g/mol and an acid value of 150mgKOH/g;
resin IV: allyl acrylate-allyloxy trimethylsilane copolymer having a number average molecular weight of 50000g/mol, an acid value of 150mgKOH/g, and a content of structural unit B of 50wt%;
photosensitive monomer:
monomer I: the molecular weight of the diethoxy bisphenol A dimethacrylate is 362g/mol, and the brand: 413550 from Sigma-Aldrich;
monomer II: bisphenol A dimethacrylate with molecular weight of 364g/mol and brand: 156329 available from Sigma-Aldrich;
monomer III: ethoxylated trimethylolpropane triacrylate, molecular weight 428g/mol, brand: 409073 from Sigma-Aldrich;
and (3) a photoinitiator:
initiator I: phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
initiator II: 4-azidobenzo-hemimethanone;
initiator III: 1-p-methylthiophenyl-2-methyl-2-morpholinyl-1-propanone;
photosensitizer:
photosensitizer I:2, 3-bis (4-dimethylaminobenzoyl) cyclopentane;
Photosensitizer II:1, 3-bis (4-methylaminobenzyl) propanone;
organic silver salt:
silver salt I: silver 2-ethylhexanoate; silver salt II: silver oxalate;
organic solvent:
solvent I: ethylene glycol mono-n-propyl ether; solvent II: terpineol;
additive:
dispersing agent: alkylphenol ethoxylates, brand 56741, available from Sigma-Aldrich;
an antioxidant: butyl hydroxy anisole (hereinafter referred to as BHA);
and (3) a plasticizer: polyethylene glycol;
leveling agent: fluorine modified acrylic ester, brand RF-7377, available from Zhejiang Ke Rui chemical Co., ltd;
silane coupling agent: dimethyl diethoxysilane (hereinafter referred to as DDS).
Example 1
This example illustrates that the UV-sensitive lithographic silver paste of the present invention was prepared according to the formulation and method shown in Table 1. The method for preparing the ultraviolet photosensitive silver paste comprises the following steps:
(1) First mixing the components in the component A to obtain a mixture I; and
performing second mixing on each component in the component B to obtain a mixture II;
the conditions for the first mixing are: stirring at 30deg.C for 60min at 200 rpm;
the conditions for the second mixing are: the stirring is carried out under the stirring condition, the stirring rotating speed is 500rpm, the temperature is 40 ℃, and the time is 90min;
(2) Sequentially carrying out third mixing and fourth mixing on the mixture I and the mixture II to obtain silver paste J1;
the conditions for the third mixing are: in a gravity mixer at a rotation speed of 50rpm and a temperature of 55 ℃ for 60min;
the fourth mixing conditions were: the mixing was carried out in a mixer having a roll gap of 30 μm and a roll temperature of 60℃for 3 hours.
The remaining examples and comparative examples of the present invention were carried out according to the formulations and methods in table 1.
TABLE 1
/>
Table 1, below
/>
Table 1, below
/>
Table 1, below
/>
Table 1, below
/>
Test case
The ultraviolet-sensitive photo-etching silver pastes prepared in the examples and comparative examples were prepared into microelectrodes according to the preparation procedure shown in fig. 1, specifically as follows:
coating the ultraviolet lithography silver paste on a glass substrate through a silk screen (stainless steel number 325) by a silk screen printer; after printing, standing and leveling the substrate for 20min, placing the substrate in an oven at 80 ℃ for drying for 20min, and naturally cooling to room temperature to obtain the substrate with the thickness of the silver paste film of 10 mu m;
a photomask was placed on top of the silver paste film at 300mJ/cm 2 Ultraviolet light (wavelength of 375nm, light intensity of 20 mW/cm) 2 ) Exposing for 50s; then at 30℃and 1.0kg/cm by a developing apparatus 2 At a spray pressure of 0.3wt% Na 2 CO 3 Developing the silver paste film by an alkaline aqueous solution, and dissolving and eluting to obtain an electrode pattern;
placing the microelectrode pattern in a high-temperature sintering furnace for sintering and curing, wherein the sintering process conditions are as follows: raising the temperature from room temperature (25+/-2 ℃) to 250 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature at 250 ℃ for 1h; then raising the temperature from 250 ℃ to 500 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature at 500 ℃ for 1h; finally, raising the temperature from 500 ℃ to 650 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature at 650 ℃ for 1h to obtain the microelectrode;
the prepared microelectrode was subjected to the following performance tests, in particular as follows:
(1) Observing the resolution image of the microelectrode pattern by using an optical microscope (manufacturer: olympus, model: STM 6), and obtaining resolution;
(2) Obtaining images and sizes of microelectrode wires by adopting a scanning electron microscope;
(3) The conductivity (conductivity) of the microelectrode pattern was obtained by a four-probe method using a current source (manufacturer: keithley, model: 220) and an electrometer amplifier (manufacturer: keithley, model: 2010);
(4) The adhesion data of the silver paste to the substrate were obtained by the scotch tape method with reference to standard ASTM D3359.
TABLE 2
As can be seen from the results of Table 2, the ultraviolet photosensitive silver paste prepared by the composition and the method provided by the invention can avoid undercut and edge curl, and can be used for preparing microelectrodes with high resolution, high adhesive force and high conductivity.
Fig. 2 is an SEM image of microelectrode wires prepared by ultraviolet-sensitive photoetching silver paste prepared in example 1. Similar to the SEM image of the microelectrode wire prepared by the ultraviolet-sensitive optical silver paste prepared by the rest examples, the SEM image of the microelectrode wire prepared by the ultraviolet-sensitive optical silver paste prepared by the example 1 is exemplarily provided in the invention.
As can be seen from fig. 2, the conductive particles are tightly bonded, and the electrode wires are smooth and neat, with higher resolution.
Fig. 3 is an SEM image of a cross section of a microelectrode prepared by using the ultraviolet-sensitive photolithography silver paste prepared in example 1. Similar to the SEM image of the cross section of the microelectrode prepared by using the ultraviolet-sensitive optical silver paste prepared in the rest examples, the SEM image of the cross section of the microelectrode prepared by using the ultraviolet-sensitive optical silver paste prepared in example 1 is exemplarily provided in the present invention.
As can be seen from fig. 3, the electrode line section is aligned up and down without undercut and edge curl.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A composition for preparing ultraviolet photosensitive silver paste is characterized in that the composition contains a component A and a component B,
the component A contains conductive particles and an inorganic binder which is optionally contained; the conductive particles contain particles I and particles II; the particles I are selected from at least 2 of flake silver powder, spherical silver powder and nano silver powder, the volume average particle size of the flake silver powder and the spherical silver powder is 0.6-10 mu m, and the volume average particle size of the nano silver powder is 50-500nm; the particles II are selected from at least one of metal simple substance particles and alloy particles, the volume average particle diameter of the particles II is 1-10 mu m, and the melting point is 100-650 ℃;
the component B contains photopolymerization resin, photosensitive monomer, photoinitiator, photosensitizer, additive and optionally organic silver salt and organic solvent; the additive comprises a dispersing agent, an antioxidant, a plasticizer, a leveling agent and a silane coupling agent;
the composition comprises, based on the total weight of the composition, 50-80wt% of conductive particles, 0-8wt% of inorganic binder, 5-20wt% of photopolymerized resin, 0-10wt% of organic silver salt, 5-15wt% of photosensitive monomer, 0.01-7wt% of photoinitiator, 0.01-3wt% of photosensitizer, 0-15wt% of organic solvent, 0.01-5wt% of additive, and
The content of the component A is 50-80wt%; the content of the component B is 20-50wt%.
2. The composition of claim 1, wherein the particles I are present in an amount by weight of 1:0.5-1.5:0.5 to 1.5 of a combination of the flake silver powder, the spherical silver powder, and the nano silver powder; and/or the number of the groups of groups,
the content weight ratio of the particles I to the particles II is 10-15:1, a step of; and/or the number of the groups of groups,
the inorganic binder is selected from B 2 O 3 、PbO-B 2 O 3 -SiO 2 ZnO-based glass frit and Bi 2 O 3 -B 2 O 3 -SiO 2 At least one of the ZnO glass powders.
3. The composition of claim 1 or 2, wherein the elemental metal in the elemental metal particles is selected from at least one of indium, tin, bismuth, cadmium, lead, and antimony; and/or the number of the groups of groups,
the alloy in the alloy particles is at least one selected from bismuth-tin alloy, lead-tin alloy, tin-antimony-copper alloy and zinc-magnesium-copper alloy;
preferably, the particle II is a mixture with a content weight ratio of 1:0.1-1:0.4-1.6:0.1 to 1.5 of bismuth powder, tin powder, antimony powder and zinc-magnesium-copper alloy powder.
4. A composition according to any one of claims 1 to 3, wherein the photopolymerizable resin is selected from at least one of an acrylic monomer homopolymer and an acrylic monomer copolymer;
Preferably, the acrylic monomer copolymer has a number average molecular weight of 5000 to 100000g/mol and an acid value of 50 to 300mgKOH/g;
preferably, the acrylic monomer copolymer contains at least one of the structural unit a and the structural unit B; and the structural unit A is an acrylic structural unit containing an epoxy group, and the structural unit B is an acrylic structural unit containing a siloxane group;
preferably, the content of the structural unit A is 10 to 50wt% and the content of the structural unit B is 5 to 50wt%.
5. The composition according to any one of claims 1 to 4, wherein the photoactive monomer is selected from at least one of acrylate monomers having a molecular weight of 360-600 g/mol;
preferably, the photosensitive monomer is selected from at least one of decaethoxylated bisphenol a diacrylate, tetraethoxylated bisphenol a diacrylate, diethoxylated bisphenol a dimethacrylate and bisphenol a dimethacrylate; and/or the number of the groups of groups,
the photoinitiator is at least one selected from free radical polymerization photoinitiators;
preferably, the photoinitiator is selected from at least one of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 4-azidobenzo-hemiketone, N-phenylthioacridone and benzothiazole disulfide; and/or the number of the groups of groups,
The photosensitizer is at least one selected from N-phenylethanolamine, 2, 4-diethylthioxanthone, isopropylthioxanthone, 2, 3-bis (4-dimethylaminobenzoyl) cyclopentane, 2, 6-bis (4-dimethylaminobenzoyl) bis (dimethylamino) benzophenone, 4-bis (dimethylamino) dimethyl ketone, 2, 6-bis-p-dimethylaminobenzylidene indenone, 2- (p-dimethylaminophenyl vinyl) isothiazole, 1, 3-bis (4-dimethylaminophenyl vinyl) isothiazole and 1, 3-bis (4-methylaminobenzyl) acetone.
6. The composition of any of claims 1-5, wherein the organic silver salt is selected from at least one of silver acetate, silver propionate, silver butyrate, silver oxalate, silver benzoate, silver 2-ethylhexanoate, silver picrate, and silver alginate; and/or the number of the groups of groups,
the organic solvent is at least one selected from terpineol, diethylene glycol butyl ether acetate, N-dimethylacetamide, N-methyl formamide, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, dimethyl sulfoxide, ethoxy-2-propanol, ethylene glycol mono-N-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether and diethylene glycol monomethyl ether acetate.
7. A method of preparing an ultraviolet-sensitive optical silver paste, characterized in that the method is carried out using the composition according to any one of claims 1 to 6, comprising: in a yellow light clean room with the pressure of 0.10-0.15 MPa:
(1) First mixing the components in the component A to obtain a mixture I; and
performing second mixing on each component in the component B to obtain a mixture II;
(2) And sequentially carrying out third mixing and fourth mixing on the mixture I and the mixture II.
8. The method of claim 7, wherein the first mixing conditions at least satisfy: stirring at 20-60deg.C for 30-100min at 100-300 rpm; and/or the number of the groups of groups,
the conditions of the second mixing at least satisfy: stirring at 200-500rpm at 40-70deg.C for 30-100min; and/or the number of the groups of groups,
the conditions of the third mixing at least satisfy: the process is carried out in a gravity mixer, the rotating speed is 20-60rpm, the temperature is 50-70 ℃ and the time is 50-90min; and/or the number of the groups of groups,
the fourth mixing condition at least satisfies: the process is carried out in a mixer, the roll gap of the mixer is 20-50 mu m, the roll temperature is 50-60 ℃ and the time is 3-5h.
9. An ultraviolet-sensitive optical silver paste prepared by the method of claim 7 or 8.
10. Use of the ultraviolet sensitive optical silver paste of claim 9 for preparing microelectrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310598138.5A CN116841120A (en) | 2023-05-25 | 2023-05-25 | Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310598138.5A CN116841120A (en) | 2023-05-25 | 2023-05-25 | Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116841120A true CN116841120A (en) | 2023-10-03 |
Family
ID=88166054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310598138.5A Pending CN116841120A (en) | 2023-05-25 | 2023-05-25 | Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116841120A (en) |
-
2023
- 2023-05-25 CN CN202310598138.5A patent/CN116841120A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5654588B2 (en) | Electrode and manufacturing method thereof | |
| JP3674501B2 (en) | Photosensitive copper paste, method for forming copper pattern, and method for producing ceramic multilayer substrate | |
| JP3113636B2 (en) | Heat-assisted light-sensitive composition and method therefor | |
| JP3428483B2 (en) | Pattern forming method, manufacturing method of plasma display rib substrate, manufacturing method of plasma display | |
| KR20140115316A (en) | Conductive paste and method for producing conductive pattern | |
| JP3528669B2 (en) | Method of forming conductor pattern and method of manufacturing ceramic multilayer substrate | |
| JP2013507772A (en) | Electrode including oxidation-resistant boron oxide layer and method for manufacturing the same | |
| JP2012216827A (en) | Manufacturing method of solar cell electrode and solar cell electrode manufactured by using the same | |
| JP4062805B2 (en) | Photosensitive conductive paste for firing and method for forming fine electrode pattern | |
| JP4898251B2 (en) | Method for forming conductive pattern, composition for forming conductive pattern, and electronic component having conductive pattern | |
| JP3785480B2 (en) | Paste-like conductive resin composition and method for forming sintered body thereof | |
| JP2004055402A (en) | Conductive paste composition, transcription film for electrode formation, and electrode for plasma display | |
| CN116841120A (en) | Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof | |
| KR101306778B1 (en) | Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof | |
| JP5533043B2 (en) | Photosensitive conductive paste and method for producing conductive pattern | |
| JP2018120652A (en) | Conductive pattern forming film | |
| JP2004054085A (en) | Photosensitive conducttor paste | |
| JP2007217608A (en) | Ultraviolet curable paste, offset printing apparatus, and method for offset printing | |
| KR102208100B1 (en) | Conductive paste, touch panel, and method for producing conductive pattern | |
| US9846362B2 (en) | Conductive paste and method of producing conductive pattern | |
| JPH06228442A (en) | Photo-polymerizable electrically conductive paste | |
| JP6566027B2 (en) | Photosensitive conductive paste and method for manufacturing substrate with conductive pattern | |
| KR101064846B1 (en) | Paste composition for offset printing and flat panel display device using the smae | |
| JPH06231613A (en) | Conductive paste of photopolymerization type | |
| CN116543951B (en) | Silver paste for UV (ultraviolet) curing type flexible circuit board, preparation method and application method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |