KR101196797B1 - Composition of catalyst precursor resin for shielding EMI and manufacturing method metal pattern for shielding EMI using the same - Google Patents
Composition of catalyst precursor resin for shielding EMI and manufacturing method metal pattern for shielding EMI using the same Download PDFInfo
- Publication number
- KR101196797B1 KR101196797B1 KR1020070052110A KR20070052110A KR101196797B1 KR 101196797 B1 KR101196797 B1 KR 101196797B1 KR 1020070052110 A KR1020070052110 A KR 1020070052110A KR 20070052110 A KR20070052110 A KR 20070052110A KR 101196797 B1 KR101196797 B1 KR 101196797B1
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- pattern
- resin composition
- catalyst precursor
- precursor resin
- Prior art date
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- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 title claims description 8
- 239000011347 resin Substances 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 239000011342 resin composition Substances 0.000 claims abstract description 57
- 238000007772 electroless plating Methods 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229940096017 silver fluoride Drugs 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 100
- 238000007747 plating Methods 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 16
- -1 Phthalic acid ester Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical class [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000018109 developmental process Effects 0.000 claims description 6
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 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 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000007645 offset printing Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000007261 regionalization Effects 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride 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
- 239000007787 solid Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- RXEXJCURLVRHCR-UHFFFAOYSA-N acetic acid;3-methoxyprop-1-ene Chemical compound CC(O)=O.COCC=C RXEXJCURLVRHCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011976 maleic acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
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- 239000005020 polyethylene terephthalate Substances 0.000 claims 2
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- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 claims 1
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- MNRJUMUSNWEQAU-UHFFFAOYSA-N C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C=C)(=O)O Chemical compound C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(C=C)(=O)O MNRJUMUSNWEQAU-UHFFFAOYSA-N 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 1
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- 230000008021 deposition Effects 0.000 abstract description 6
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- 230000003628 erosive effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
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- 230000000052 comparative effect Effects 0.000 description 6
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- 238000007796 conventional method Methods 0.000 description 5
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- 230000007547 defect Effects 0.000 description 3
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- H05K1/00—Printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
본 발명은 전자파 차폐용 촉매 전구체 수지 조성물 및 이를 이용한 전자파 차폐용 금속 패턴 제조방법에 관한 것이다. 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물은, 카르복시기를 포함하는 단량체(C11), 및 그 내부에 포함된 질소에 지용성 관능기가 치환된 말레이미드 단량체(C12)를 포함하여 이루어진 공중합체수지(C1); 팔라듐(Pd) 입자, 은(Ag) 입자, 및 플루오르화 은(Ag)이온 유기착화물 중 선택된 하나의 촉매(C2); 에틸렌성 불포화 결합을 포함하는 다관능성 단량체(C3); 광개시제(C4); 및 유기용매(C5);를 포함하여 이루어지는 것을 특징으로 한다. 본 발명에 따르면, 촉매 패턴의 침식을 최소화하면서 촉매의 유실을 방지할 수 있으며, 증착속도가 향상되어 무전해 도금 후 균일하고 미세한 금속패턴으로 형성할 수 있다.The present invention relates to a catalyst precursor resin composition for electromagnetic shielding and a method for producing a metal pattern for electromagnetic shielding using the same. The catalyst precursor resin composition for electromagnetic wave shielding according to the present invention is a copolymer resin (C1) comprising a monomer (C11) containing a carboxyl group and a maleimide monomer (C12) substituted with a fat-soluble functional group in nitrogen contained therein. ); A catalyst (C2) selected from palladium (Pd) particles, silver (Ag) particles, and silver fluoride (Ag) ion organic complexes; Polyfunctional monomers (C3) containing ethylenically unsaturated bonds; Photoinitiator (C4); And an organic solvent (C5). According to the present invention, the loss of the catalyst can be prevented while minimizing the erosion of the catalyst pattern, and the deposition rate can be improved to form a uniform and fine metal pattern after the electroless plating.
전자파차폐, 금속패턴, 촉매전구체, 내화학성, 무전해 도금, 촉매유실 Electromagnetic shielding, metal pattern, catalyst precursor, chemical resistance, electroless plating, catalyst loss
Description
본 명세서에 첨부되는 다음의 도면들은 본 발명의 바람직한 실시예를 예시하는 것이며, 후술하는 발명의 상세한 설명과 함께 본 발명의 기술사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 아니 된다.The following drawings attached to this specification are illustrative of preferred embodiments of the present invention, and together with the detailed description of the invention to serve to further understand the technical spirit of the present invention, the present invention is a matter described in such drawings It should not be construed as limited to.
도 1은 본 발명의 실시예에 따라 준비된 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 전자파 차폐용 금속 패턴을 제조하는 방법을 설명하기 위한 공정 흐름도이다.1 is a process flow chart for explaining a method of manufacturing an electromagnetic shielding metal pattern using the catalyst precursor resin composition for electromagnetic shielding prepared according to an embodiment of the present invention.
도 2는 본 발명에 대비되는 비교예에 따라 준비된 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 전자파 차폐용 금속 패턴을 제조하는 방법을 설명하기 위한 공정 흐름도이다.FIG. 2 is a process flowchart illustrating a method of manufacturing a metal pattern for electromagnetic wave shielding using the catalyst precursor resin composition for electromagnetic wave shielding prepared according to a comparative example according to the present invention.
본 발명은 전자파 차폐용 촉매 전구체 수지 조성물 및 이를 이용한 전자파 차폐용 금속 패턴 제조방법에 관한 것으로서, 더욱 상세하게는 카르복시기를 갖는 단량체와 질소에 지용성 관능기가 치환된 말레이미드 단량체를 포함하여 이루어진 공중합체수지에 촉매와 에틸렌성 불포화결합을 함유하는 다관능 단량체 등을 사용함으로써 2단계의 무전해 도금법에 의해 전자파 차폐용 촉매 전구체 수지 조성물 및 이를 이용한 전자파 차폐용 금속 패턴 제조방법에 관한 것이다.The present invention relates to a catalyst precursor resin composition for electromagnetic wave shielding and a method for producing a metal pattern for electromagnetic wave shielding using the same, and more particularly, to a copolymer resin comprising a monomer having a carboxyl group and a maleimide monomer substituted with nitrogen-soluble functional groups. The present invention relates to a catalyst precursor resin composition for electromagnetic wave shielding and a method for producing a metal pattern for electromagnetic wave shielding using the same by using a multifunctional monomer containing a catalyst and an ethylenically unsaturated bond.
최근 다양한 방식의 디스플레이가 상용화되면서 이러한 디스플레이로부터 발생되는 전자기적인 노이즈(Noise)의 방해 현상(Electromagnetic Interference, EMI라 약하기도 함)으로 인한 인체의 유해성 및 기기의 오작동 등이 큰 문제점으로 대두되고 있다. 이러한 문제를 해결하기 위하여 디스플레이의 전면에 도전성 차폐(Shielding)막을 형성하여 전자파의 진행방향을 왜곡시킨 후, 접지하여 방출시키는 방법이 사용되고 있다.Recently, as various types of displays are commercially available, harmful effects of human body and malfunction of devices due to electromagnetic interference (also referred to as EMI) generated from such displays have emerged as major problems. In order to solve this problem, a conductive shielding film is formed on the front of the display to distort the traveling direction of the electromagnetic wave, and then grounded and emitted.
CRT, PDP 등의 디스플레이 장치 전면으로부터 발생되는 전자파 노이즈의 차폐하기 위한 종래의 방법으로서, 투명성 기재 상에 금속 또는 금속 산화물을 증착하고 얇은 도전성 막을 형성하는 방법이 알려져 있다. 그러나, 종래의 위와 같은 방법은 투명성을 제공하기 위해 막을 얇게 증착하여야 하는데, 이렇게 박막으로 증착된 도전층은 그 표면 저항이 너무 커져서 충분한 전차파 차폐 효과를 얻을 수 없는 문제점이 존재하고 있다.As a conventional method for shielding electromagnetic noise generated from the front surface of a display device such as a CRT or PDP, a method of depositing a metal or metal oxide on a transparent substrate and forming a thin conductive film is known. However, the conventional method as described above has to deposit a thin film in order to provide transparency, there is a problem that the conductive layer deposited in this thin film is so large that the surface resistance is too large to obtain a sufficient electric wave shielding effect.
따라서, 전자파 차폐 효과를 달성하기 위한 목적으로 박막으로 증착된 도전층을 형성하는 방법을 대신하여 금속 호일 에칭(Metal foil etching) 방법이 이용되고 있다. 이는 투명 기재 위에 동박을 점착하여 노광공정을 진행한 후, 포토레지 스터 패턴을 형성하고, 이후 식각 공정을 진행하여 구리 패턴을 형성하는 방법이다. 그러나 상기 금속 호일 에칭 방법은 공정이 길고 복잡하며, 많은 양의 금속 폐기물이 배출되어 친환경적이지 못한 문제점이 지적되고 있다. 또한 공정 진행상 구리 패턴의 교점 살찜이 발생되는 문제점도 지적되고 있다.Therefore, a metal foil etching method is used instead of the method of forming a conductive layer deposited as a thin film for the purpose of achieving the electromagnetic shielding effect. This is a method of forming a copper pattern by adhering copper foil on a transparent substrate and then performing an exposure process, and then forming a photoresist pattern and then performing an etching process. However, it is pointed out that the metal foil etching method has a long and complicated process, and a large amount of metal waste is discharged, which is not environmentally friendly. It is also pointed out that the process of the intersection of the copper pattern occurs during the process.
전술한 두 가지의 방법 이외에도 스크린 프린팅법, 오프셋 프린팅법 등의 프린팅 방식을 이용하여 도전성 페이스트의 패턴을 형성하고 이를 다시 무전해 또는 도금 처리하여 전자파 차폐막을 형성하는 것이 보고되고 있다. 그러나, 프린팅 방식을 이용한 방법은 형성되는 인쇄회로의 정밀도에 한계가 있으며, 요철 부분으로 도전성 물질들이 스며드는 문제점이 지적되고 있다.In addition to the two methods described above, it has been reported to form a pattern of a conductive paste using a printing method such as a screen printing method and an offset printing method, and to form an electromagnetic shielding film by electrolessly or plating the same. However, the method using the printing method has a limitation in the accuracy of the printed circuit formed, there has been pointed out a problem that the conductive material is permeated into the uneven portion.
또한, 다른 방법으로, 사진 현상법에 의해 촉매층을 형성하고 무전해 도금 처리하는 방법이 제시되고 있으나, 이러한 방법은 패턴 특성이 우수하며 미세 패턴 형성이 가능한 장점이 있지만, 강염기 수용액에서의 패턴 탈착이 일어나거나 무전해 도금시 수반될 수 있는 여러 문제, 예컨대 공정 진행시의 촉매의 유실, 증착성이나 접착성의 약화 등에 대한 해결 방법들이 구체적으로 제시되어 있지 않다는 점에서 그 실용화에는 여러 한계가 노출되고 있다.In addition, a method of forming a catalyst layer and performing an electroless plating process by a photo developing method has been proposed as another method. However, such a method has an advantage of excellent pattern characteristics and fine pattern formation, but pattern desorption in a strong base aqueous solution. Various limitations are exposed to the practical use in that it does not present specific solutions to problems that may occur during electroless plating, such as loss of catalyst during the process, weakness of deposition or adhesion, and the like. .
전술한 종래의 여러 방법이 갖는 기술적 단점을 극복하기 위한 노력이 관련업계에서 꾸준하게 진행되어 왔으며, 이러한 기술적 배경 하에서 본 발명이 안출되었다.Efforts to overcome the technical drawbacks of the aforementioned various conventional methods have been steadily progressed in the related art, and the present invention has been devised under such technical background.
본 발명이 이루고자 하는 기술적 과제는, 전자파 차폐용 금속 패턴의 특성이 우수하면서, 미세패턴의 형성이 가능하고, 무전해 도금 등의 습식 공정시 촉매의 유실이 적으며, 금속 패턴의 접착성 및 증착성이 우수한 전자파 차폐용 금속 패턴을 제공하는 데에 있으며, 이러한 기술적 과제를 달성할 수 있는 전자파 차폐용 촉매 전구체 수지 조성물 및 이를 이용한 전자파 차폐용 금속 패턴 제조방법을 제공함에 본 발명의 목적이 있다.The technical problem to be achieved by the present invention is excellent in the characteristics of the metal pattern for electromagnetic shielding, it is possible to form a fine pattern, less loss of the catalyst during the wet process such as electroless plating, adhesion and deposition of the metal pattern An object of the present invention is to provide a metal pattern for shielding electromagnetic waves with excellent properties, and to provide a catalyst precursor resin composition for shielding electromagnetic waves and a method for producing a metal pattern for shielding electromagnetic waves using the same, which can achieve such a technical problem.
전술한 본 발명이 이루고자 하는 기술적 과제를 달성하기 위해 제공되는 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물은, 카르복시기를 포함하는 단량체(C11), 및 그 내부에 포함된 질소에 지용성 관능기가 치환된 말레이미드 단량체(C12)를 포함하여 이루어진 공중합체수지(C1); 팔라듐(Pd) 입자, 은(Ag) 입자, 및 플루오르화 은(Ag)이온 유기착화물 중 선택된 하나의 촉매(C2); 에틸렌성 불포화 결합을 포함하는 다관능성 단량체(C3); 광개시제(C4); 및 유기용매(C5);를 포함하여 이루어지는 것을 특징으로 한다.The catalyst precursor resin composition for electromagnetic wave shielding according to the present invention provided to achieve the technical problem to be achieved by the present invention described above is a monomer (C11) containing a carboxyl group, and a fat-soluble functional group is substituted for nitrogen contained therein. Copolymer resin (C1) comprising maleimide monomer (C12); A catalyst (C2) selected from palladium (Pd) particles, silver (Ag) particles, and silver fluoride (Ag) ion organic complexes; Polyfunctional monomers (C3) containing ethylenically unsaturated bonds; Photoinitiator (C4); And an organic solvent (C5).
전술한 본 발명이 이루고자 하는 기술적 과제를 달성하기 위해 제공되는 본 발명에 따르는 전자파 차폐용 금속 패턴 제조 방법의 하나는, (S11) 제1항 내지 제18항 중 선택된 하나의 항에 따르는 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 기재에 촉매패턴을 형성하는 단계; 및 (S12) 상기 (S1)단계의 전자파 차폐용 촉매 전구체 수지 조성물 성분 중 촉매(C2)로서 팔라듐(Pd) 입자 또는 은(Ag) 입자가 사용된 경우에는 상기 형성된 촉매패턴에 2단계의 무전해 도금법을 진행하여 금속패턴을 형성하는 단계;를 포함하여 진행하는 것을 특징으로 한다.One of the electromagnetic wave shielding metal pattern manufacturing method according to the present invention provided to achieve the technical problem to be achieved by the present invention described above, (S11) for electromagnetic wave shielding according to any one of the claims selected from claim 1 to 18. Forming a catalyst pattern on the substrate using the catalyst precursor resin composition; And (S12) when palladium (Pd) particles or silver (Ag) particles are used as the catalyst (C2) among the catalyst precursor resin composition components for electromagnetic wave shielding in the step (S1), two steps of electrolessness are performed on the formed catalyst pattern. Forming a metal pattern by the plating method; characterized in that it proceeds, including.
전술한 본 발명이 이루고자 하는 기술적 과제를 달성하기 위해 제공되는 본 발명에 따르는 전자파 차폐용 금속 패턴 제조 방법의 다른 하나는, (S21) 제1항 내지 제18항 중 선택된 하나의 항에 따르는 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 기재에 촉매패턴을 형성하는 단계; (S22) 상기 (S1)단계의 전자파 차폐용 촉매 전구체 수지 조성물 성분 중 촉매(C2)로서 플루오르화 은(Ag)이온 유기착화물이 사용된 경우에는 상기 형성된 촉매패턴을 환원시키는 단계; 및 (S23) 상기 환원된 촉매패턴에 2단계의 무전해 도금법을 진행하여 금속패턴을 형성하는 단계;를 포함하여 진행하는 것을 특징으로 한다.Another method of manufacturing a metal pattern for electromagnetic shielding according to the present invention provided to achieve the technical problem to be achieved by the present invention described above, (S21) electromagnetic shielding according to any one of the items selected from claims 1 to 18. Forming a catalyst pattern on the substrate using the catalyst precursor resin composition for the catalyst; (S22) reducing the formed catalyst pattern when the silver fluoride (Ag) ion organic complex is used as the catalyst (C2) in the catalyst precursor resin composition component for electromagnetic wave shielding in the step (S1); And (S23) forming a metal pattern by performing a two-step electroless plating method on the reduced catalyst pattern.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 설명하고, 발명에 대한 이해를 돕기 위해 첨부도면을 참조하여 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않아야 한다. 본 발명의 실시예들은 당 업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 유기고분자수지인 공중합체수지(C1)는 패턴을 형성하기 위해 염기 현상액에 대한 충분한 용해도가 확보되어야 하므로, 카르복시기를 갖는 단량체(C11)를 포함하는 것이 바람직하다. 상기 카르복시기를 갖는 단량체(C11)은, 아크릴산, 메타크릴산, 크로톤산, 이타콘산, 말레인산, 퓨마린산, 모노메틸말레인산, 이소프렌술폰산, 스티렌술폰산 또는 5-노보넨-카르복실산 등과 같은 불포화 카르복시산이 이용될 수 있으 며, 반드시 이에 한정되는 것은 아니다. 한편, 상기 예시된 불포화 카르복시산은 단독 또는 둘 이상의 물질이 함께 이용될 수 있음은 자명하다. 카르복실기 함유한 단량체와 공중합 가능한 단량체로는 특별히 이에 한정하지는 않으며, 불포화 이중결합을 갖는 화합물이면 바람직하게 이용될 수 있다.The copolymer resin (C1), which is an organic polymer resin included in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention, must have sufficient solubility in a base developer to form a pattern, and thus includes a monomer (C11) having a carboxyl group. It is desirable to. The monomer (C11) having the carboxyl group is an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid or 5-norbornene-carboxylic acid. It may be used, but is not necessarily limited thereto. On the other hand, it is apparent that the above-mentioned unsaturated carboxylic acids may be used alone or in combination of two or more materials. The monomer copolymerizable with the carboxyl group-containing monomer is not particularly limited, and may be preferably used as long as it is a compound having an unsaturated double bond.
또한, 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 유기고분자수지인 공중합체수지(C1)는 내화학성 및 촉매 전구체의 유실을 최소하기 위하여 그 내부에 포함된 질소에 지용성 관능기가 치환된 말레이미드(maleimide) 단량체를 포함하여 이루어지면 바람직하다. 상기 질소에 지용성 관능기가 치환된 말레이미드 단량체는, N-에틸말레이미드, N-로필말레이미드, N-메톡시카르보닐말레이미드, N-푸르푸릴말레이미드, N-사이클로헥실말레이미드, N-부틸말레이미드, 2,5-다이옥소-피롤린-1-카르복사아마이드, 3,4-다이클로로메틸-피롤-2,5-다이온, N-벤질말레이미드, N-페닐말레이미드, 3-메틸-N-페닐말레이미드, N-(오르소-토일)-N-페닐말레이미드, N-(4-플루오르페닐)말레이미드, N-(2,6-자일)말레이미드), 3-클로로-1-페닐-파이롤-2,5-다이온, N-(2-클로로페닐)-말레이미드, N-(1-나프탈릴)-말레이미드, 1-(2-트라이플로오루메틸-페닐)-피롤-2,5-다이온 등을 들 수 있으며, 반드시 이에 한정되는 것은 아니다. 또한, 상기 예시된 물질들은 단독 또는 이종 이상의 물질이 함께 사용될 수도 있음은 자명하다.In addition, the copolymer resin (C1), which is an organic polymer resin included in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention, has a fat-soluble functional group substituted with nitrogen contained therein to minimize chemical resistance and loss of the catalyst precursor. It is preferred to include maleimide monomers. The maleimide monomer in which the fat-soluble functional group is substituted for the nitrogen includes N-ethyl maleimide, N-rofilmaleimide, N-methoxycarbonyl maleimide, N-furfuryl maleimide, N-cyclohexyl maleimide, and N-. Butyl maleimide, 2,5-dioxo-pyrroline-1-carboxamide, 3,4-dichloromethyl-pyrrole-2,5-dione, N-benzylmaleimide, N-phenylmaleimide, 3 -Methyl-N-phenylmaleimide, N- (ortho-toyl) -N-phenylmaleimide, N- (4-fluorophenyl) maleimide, N- (2,6-xyl) maleimide), 3- Chloro-1-phenyl-pyrrole-2,5-dione, N- (2-chlorophenyl) -maleimide, N- (1-naphthalyl) -maleimide, 1- (2-trifluoromethyl- Phenyl) -pyrrole-2,5-dione and the like, but are not necessarily limited thereto. In addition, it is apparent that the above-exemplified materials may be used alone or in combination of two or more materials.
특히, 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 공중합체수지를 구성하는 말레이미드 단량체는 내화학성 측면에서 그 내부에 포함된 질소에 방향족 관능기가 치환된 것이 이용되면 바람직하나, 반드시 이에 한정되 는 것은 아니다. 한편, 공중합체수지에 포함될 수 있는 다른 단량체로는 그 내부에 공중합에 참가할 수 있는 활성화된 불포화 결합을 갖고 있는 단량체라면 바람직하게 이용될 수 있다. 한편, 투명기재와 흡착력과 내화학성을 고려하면 방향족 관능기를 갖고 있는 아크릴레이트가 바람직하다.In particular, the maleimide monomer constituting the copolymer resin included in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention is preferably used in that the aromatic functional group is substituted for nitrogen contained therein in terms of chemical resistance, It is not limited. On the other hand, the other monomer that can be included in the copolymer resin can be preferably used as long as it has a monomer having an activated unsaturated bond that can participate in the copolymerization therein. On the other hand, in consideration of the transparent substrate, the adsorptivity, and the chemical resistance, an acrylate having an aromatic functional group is preferable.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함에 포함되는 유기고분자수지인 공중합체수지는 상기한 바와 같이, 카르복시기를 갖는 단량체와 그 내부에 포함된 질소에 지용성 관능기가 치환된 말레이미드 단량체의 공중합체수지로서 팔라듐 또는 은 촉매와의 호환성이 높아 저장성 및 조성물의 안정성이 우수하며, 현상성 및 패턴 특성을 확보할 수 있다.As described above, the copolymer resin, which is an organic polymer resin, included in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention, may be a monomer having a carboxyl group and a maleimide monomer in which a fat-soluble functional group is substituted for nitrogen contained therein. As a copolymer resin, it is highly compatible with a palladium or silver catalyst, and thus has excellent storage properties and stability of the composition, and developability and pattern characteristics can be secured.
상기 공중합체수지의 중량평균분자량은 3,000 내지 30,000이면 바람직하다. 상기 공중합체수지의 중량평균분자량에 대한 수치범위와 관련하여, 상기 하한에 미달하면 현상시 경화가 양호하게 진행되지 않아 접착특성이 저하되며 미세패턴의 형상이 좋지 않은 문제점이 발생하여 바람직하지 않으며, 상기 상한을 초과하면 현상액의 용해도가 필요 이상으로 높아져 패턴 박막의 질이 저하되어 바람직하지 못하다. 한편, 상기 공중합체수지의 중량평균분자량이 5,000 내지 15,000인 경우에는 더욱 바람직하다.The weight average molecular weight of the copolymer resin is preferably 3,000 to 30,000. With respect to the numerical range for the weight average molecular weight of the copolymer resin, if the lower limit is less than the lower limit, the curing does not proceed well, the adhesive properties are deteriorated and the shape of the fine pattern is not good, it is not preferable, When the above upper limit is exceeded, the solubility of the developing solution becomes higher than necessary and the quality of the pattern thin film is deteriorated, which is not preferable. On the other hand, the weight average molecular weight of the copolymer resin is more preferably 5,000 to 15,000.
상기 공중합체수지의 산가는 90 내지 450㎎ KOH/g이면 미세 패턴 형성에 바람직하다. 상기 공중합체수지의 산가에 대한 수치범위와 관련하여, 상기 하한에 미달하면 알칼리 현상액에 대한 코팅박막의 용해도가 낮아 현상이 불량하게 진행되어 바람직하지 못하며, 상기 상한을 초과하면 용해도가 너무 높아 단선이나 이탈 등의 패턴 불량이 발생하기 쉬워져 바람직하지 못하다. 한편, 상기 공중합체수지의 산가가 200 내지 350㎎ KOH/g인 경우에는 더욱 바람직하다.The acid value of the copolymer resin is 90 to 450 mg KOH / g is preferable for forming a fine pattern. In relation to the numerical range of the acid value of the copolymer resin, if the lower limit is less than the lower limit, the solubility of the coating thin film in the alkaline developer is low, so the development is poor, and if the upper limit is exceeded, the solubility is too high, so that It is unpreferable because pattern defects, such as a deviation, generate easily. On the other hand, when the acid value of the copolymer resin is 200 to 350 mg KOH / g is more preferable.
상기 말레이미드 단량체는, 상기 공중합체수지를 구성하는 전체 단량체 양의 5 내지 50 중량%이면 패턴의 내화학성 및 촉매 유실 방지 측면에서 바람직하다. 상기 말레이미드 단량체의 함량에 대한 수치범위와 관련하여, 상기 하한에 미달하면 충분한 내화학성을 얻기 힘들어짐으로써 패턴 결함 발생이 용이하여 바람직하지 못하며, 상기 상한을 초과하면 정교한 패턴 폭을 확보하기 어려워 바람직하지 못하다. 한편, 상기 말레이미드 단량체의 함량이 상기 공중합체수지를 구성하는 전체 단량체 양의 10 내지 30 중량%인 경우에는 더욱 바람직하다.The maleimide monomer is preferably 5 to 50% by weight of the total monomer amount constituting the copolymer resin in view of chemical resistance of the pattern and prevention of catalyst loss. Regarding the numerical range for the content of the maleimide monomer, if it falls below the lower limit, it is difficult to obtain sufficient chemical resistance, which is not preferable because of easy occurrence of pattern defects, and when the upper limit is exceeded, it is difficult to secure a precise pattern width. I can't. On the other hand, when the content of the maleimide monomer is 10 to 30% by weight of the total monomer amount constituting the copolymer resin is more preferable.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 촉매(C2)는, 팔라듐입자, 은입자 또는 은이온 유기착화물이 이용될 수 있다. 상기 조성물에 포함되는 촉매(C2)는, 상기 조성물 중 용매를 제외한 유기고형분 중량 대비 2 내지 40 중량%이면 바람직하다. 상기 촉매(C2)의 함량에 대한 수치범위와 관련하여, 상기 하한에 미달하면 촉매의 양이 충분하지 않아 무전해 도금시 금속의 증착속도가 현저히 낮고, 균일한 구리 도금박막의 형성이 어려워져 바람직하지 못하며, 상기 상한을 초과하면 현상성이 떨어져 패턴 특성이 저하되어 균일한 미세 촉매 패턴을 형성하기 어렵고, 패턴의 형상이 우수하지 못하며, 조성물의 저장성이 현저히 저하되어 바람직하지 못하다. 한편, 상기 촉매(C2)의 함량이 상기 조성물 중 용매를 제외한 유기고형분 중량 대비 5 내지 20 중량%이면 더욱 바람직하다.As the catalyst (C2) included in the catalyst precursor resin composition for shielding electromagnetic waves according to the present invention, palladium particles, silver particles or silver ion organic complexes may be used. The catalyst (C2) contained in the composition is preferably 2 to 40% by weight based on the weight of organic solids excluding the solvent in the composition. Regarding the numerical range for the content of the catalyst (C2), if the lower limit is less than the lower limit, the amount of the catalyst is not sufficient, the deposition rate of the metal during electroless plating is significantly low, and it is difficult to form a uniform copper plating thin film. If the upper limit is exceeded, the developability is poor, and the pattern characteristic is lowered, making it difficult to form a uniform fine catalyst pattern, the shape of the pattern is not excellent, and the shelf life of the composition is significantly lowered, which is not preferable. On the other hand, the content of the catalyst (C2) is more preferably 5 to 20% by weight based on the weight of the organic solids excluding the solvent in the composition.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 에틸 렌성 불포화 결합을 포함하는 다관능성 단량체(C3)는, 광경화를 촉진하고 현상성을 향상시키며, 무전해 도금시 촉매 형성막의 접착성, 내화학성 등을 향상시키는 데에 기여한다. 상기 다관능성 단량체(C3)는, 에틸렌글리콜디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 에틸렌기의 수가 2 내지 14인 폴리에틸렌글리콜 디아크릴레이트, 또는 폴리에틸렌글리콜 디메타아크릴레이트, 트리메틸올프로판트리 아크릴레이트, 트리메틸올프로판트리메타크릴레이트, 펜타에리스리톨 트리아크릴레이트, 펜타에리스리톨트리메타크릴레이트, 펜타에리스리톨 테트라아크릴레이트, 펜타에리스리톨테트라메타크릴레이트, 프로필렌기의 수가 2 내지 14인 프로필렌글리콜디아크릴레이트, 또는 프로필렌글리콜디메타크릴레이트, 디펜타에리스리톨펜타아크릴레이트, 디펜타에리스리톨 펜타메타크릴레이트, 디펜타에리스리톨헥사아크릴레이트, 디펜타 에리스리톨헥사메타크릴레이트 등의 다가 알코올과 α,β-불포화 카르복실산을 에스테르화하여 얻어지는 화합물; 트리메틸올프로판 트리글리시딜에테르아크릴산 부가물, 비스페놀 A 디글리시딜에테르아크릴산 부가물등의 글리시딜기를 함유하는 화합물에 아크릴산 또는 메타아크릴산을 부가하여 얻어지는 화합물; β-히드록시에틸아크릴레이트 또는 β-히드록시에틸메타크릴레이트의 프탈산에스테르, β-히드록시에틸아크릴레이트 또는 β-히드록시에틸메타크릴레이트의 톨루엔디이소시아네이트의 부가물 등의 수산화기 또는 에틸렌성 불포화 결합을 갖는 화합물과 다가 카르복실산과의 에스테르 화합물, 또는 폴리이소시아네이트와의 부가물 등을 들 수 있으며, 반드시 이에 한정되는 것은 아니다. 한편, 상기 예시된 물질은 단독 또는 둘 이상의 물질이 함께 사용될 수 있음은 자명하다.The multifunctional monomer (C3) comprising an ethylenically unsaturated bond included in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention promotes photocuring and improves developability, and provides adhesion of the catalyst-forming film during electroless plating, Contribute to improving chemical resistance and the like. The polyfunctional monomer (C3) is ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate having a number of ethylene groups of 2 to 14, or polyethylene glycol dimethacrylate, trimethylolpropane triacrylate , Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, propylene glycol diacrylate having 2 to 14 propylene groups, or Polyhydric alcohols such as propylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and α, β-unsaturated carboxylic acids Esterification W obtained compound; Compounds obtained by adding acrylic acid or methacrylic acid to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Hydroxyl groups or ethylenic unsaturations such as phthalic acid esters of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate, adducts of toluene diisocyanate of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate The ester compound of the compound which has a bond, and polyhydric carboxylic acid, or the adduct of polyisocyanate, etc. are mentioned, It is not necessarily limited to this. On the other hand, it is apparent that the above exemplified materials may be used alone or in combination of two or more materials.
상기 다관능성 단량체(C3)는 에틸렌성 불포화 결합을 갖는 관능기수가 3 이상인 것이 미세 촉매패턴의 형상 및 무전해 도금시 내화학성 접착 특성의 측면에서 바람직하다.The polyfunctional monomer (C3) is preferably three or more functional groups having an ethylenically unsaturated bond in view of the shape of the fine catalyst pattern and chemical resistance adhesive properties during electroless plating.
상기 다관능성 단량체는, 그 함량이 상기 공중합체수지(C1) 100중량부에 대하여 20 내지 150 중량부이면 바람직하다. 상기 다관능성 단량체의 함량에 관한 수치범위와 관련하여, 상기 하한에 미달하면, 충분히 경화되지 않아, 촉매에 의한 미세 패턴 형성이 어렵고 무전해 도금시 용해 및 박리 등의 불량이 발생할 수 있어 바람직하지 못하며, 상기 상한을 초과하면 코팅성이 감소되고 내부까지 균일하게 경화되지 않아 미세 촉매 패턴을 형성하기 어렵기 때문에 바람직하지 못하다.The content of the multifunctional monomer is preferably 20 to 150 parts by weight based on 100 parts by weight of the copolymer resin (C1). Regarding the numerical range of the content of the multifunctional monomer, if it is less than the lower limit, it is not sufficiently cured, it is difficult to form a fine pattern by the catalyst, and it is not preferable because defects such as dissolution and peeling may occur during electroless plating. If the upper limit is exceeded, the coating property is reduced and not uniformly cured to the inside, which is not preferable because it is difficult to form a fine catalyst pattern.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 광개시제(C4)는 아세토페논류, 벤조페논류, 미히라(Michler) 벤조일벤조에이트, α-아밀록심에스테르, 및 티옥산톤류로 구성되는 그룹으로부터 선택된 하나의 물질로서, 반드시 이에 한정되는 것은 아니다. 한편, 위 예시된 광개시제는 단독 또는 이종 이상의 물질이 함께 이용될 수 있음은 자명하다. 상기 광개시제(C4)는, 그 함량이 상기 공중합체수지(C1) 100 중량부에 대하여 1 내지 25 중량부이면 바람직하다. 상기 광개시제에 대한 수치범위를 벗어나는 경우에는 패턴 형성이 이루어지지 않아 바람직하지 못하다. 한편, 상기 광개시제의 함량이 상기 공중합체수지(C1) 100 중량부에 대하여 5 내지 20 중량부이면 더욱 바람직하다.Photoinitiator (C4) included in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention is a group consisting of acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, and thioxanthones One material selected from, but is not necessarily limited thereto. On the other hand, it is apparent that the photoinitiator exemplified above may be used alone or in combination of two or more materials. The photoinitiator (C4) is preferably 1 to 25 parts by weight based on 100 parts by weight of the copolymer resin (C1). If it is out of the numerical range for the photoinitiator, the pattern is not formed, which is not preferable. On the other hand, the photoinitiator is more preferably 5 to 20 parts by weight based on 100 parts by weight of the copolymer resin (C1).
전술한 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물은 그 필요에 따라, 상기 광증감제(C6)가 상기 공중합체수지와 광개시제의 총량을 기준으로 100중량부에 대하여 최대 10중량부, 바람직하게는 0.1 내지 10 중량부로 사용될 수 있다. 상기 광증감제의 사용 함량에 대한 수치범위와 관련하여, 상기 상한을 초과하면 패턴의 정확성이 저하되므로 바람직하지 못하다. 상기 광증감제(C6)는, n-부틸아민, 트리에틸아민 또는 트리-n-부틸포스파인 등이 이용될 수 있으나, 반드시 이에 한정되는 것은 아니다. 한편, 상기 광증감제(C6)로 예시된 물질은 단독 또는 둘 이상이 함께 사용될 수 있음은 자명하다.In the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention described above, the photo-sensitizer (C6) is preferably 10 parts by weight based on 100 parts by weight based on the total amount of the copolymer resin and the photoinitiator, preferably 10 parts by weight. May be used in an amount of 0.1 to 10 parts by weight. Regarding the numerical range for the content of the photosensitizer, exceeding the upper limit is not preferable because the accuracy of the pattern is lowered. As the photosensitizer (C6), n-butylamine, triethylamine or tri-n-butylphosphine may be used, but is not necessarily limited thereto. On the other hand, it is apparent that the materials exemplified as the photosensitizer (C6) may be used alone or two or more together.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물에 포함되는 유기용매(C5)는, 메탄올, 에탄올, n-프로파놀, 이소프로판올, 에틸렌글리콜, 또는 프로필렌글리콜과 같은 알코올류; 아세톤, 메틸에틸케톤, 시클로헥사논, 또는 n-메틸-2-피롤리돈과 같은 케톤류; 톨루엔, 크실렌, 또는 테트라메틸벤젠과 같은 방향족 탄화수소류; 셀로솔브, 메틸셀로솔브, 에틸셀로솔브, 3-메토시프로필렌아세테이트, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜 에틸에테르, 디프로필렌글리콜모노메틸에테르, 또는 디프로필렌 글리콜에틸 에테르와 같은 글리콜에테르류; 에틸아세테이트, 부틸아세테이트, 셀로솔브아세테이트, 에틸셀로솔브아세테이트, 부틸셀로솔브아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 또는 프로필렌글리콜에틸에테르 아세테이트와 같은 아세테이트류; N,N-다이메틸아세타아마이드, N,N-다이메틸포름아마이드, 아세토나이트라이드와 같은 아마이드류 등으로 구성되는 그룹으로부터 선택된 물질이 사용될 수 있으며, 반드시 이에 한정되는 것은 아니다. 한편, 상기 유기용매로서 예시된 물질들은 단독 또는 둘 이상이 함께 사용될 수도 있음은 자명하다.The organic solvent (C5) contained in the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention includes alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, or propylene glycol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, or n-methyl-2-pyrrolidone; Aromatic hydrocarbons such as toluene, xylene, or tetramethylbenzene; Glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, 3-methoxypropylene acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol ethyl ether; Acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, or propylene glycol ethyl ether acetate; A material selected from the group consisting of N, N-dimethylacetamide, N, N-dimethylformamide, amides such as acetonitrile, and the like may be used, but is not necessarily limited thereto. On the other hand, it is apparent that the materials exemplified as the organic solvent may be used alone or two or more together.
본 발명이 이루고자 하는 기술적 과제를 달성하기 위해 제공되는 전자파 차폐용 금속 패턴 제조 방법 중, 전술한 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 촉매패턴을 형성하는 단계(S11 또는 S21)에서 사용되는 기재는 투명 재질을 갖는 소재이면 바람직하며, 유리, 폴리카보네이트, 아크릴수지, 폴리에스터(PET), 트리아세테이트 셀룰로스(TAC), 폴리염화비닐수지, 폴리아마이드수지, 폴리이미드수지 등의 재질로 이루어진 시트 또는 필름 등이 사용될 수 있으며, 반드시 이에 한정되는 것은 아니다. 상기 촉매 패턴의 형성단계(S1)는, 노광 및 현상에 의한 패턴형성법, 오프셋 프린팅법, 잉크젯 프린팅법, 임프린트법, 및 스크린 프린팅법 중 선택된 하나의 방법이 이용되면 바람직하며, 반드시 이에 한정되는 것은 아니다.The substrate used in the step (S11 or S21) of forming a catalyst pattern using the above-mentioned catalyst precursor resin composition for electromagnetic wave shielding of the electromagnetic shielding metal pattern manufacturing method provided to achieve the technical problem to be achieved by the present invention A material having a transparent material is preferable, and a sheet or film made of a material such as glass, polycarbonate, acrylic resin, polyester (PET), triacetate cellulose (TAC), polyvinyl chloride resin, polyamide resin, or polyimide resin Etc. may be used, but is not necessarily limited thereto. The forming of the catalyst pattern (S1) is preferably performed using one method selected from a pattern forming method, an offset printing method, an inkjet printing method, an imprint method, and a screen printing method by exposure and development, and the present invention is not limited thereto. no.
상기 촉매 패턴을 형성하는 방법 중, 노광 및 현상하여 패턴을 형성하는 방법은, 먼저 상기 기재에 본 발명에 따른 전자파 차폐용 촉매 전구체 수지 조성물을 도포하고, 이어서 금속 촉매 전구체 수지막을 형성하는 단계로 진행하면 바람직하다. 이때, 상기 도포방법은 롤 코팅, 그라비아 코팅, 딥 코팅, 바 코팅, 스프레이 코팅, 또는 스핀 코팅 등의 코팅방법을 이용하며, 이러한 예시된 방법에 특별히 제한되지 않으나, 도포액의 특성이나 도포량에 따라 최적의 방법이 선택될 수 있음은 자명하다. 이러한 도포 및 수지막 형성 이후, 상기 코팅된 금속 촉매 수지막을 노광 및 현상하여 촉매막 패턴을 형성한다. 상기 수지막에 대한 노광 및 현상 공정은 일반적으로 알려져 있는 방법을 이용할 수 있다. 상기 노광 공정은, 노광 패턴을 갖는 마스크를 이용하여 접촉 또는 비접촉 노광 방식 등으로 노광시킬 수 있으며, 이때 사용되는 광원은, 할로겐램프, 고압수은등, 메탈할라이드램프 등의 광원이 사용될 수 있으나, 반드시 이에 한정되는 것은 아니다. 한편, 상기 현상공정은 스프레이법 또는 침지법에 의해 진행할 수 있다.Among the methods of forming the catalyst pattern, a method of exposing and developing the pattern to form the pattern firstly applies the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention to the substrate, and then proceeds to forming a metal catalyst precursor resin film. Is preferable. In this case, the coating method uses a coating method such as roll coating, gravure coating, dip coating, bar coating, spray coating, or spin coating, and the like, but is not particularly limited to these illustrated methods, depending on the characteristics of the coating liquid or the coating amount. It is obvious that the optimal method can be chosen. After such coating and resin film formation, the coated metal catalyst resin film is exposed and developed to form a catalyst film pattern. The exposure and the image development process to the said resin film can use the method generally known. The exposure process may be performed by contact or non-contact exposure using a mask having an exposure pattern. In this case, a light source such as a halogen lamp, a high pressure mercury lamp, or a metal halide lamp may be used. It is not limited. In the meantime, the developing step may be performed by a spray method or a dipping method.
이로부터 형성되는 촉매 패턴은, 그 라인 폭이 30㎛ 이하이면 바람직하며, 그 라인 폭이 20㎛ 이하로 형성되면 더욱 바람직하다. 또한 본 발명에 따르는 조성물을 이용하면, 그 라인 폭이 10㎛ 이하인 미세 패턴을 형성할 수도 있다. 또한, 상기 촉매 패턴은, 가시광선에 대한 개구율이 60% 이상이면 바람직하며, 그 개구율이 70 % 이상이면 더욱 바람직하다.The catalyst pattern formed from this is preferable if the line width is 30 micrometers or less, and it is more preferable if the line width is formed in 20 micrometers or less. In addition, using the composition according to the present invention, it is also possible to form a fine pattern having a line width of 10 m or less. Moreover, the said catalyst pattern is preferable in it being 60% or more of aperture ratio with respect to visible light, and more preferable in it being 70% or more of aperture ratio.
상기 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 촉매 패턴을 형성하는 경우, 그 조성물 중 촉매로서 사용된 물질에 따라 공정 진행을 달리하므로, 이를 구별하여 설명하기로 한다.When the catalyst pattern is formed using the catalyst precursor resin composition for electromagnetic wave shielding, the process proceeds differently according to the material used as the catalyst in the composition, and thus it will be described separately.
상기 전자파 차폐용 촉매 전구체 수지 조성물 중 촉매로서 사용되는 물질이 팔라듐(Pd) 입자 또는 은(Ag) 입자인 경우에는 상기와 같이 촉매 패턴을 형성(S11)한 후, 별도의 환원공정을 진행하지 않고 곧바로 2단계 무전해 도금법(S12)을 진행할 수 있다.When the material used as the catalyst in the catalyst precursor resin composition for electromagnetic wave shielding is palladium (Pd) particles or silver (Ag) particles, the catalyst pattern is formed as described above (S11), and then a separate reduction process is not performed. Immediately, the two-step electroless plating method (S12) can be performed.
이와 달리, 상기 전자파 차폐용 촉매 전구체 수지 조성물 중 촉매로서 사용되는 물질이 은이온 유기착화물 전구체인 경우에는 상기와 같이 촉매 패턴을 형성(S21)한 후 무전해 도금 특성을 향상시키기 위해 별도의 환원 공정(S22)을 진행한 이후에 2단계 무전해 도금법(S23)을 진행하는 것이 바람직하다. 상기 은이온 유기착화물 전구체의 환원은 본 발명과 관련된 기술 분야에서 일반적으로 적용 가능 한 공지의 방법을 이용하여 진행될 수 있으며, 환원제를 사용하거나 가열 및 UV 노광을 함께 이용하거나, 가열 또는 UV 노광의 어느 하나의 방법에 의해 환원시킬 수 있으며, 반드시 이에 한정되는 것은 아니다.On the contrary, in the case where the material used as the catalyst in the catalyst precursor resin composition for electromagnetic shielding is a silver ion organic complex precursor, a catalyst pattern is formed as described above (S21) and then a separate reduction is performed to improve the electroless plating property. It is preferable to proceed with a two-step electroless plating method (S23) after going through a process (S22). Reduction of the silver ion organic complex precursor may be carried out using a known method generally applicable in the art related to the present invention, using a reducing agent or using heating and UV exposure, or by heating or UV exposure. It can be reduced by either method, but is not necessarily limited thereto.
상기와 같이, 환원제를 사용하여 은이온 유기착화물 전구체를 환원시키는 경우에는 소듐보레인하이드라이드(NaBH4)나 아스코르브산(Ascorbic acid) 수용액 등의 환원제를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다. 상기와 같이 환원제 수용액을 이용하는 경우에는 그 농도가 0.01 내지 1.0 M이면 바람직하다. 한편, 무전해 도금 용액에 의해 자발적으로 환원이 이루어지는 경우에는 별도의 환원제를 사용하지 아니할 수도 있음은 자명하다. 상기 환원제를 이용한 환원방법이 습식 공정인 것과는 달리 상기 UV 노광 또는 가열 방식에 의한 은이온 유기착화물 전구체의 환원방법은 촉매 유실의 문제를 감소시키거나 방지시킬 수 있는 점에서 바람직하다.As described above, when reducing the silver ion organic complex precursor using a reducing agent, a reducing agent such as sodium borane hydride (NaBH 4 ) or an ascorbic acid aqueous solution may be used, but is not limited thereto. . When using a reducing agent aqueous solution as mentioned above, it is preferable that the density | concentration is 0.01-1.0 M. On the other hand, when the reduction is spontaneous by the electroless plating solution, it is obvious that a separate reducing agent may not be used. Unlike the reduction method using the reducing agent is a wet process, the reduction method of the silver ion organic complex precursor by the UV exposure or the heating method is preferable in that it can reduce or prevent the problem of catalyst loss.
상기 2단계 무전해 도금법(S12 또는 S23)은, 가격 및 전자파 차폐 성능 측면에서 구리 도금 또는 은 도금을 형성하면 바람직하다. 무전해 구리 도금은 종래 일반적으로 알려져 있는 구리 도금액을 사용하여 행할 수 있으며, 황산동과 같은 금속 이온염, 포르말린 같은 환원제, EDTA 같은 착화제 및 미량의 기타 첨가제를 포함하는 도금액 등을 이용하여 진행할 수 있으며, 반드시 이에 한정되는 것은 아니다.The two-step electroless plating method (S12 or S23) is preferable to form copper plating or silver plating in view of cost and electromagnetic shielding performance. Electroless copper plating may be performed using a copper plating solution, which is generally known in the art, and may be performed using a metal ion salt such as copper sulfate, a reducing agent such as formalin, a plating solution containing a complexing agent such as EDTA, and a small amount of other additives. However, the present invention is not limited thereto.
종래에 이용되던 무전해 도금법은, 그 진행 과정에서 촉매 패턴의 침식 또는 촉매 유실 등의 문제점이 발생하여 무전해 도금시 용액을 교반하기 어렵게 되고, 이로 인하여 도금 속도를 증가시키는 데에 기술적 한계에 봉착하고 있으며, 도금이 느리게 진행되기 때문에 촉매 패턴이 스웰링되는 현상이 발생하는 등의 여러 문제점이 제기되고 있다.In the electroless plating method used in the related art, problems such as erosion of catalyst patterns or loss of catalyst occur during the process, and thus it is difficult to stir the solution during electroless plating, which leads to technical limitations in increasing the plating speed. Since the plating proceeds slowly, various problems such as swelling of the catalyst pattern occur.
따라서, 본 발명에서는 종래에 제기되는 문제점을 해결함과 동시에 도금 속도의 개선을 위하여 하기와 같이 2단계로 구분되는 도금 공정을 진행하게 되었다.Accordingly, in the present invention, the plating process divided into two steps is performed in order to solve the problems posed in the related art and to improve the plating speed.
그 첫 번째 단계는, 초기 도금 단계(S12a 또는 S23a)로서, 포토리소그래피를 통해 형성된 촉매 패턴 상에 존재하는 촉매를 이용하여, 교반없이 무전해 도금을 수행하여, 촉매 패턴 표면을 완전히 덮는 금속 박막을 형성한다. 상기 초기 도금 단계(S12a 또는 S23a)는, 도금이 진행되는 도중 교반이 수반되지 않으므로 종래의 방법과 달리 촉매의 유실이 적으며, 무전해 도금 용액 내에서의 고분자 수지의 내화학성 및 접착성의 특성이 우수하게 유지되는 장점이 발현된다.The first step is an initial plating step (S12a or S23a), which is performed by electroless plating without agitation using a catalyst present on the catalyst pattern formed through photolithography to completely cover the metal film surface. Form. Since the initial plating step (S12a or S23a) is not accompanied by agitation during the plating process, there is little loss of catalyst unlike the conventional method, and the chemical resistance and adhesiveness of the polymer resin in the electroless plating solution Advantages that remain good are manifested.
이후, 상기 초기 도금 단계(S12a 또는 S23a)를 진행한 후, 촉매 패턴을 구리 박막으로 완전히 덮을 수 있도록 구리 박막을 성장시키는 두 번째 단계(S12b 또는 S12b)를 진행한다. 상기 구리 박막을 성장시키는 단계(S12b 또는 S23b)에서는 구리 박막이 형성된 이후, 무전해 도금 속도를 증가시키기 위한 목적에서, 상기 초기 도금 단계(S12a 또는 S23a)와 달리 교반 작업을 수반하여 진행한다.Thereafter, after the initial plating step (S12a or S23a), the second step (S12b or S12b) to proceed to grow the copper thin film so as to completely cover the catalyst pattern with the copper thin film. In the step of growing the copper thin film (S12b or S23b), after the copper thin film is formed, in order to increase the electroless plating rate, unlike the initial plating step (S12a or S23a) is carried out with a stirring operation.
전술한 바와 같이 진행되는 2단계 무전해 도금법(S12 또는 S23)은, 초기 도금 단계(S12a 또는 S23a)에서는 용액 교반을 행하지 않으므로 강염기의 무전해 도금 용액 내에서 고분자 수지인 촉매 패턴의 침식을 최소화하고 촉매의 유실을 방지 할 수 있으며, 박막 성장 단계(S12b 또는 S23b) 에서는 용액 교반을 수반함으로써 무전해 도금의 속도를 향상시킬 수 있으므로 공정 시간을 단축시킬 수 있는 장점이 있다.As described above, the two-step electroless plating method (S12 or S23) does not perform solution stirring in the initial plating step (S12a or S23a), thereby minimizing the erosion of the catalyst pattern, which is a polymer resin, in the electroless plating solution of the strong base. The loss of the catalyst can be prevented, and in the thin film growth step (S12b or S23b), the speed of the electroless plating can be improved by accompanied by the stirring of the solution, thereby reducing the process time.
전술한 조성물 및 이를 이용하는 제조방법에 의해 제조되는 전자파 차폐막의 두께는 도금욕의 금속염 또는 금속 이온 농도, 도금 온도, 증착 시간 등에 의하여 제어할 수 있다. 상기 전자파 차폐막은, 그 두께가 0.3 내지 10 ㎛이면 바람직하다. 상기 전자파 차폐막의 두께에 대한 수치범위와 관련하여, 상기 수치범위를 만족하는 경우에는 전자파 차폐를 위한 충분한 도전성을 확보할 수 있어 바람직하다. 특히, 상기 상한을 초과하는 경우에는 도금 공정 시간이 오래 걸려, 생산성이 저하되며, 선폭이 굵어져 개구율이 낮아지며, 무아레 현상이 쉽게 발생할 수 있다. 한편, 상기 전자파 차폐막의 두께가 0.5㎛이상이면 더욱 바람직하다.The thickness of the electromagnetic shielding film prepared by the above-described composition and the manufacturing method using the same may be controlled by the metal salt or metal ion concentration of the plating bath, the plating temperature, the deposition time, and the like. It is preferable that the said electromagnetic wave shielding film is 0.3-10 micrometers in thickness. Regarding the numerical range for the thickness of the electromagnetic shielding film, when the numerical range is satisfied, sufficient conductivity for electromagnetic shielding can be secured. In particular, when the upper limit is exceeded, the plating process takes a long time, the productivity is lowered, the line width is thickened, the opening ratio is lowered, and the moire phenomenon may easily occur. On the other hand, it is more preferable if the thickness of the said electromagnetic wave shielding film is 0.5 micrometer or more.
전술한 바와 같이, 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물 및 이를 이용한 전자파 차폐용 금속 패턴 제조 방법에 따라 제조된 전자파 차례용 금속 패턴은 우수한 전자파 차폐능을 발현하고 있으므로, CRT, PDP, 액정, EL 등의 디스플레이 전면으로부터 발생되는 전자파 차폐막이나 연성 회로 기판의 배선 형성에 사용하기에 바람직하다.As described above, the electromagnetic wave shielding metal pattern prepared according to the electromagnetic wave shielding catalyst precursor resin composition and the electromagnetic wave shielding metal pattern manufacturing method using the same exhibits excellent electromagnetic shielding ability, and thus, CRT, PDP, liquid crystal It is suitable for use in forming wirings of electromagnetic wave shielding films and flexible circuit boards generated from the front surface of displays such as EL and the like.
< 실시예(Sa1 내지 Sa3) ><Examples (Sa1 to Sa3)>
유기고분자수지(Organic Polymer Resin ( 중합체수지Polymer resin ) 준비() Ready( Sa1Sa1 ))
250㎖ 플라스크에 5.0g의 메틸메타크릴레이트(Methyl methacrylate, MMA), 3.0g의 N-페닐 말레이미드(N-Phenyl Maleimide, NPMI), 8.0g의 메틸메타크릴릭액시 드(Methyl methacrylic acid, MAA), 2.0g의 벤질메타크릴레이트(Benzyl Methacrylate, BzMA), 2.0g의 스티렌을 3-메톡시부틸아세테이트(3-Methoxybutylacetate)와 디프로필렌글리콜 모노메틸 에테르(Dipropyleneglycol monomethyl ether, DPM)가 1:1 중량비로 혼합된 용매 60.33g에 녹인 후, 0.4g의 3-머캅토프로피오닉액스드(3-mercaptopropionic acid, MPA)를 첨가하여 교반하였다. 상기 혼합 용액을 질소 분위기 하에서 60℃로 승온시킨 후, 1시간 동안 교반하였다. 이후, 상기 사용된 혼합 용매 5.0g에 0.6g의 2,2'-아조비스(2,4-디메틸발레로니트릴[2,2'-Azobis(2,4-dimethyl valeronitrile)]을 녹여 준비된 용액을 60℃의 온도에서 상기 혼합 용액에 첨가한 후, 4시간 동안 같은 온도에서 반응을 수행하였다. 상기와 같은 방법으로 수득된 유기 고분자 수지의 산가는 292.23㎎KOH/g, 중량 평균 분자량은 8,616 임을 확인하였다.In a 250 ml flask, 5.0 g of methyl methacrylate (MMA), 3.0 g of N-phenyl maleimide (NPMI) and 8.0 g of methyl methacrylic acid (MAA) ), 2.0 g of Benzyl Methacrylate (BzMA), 2.0 g of Styrene is 3-Methoxybutylacetate and Dipropyleneglycol monomethyl ether (DPM) After dissolving in 60.33 g of the mixed solvent by weight, 0.4 g of 3-mercaptopropionic acid (MPA) was added and stirred. The mixed solution was raised to 60 ° C. under a nitrogen atmosphere, and then stirred for 1 hour. Thereafter, 0.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 5.0 g of the mixed solvent used to prepare a solution. After addition to the mixed solution at a temperature of 60 ° C., the reaction was carried out at the same temperature for 4 hours.The acid value of the organic polymer resin obtained in the same manner was 292.23 mgKOH / g, and the weight average molecular weight was 8,616. It was.
촉매 전구체 수지 조성물 준비(Preparation of the catalyst precursor resin composition Sa2Sa2 ))
상기 (Sa1)단계에서 수득된 유기고분자수지 용액 28.7055g, 디펜타에리스리톨 헥사아크릴레이트(dipentaerythritol hexa-acrylate, DPHA)용액 (PGMEA 내에 50중량%로 존재함) 12.5006g, 광개시제 알파-하이드록시케톤(α-Hydroxyketone, 상품명 IRGACURE2010) 0.8651g, 실버트리플루오로아세테이트(Silvertrifluoroacetate, AgO2CCF3) 1.2856g, 접착증진제(adhesion promoter)로서 상품명 KBM503 100% 0.2093g, 습윤제(wetting agent)로서 메틸에틸케톤(MethylEthylKetone, MEK) 용액 내에 상품명 BYK331이 10 중량%가 포함된 물질 0.2417g, 및 추가 용매로서 메틸에틸케톤(methyl ethyl kentone, MEK) 26.1921g을 혼합하여 교반기를 통해 교반 후 전자파 차폐용 촉매 전구체 수지조성물 70.0000g을 준비하였다.28.7055 g of the organic polymer resin solution obtained in step (Sa1), dipentaerythritol hexa-acrylate (DPHA) solution (present in 50% by weight in PGMEA) 12.5006 g, photoinitiator alpha-hydroxyketone ( α-Hydroxyketone, trade name IRGACURE2010) 0.8651 g, Silver trifluoroacetate (AgO 2 CCF 3 ) 1.2856 g, brand name KBM503 100% 0.2093 g as an adhesion promoter, methyl ethyl ketone (wetting agent) 0.2417 g of a substance containing 10 wt% of BYK331 by MethylEthylKetone, MEK) solution, and 26.1921 g of methyl ethyl ketone (MEK) as an additional solvent were mixed and stirred through a stirrer, and then a catalyst precursor resin composition for electromagnetic wave shielding. 70.0000 g were prepared.
미세 금속 패턴 형성(Fine metal pattern formation ( Sa3Sa3 ))
전술한 (Sa1) 및 (Sa2)단계에 따라 준비된 촉매 전구체 수지조성물을 사용하여 미세 금속 패턴을 형성하며, 그 구체적인 진행 단계는 첨부된 도 1을 참조하여 설명하기로 한다.A fine metal pattern is formed using the catalyst precursor resin composition prepared according to the above-described steps (Sa1) and (Sa2), and a detailed progress step thereof will be described with reference to FIG. 1.
도 1은 본 발명의 실시예에 따라 준비된 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 전자파 차폐용 금속 패턴을 제조하는 방법을 설명하기 위한 공정 흐름도이다.1 is a process flow chart for explaining a method of manufacturing an electromagnetic shielding metal pattern using the catalyst precursor resin composition for electromagnetic shielding prepared according to an embodiment of the present invention.
(1-1) 코팅(1-1) coating
두께가 100㎛인 PET 필름에 갭사이즈가 10㎛인 마이어 바(Meyer bar)를 이용하여 상기 (Sa2)단계에서 준비된 촉매 전구체 수지 조성물을 750㎚의 두께로 바코팅하였다.The catalyst precursor resin composition prepared in step (Sa2) was barcoated to a thickness of 750 nm using a Meyer bar having a gap size of 10 μm on a PET film having a thickness of 100 μm.
(1-2) 전 열경화(1-2) Total Heat Curing
상기 바코팅 후, 100℃의 온도 조건에서 90초 동안 전 열경화(1차 열경화)시켰다.After the bar coating, the entire heat curing (primary heat curing) for 90 seconds at a temperature of 100 ℃.
(1-3) 노광(1-3) exposure
접촉방식으로 20㎛의 메쉬 패턴을 갖는 포토마스크를 이용하여 파장이 375㎚인 자외선을 이용하여 195mJ/㎠의 에너지량을 조사하여 상기 촉매 패턴을 노광시켰 다.The catalyst pattern was exposed by irradiating an energy amount of 195 mJ / cm 2 using a photomask having a mesh pattern of 20 μm as a contact method using ultraviolet rays having a wavelength of 375 nm.
(1-4) 현상(1-4) phenomenon
염기성 수용액 ENF사의 ECC-100(pH 13)을 상기 노광된 촉매패턴에 144초 동안 스프레이 방식으로 분무한 후, 이를 초순수(DI)로 세정하고 질소를 블로잉(blowing)함으로써 현상시켰다.ECC-100 (pH 13) from ENF, a basic aqueous solution, was sprayed onto the exposed catalyst pattern for 144 seconds, and then developed by washing with ultrapure water (DI) and blowing nitrogen.
(1-5) 후 열경화(1-5) after heat curing
상기 현상 후, 100℃의 온도 조건에서 300초 동안 후 열경화(2차 열경화)시켰다. 상기 (1-5)단계의 열경화는 전술한 (1-2)단계의 열경화와 동일한 온도 조건에서 진행하나, 그 경화시간은 더 길게 진행하였다.After the development, it was post-cured (secondary thermosetting) for 300 seconds at a temperature of 100 ℃. The thermal curing of step (1-5) proceeds at the same temperature conditions as the thermal curing of step (1-2), but the curing time is longer.
상기 (1-1) 내지 (1-5)단계는 기재에 촉매 패턴을 형성하는 단계(S11 또는 S21)의 세부적인 공정 진행 단계를 설명한 것이다.Steps (1-1) to (1-5) describe the detailed process steps of forming the catalyst pattern on the substrate (S11 or S21).
(1-6) 환원(1-6) reduction
상기 후 열경화된 촉매패턴에 365㎚의 파장을 갖는 자외선을 이용하여 3.6J/㎠의 에너지량을 조사함으로써 촉매 금속을 환원시켰다. 상기 (1-6)단계는 촉매 패턴을 형성하는 단계(S2)에 이어 진행된 촉매 패턴의 환원단계(S22)에 해당한다.The catalyst metal was reduced by irradiating an amount of energy of 3.6 J / cm 2 to the thermally cured catalyst pattern using ultraviolet light having a wavelength of 365 nm. Step (1-6) corresponds to the step of reducing the catalyst pattern (S22) that is performed after the step of forming the catalyst pattern (S2).
(1-7) 구리 무전해 도금 용액의 준비(1-7) Preparation of Copper Electroless Plating Solution
아토테크(Atotech) 사의 커버트론 코퍼 배쓰(Covertron copper bath)를 이용하여 매뉴얼에 따라 용액을 준비하였다. 이때 준비된 용액은, 그 온도가 45℃이며, 그 pH는 13.5이다. 상기 (1-7)단계의 도금 용액을 준비하는 단계는 전술한 (1-1) 내지 (1-6)단계의 시간 흐름상으로 연계된 것은 아니므로, 도 1에 제시된 바와 달 리, 별도의 공정 단계를 진행하여 도금 용액이 준비될 수 있음은 자명하다.The solution was prepared according to the manual using a Covertron copper bath manufactured by Atotech. The solution prepared at this time is 45 degreeC, and the pH is 13.5. The step of preparing the plating solution of step (1-7) is not associated with the time flow of steps (1-1) to (1-6) described above, unlike that shown in FIG. It is apparent that the plating solution may be prepared by going through the process steps.
(1-8) 초기 도금 단계 구리 무전해 도금(1-8) Initial Plating Step Copper Electroless Plating
교반하지 않는 도금 용액에 기판을 5분 간 침지시킴으로써 기판 표면에 형성된 촉매 패턴에 구리 박막이 도금되도록 하였다. 상기 (1-8)단계는 무전해 도금 단계(S12 또는 S23)의 세부 단계로서 첫단계로 진행하는 초기 도금단계(S12a 또는 S23a)에 해당한다.The thin film was plated on the catalyst pattern formed on the surface of the substrate by immersing the substrate in a plating solution that was not stirred for 5 minutes. Step (1-8) corresponds to the initial plating step (S12a or S23a) to proceed to the first step as a detailed step of the electroless plating step (S12 or S23).
(1-9) 박막 성장 단계 구리 무전해 도금(1-9) Thin Film Growth Stage Copper Electroless Plating
교반기를 이용하여 교반중인 도금 용액에 기판을 20분 간 침지시킨 후, 도금을 수행하여 금속 박막을 성장시켰다. 상기 (1-9)단계는 무전해 도금 단계(S12 또는 S23)의 세부 단계로서 첫 단계로 진행하는 초기 도금단계(S12a 또는 S23a)에 해당한다.After the substrate was immersed in the plating solution under stirring for 20 minutes using a stirrer, plating was performed to grow a metal thin film. Step (1-9) corresponds to the initial plating step (S12a or S23a) to proceed to the first step as a detailed step of the electroless plating step (S12 or S23).
전술한 본 발명에 따른 실시예의 (Sa3)단계의 세부단계인 (1-1) 내지 (1-9)단계에 따라 촉매 패턴에 대한 무전해 도금을 진행한 결과, 전자파 차폐를 위한 금속 패턴인 구리 패턴을 형성하게 되었다.As a result of the electroless plating of the catalyst pattern according to the steps (1-1) to (1-9), which are the detailed steps of the step (Sa3) of the embodiment according to the present invention, copper as a metal pattern for electromagnetic shielding A pattern was formed.
< 비교예(Sb1 내지 Sb3) ><Comparative Examples (Sb1 to Sb3)>
유기고분자수지(Organic Polymer Resin ( 중합체수지Polymer resin ) 준비() Ready( Sb1Sb1 ))
상기 본 발명에 따르는 실시예의 (Sa1) 단계와 동일한 방법으로 유기고분자수지 용액을 준비하였다.An organic polymer resin solution was prepared in the same manner as in step (Sa1) of the embodiment according to the present invention.
촉매 전구체 수지 조성물 준비(Preparation of the catalyst precursor resin composition Sb2Sb2 ))
상기 (Sb1) 단계에서 수득된 유기고분자수지 용액을 이용하고, 상기 본 발명 에 따르는 실시예의 (Sa2) 단계와 동일한 방법으로 촉매 전구체 수지조성물을 준비하였다.Using the organic polymer resin solution obtained in step (Sb1), a catalyst precursor resin composition was prepared in the same manner as in step (Sa2) of the embodiment according to the present invention.
미세 금속 패턴의 형성(Formation of fine metal patterns ( Sb3Sb3 ))
전술한 (Sb1) 및 (Sb2) 단계에 의해 준비된 촉매 전구체 수지 조성물을 이용하여 전자파 차폐용 금속 패턴을 형성하며, 그 구체적인 진행단계는 첨부된 도 2를 참조하여 설명하기로 한다.By using the catalyst precursor resin composition prepared by the above-mentioned (Sb1) and (Sb2) step to form a metal pattern for shielding electromagnetic waves, a specific step will be described with reference to the accompanying FIG.
도 2는 본 발명에 대비되는 비교예에 따라 준비된 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 전자파 차폐용 금속 패턴을 제조하는 방법을 설명하기 위한 공정 흐름도이다.FIG. 2 is a process flowchart illustrating a method of manufacturing a metal pattern for electromagnetic wave shielding using the catalyst precursor resin composition for electromagnetic wave shielding prepared according to a comparative example according to the present invention.
(2-1) 코팅(2-1) coating
상기 실시예의 (Sa3)단계 내의 (1-1)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-1) in step (Sa3) of the above embodiment.
(2-2) 전열경화(2-2) Heat Curing
상기 실시예의 (Sa3)단계 내의 (1-2)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-2) in step (Sa3) of the above embodiment.
(2-3) 노광(2-3) exposure
상기 실시예의 (Sa3)단계 내의 (1-3)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-3) in step (Sa3) of the above embodiment.
(2-4) 현상(2-4) phenomenon
상기 실시예의 (Sa3)단계 내의 (1-4)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-4) in step (Sa3) of the above embodiment.
(2-5) 후 열경화(2-5) after heat curing
상기 실시예의 (Sa3)단계 내의 (1-5)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-5) in step (Sa3) of the above embodiment.
(2-6) 환원(2-6) reduction
상기 실시예의 (Sa3)단계 내의 (1-6)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-6) in step (Sa3) of the above embodiment.
(2-7) 구리 무전해 도금 용액의 제조(2-7) Preparation of Copper Electroless Plating Solution
상기 실시예의 (Sa3)단계 내의 (1-7)단계와 동일하게 진행하였다.It proceeded in the same manner as in step (1-7) in step (Sa3) of the above embodiment.
(2-8) 구리 무전해 도금 : 교반기를 이용하여 교반중인 도금 용액에 기판을 20분간 침지하여, 도금을 수행하였다.(2-8) Copper Electroless Plating: The substrate was immersed in the plating solution under stirring for 20 minutes using a stirrer to perform plating.
전술한 바와 같이, 비교예의 (Sb3)단계의 세부단계인 (2-1) 내지 (2-7)단계는 전술한 본 발명에 따르는 실시예의 (Sa3)단계의 세부단계인 (1-1) 내지 (1-7)단계와 동일한 조건으로 진행하여다. 다만, 상기 비교예의 (Sb3)단계 내의 (2-8)단계의 진행은 상기 실시예의 (Sa3)단계 내의 (1-8) 및 (1-9)단계와는 다른 조건에 따라 진행하였다.As described above, steps (2-1) to (2-7) which are detailed steps of step (Sb3) of the comparative example are steps (1-1) to which are detailed steps of step (Sa3) of the embodiment according to the present invention described above. Proceed with the same conditions as in (1-7). However, the progress of the step (2-8) in the step (Sb3) of the comparative example was carried out under different conditions from the steps (1-8) and (1-9) in the step (Sa3) of the embodiment.
전술한 본 발명에 대비되는 비교예의 (Sb3)단계의 세부단계인 (2-1) 내지 (2-8)단계에 따라 촉매 패턴에 대한 무전해 도금을 진행한 결과, 촉매 패턴 위에 구리 박막이 형성되지 못하는 것을 확인하였다. 이로써, 본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물 및 이를 이용한 금속 패턴 제조 방법은 종래의 방법에서 도달할 수 없는 기술적 진보를 이루었음을 확인할 수 있게 되었다.As a result of performing electroless plating on the catalyst pattern according to the detailed steps (2-1) to (2-8) of the step (Sb3) of the comparative example compared to the present invention, a copper thin film was formed on the catalyst pattern. It was confirmed that not. As a result, the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention and the method of manufacturing a metal pattern using the same can be confirmed that the technical progress that cannot be reached in the conventional method.
이상에서 설명된 본 발명의 최적 실시예들이 개시되었다. 여기서 특정한 용어들이 사용되었으나, 이는 단지 당업자에게 본 발명을 상세히 설명하기 위한 목적에서 사용된 것이지 의미한정이나 특허청구범위에 기재된 본 발명의 범위를 제한하기 위해 사용된 것이 아니다. Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are only used for the purpose of describing the present invention in detail to those skilled in the art and are not intended to limit the scope of the present invention as defined in the claims or the claims.
본 발명에 따르는 전자파 차폐용 촉매 전구체 수지 조성물을 이용하여 촉매패턴을 형성하면, 촉매 패턴의 막 접착성이 우수하고, 도금 공정과 같은 습윤 공정 중의 촉매 유실이 적어 균일하고 내화학성이 뛰어난 촉매 패턴을 형성할 수 있는 장점이 있다.When the catalyst pattern is formed by using the catalyst precursor resin composition for electromagnetic wave shielding according to the present invention, the catalyst pattern is excellent in the adhesion of the catalyst pattern and the catalyst pattern is less uniform during the wet process such as the plating process. There is an advantage that can be formed.
한편, 본 발명에서 제시하는 2단계 무전해 도금법을 사용하는 경우, 촉매 패턴의 침식을 최소화하면서 촉매의 유실을 방지할 수 있으며, 증착속도가 향상되어 무전해 도금 후 균일하고 미세한 금속패턴으로 형성할 수 있다.On the other hand, when using the two-step electroless plating method proposed in the present invention, it is possible to prevent the loss of the catalyst while minimizing the erosion of the catalyst pattern, the deposition rate is improved to form a uniform and fine metal pattern after electroless plating Can be.
또한, 본 발명에 따라 제조된 금속 패턴은 우수한 전자파 차폐능을 갖고 있으므로 CRT, PDP, 액정, EL 등의 디스플레이 전면으로부터 발생되는 전자파 차폐막이나 연성 회로 기판의 배선 형성에 사용하기에 적합한 특징을 갖는다.In addition, since the metal pattern manufactured according to the present invention has excellent electromagnetic shielding ability, it has a characteristic suitable for use in forming an electromagnetic shielding film or wiring of a flexible circuit board generated from the front surface of a display such as CRT, PDP, liquid crystal, EL, and the like.
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