NO135188B - - Google Patents
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- Publication number
- NO135188B NO135188B NO123/73A NO12373A NO135188B NO 135188 B NO135188 B NO 135188B NO 123/73 A NO123/73 A NO 123/73A NO 12373 A NO12373 A NO 12373A NO 135188 B NO135188 B NO 135188B
- Authority
- NO
- Norway
- Prior art keywords
- copper
- group
- coating
- coating bath
- bath according
- Prior art date
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- 238000000576 coating method Methods 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 29
- 239000003381 stabilizer Substances 0.000 claims description 18
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000005949 Malathion Substances 0.000 claims description 7
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical group CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 claims description 7
- 229960000453 malathion Drugs 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- HBGZBVPXPDNXOV-UHFFFAOYSA-N 2-prop-2-ynoxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(OCC#C)C(=O)C2=C1 HBGZBVPXPDNXOV-UHFFFAOYSA-N 0.000 claims description 2
- PAZCLCHJOWLTGA-UHFFFAOYSA-N 2-prop-2-ynylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CC#C)C(=O)C2=C1 PAZCLCHJOWLTGA-UHFFFAOYSA-N 0.000 claims description 2
- FSYKLXZYZWJVPT-UHFFFAOYSA-N [O-]P(O)(O)=[S+]S Chemical compound [O-]P(O)(O)=[S+]S FSYKLXZYZWJVPT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 125000005543 phthalimide group Chemical group 0.000 claims 1
- 125000003375 sulfoxide group Chemical group 0.000 claims 1
- 125000004149 thio group Chemical group *S* 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 37
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- -1 copper(I) ions Chemical class 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- OBYJFWVFCFYKNY-UHFFFAOYSA-N 1-prop-2-ynylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC#C OBYJFWVFCFYKNY-UHFFFAOYSA-N 0.000 description 1
- DOTAQRZGKATJIC-UHFFFAOYSA-N 1-prop-2-ynylpyrrolidine-2,5-dione Chemical compound O=C1CCC(=O)N1CC#C DOTAQRZGKATJIC-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 1
- HOVYPEXIYGWEBP-UHFFFAOYSA-N 4-prop-2-ynoxyisoindole-1,3-dione Chemical compound C(C#C)OC1=C2C(C(=O)NC2=O)=CC=C1 HOVYPEXIYGWEBP-UHFFFAOYSA-N 0.000 description 1
- RGBONZYGHPARAC-UHFFFAOYSA-N 4-prop-2-ynylisoindole-1,3-dione Chemical compound C1=CC=C(CC#C)C2=C1C(=O)NC2=O RGBONZYGHPARAC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UOQDAXRXDLIMEB-UHFFFAOYSA-N CCS(CC)(C1=CC(C)=NC(C(C)C)=N1)=P(O)(O)O Chemical compound CCS(CC)(C1=CC(C)=NC(C(C)C)=N1)=P(O)(O)O UOQDAXRXDLIMEB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000004128 Copper(II) sulphate Substances 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IENXJNLJEDMNTE-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical class CC(O)=O.NCCN IENXJNLJEDMNTE-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZHCAAFJSYLFLPX-UHFFFAOYSA-N nitrocyclohexatriene Chemical group [O-][N+](=O)C1=CC=C=C[CH]1 ZHCAAFJSYLFLPX-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- WYMSBXTXOHUIGT-UHFFFAOYSA-N paraoxon Chemical compound CCOP(=O)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 WYMSBXTXOHUIGT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003462 sulfoxides Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 125000006000 trichloroethyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Description
Oppløsninger for strømløs kobberbelegning som benyt-ter alkalisk formaldehyd som reduksjonsmiddel for kobber(II)-ioner•er autokatalytiske og derfor hyppig ustabile, dvs. at de har en tendens til å sette fri kobber for tidlig. Mange fremgangsmåter er foreslått for å minimalisere autodekomponeringen av kobberbad for strømløs plettering. Bruken av sterke chelat-dannere,slik som etylendiamintetraeddiksyre (EDTA), er f.eks. kjent å understøtte retarderingen av autodekomponeringsgraden. Solutions for electroless copper coating that use alkaline formaldehyde as a reducing agent for copper(II) ions•are autocatalytic and therefore often unstable, i.e. they tend to release copper too soon. Many methods have been proposed to minimize the autodecomposition of copper baths for electroless plating. The use of strong chelating agents, such as ethylenediaminetetraacetic acid (EDTA), is e.g. known to support the retardation of the autodecomposition rate.
(Se US-patent nr. 3.119-709). Chelatdannelse gir imidlertid ikke helt tilfredsstillende stabilisering, og i mange tilfeller påvirkes metallavsetningshastigheten ugunstig slik at belegnings-■prosessen gjøres kommersielt ubrukbar. (See US Patent No. 3,119-709). However, chelation does not provide completely satisfactory stabilization, and in many cases the rate of metal deposition is adversely affected so that the coating process is rendered commercially unusable.
Det er også kjent at kobber(I)-ionet er ekstremt virksomt med henblikk på å fremme autodekomponeringen av oppløs-ninger for strømløs kobberbelegning. Por å redusere kobber(I)-" ionekonsentrasjonen er det foreslått å boble luft eller oksygen gjennom belegningsoppløsningen for strømløs kobberplettering. It is also known that the copper (I) ion is extremely effective with a view to promoting the auto-decomposition of solutions for electroless copper coating. To reduce the copper(I) ion concentration, it has been suggested to bubble air or oxygen through the plating solution for electroless copper plating.
(Se US-patent nr. 2.938.805). Denne fremgangsmåte omdanner kobber(I)-ionet til kobber(II)-ion og er vanligvis benyttet i denne teknikk. Når denne fremgangsmåte benyttes som eneste hjelpemiddel for stabilisering av badet, har den to store mangler. For det første er avsetningene som oppnås vanligvis mørke og ikke-metalliske av utseende, antagelig på grunn av et ytre sjikt av kobber(II)-oksyd, for det andre flyktiggjøres en stor mengde av formaldehyd på grunn av oksygenet som føres gjennom oppløsningen, og dette gjør kontrollen av den kjemiske balanse mere vanskelig. (See US Patent No. 2,938,805). This method converts the copper (I) ion to copper (II) ion and is commonly used in this technique. When this method is used as the only aid for stabilizing the bath, it has two major shortcomings. Firstly, the deposits obtained are usually dark and non-metallic in appearance, presumably due to an outer layer of copper(II) oxide, secondly, a large amount of formaldehyde is volatilized due to the oxygen carried through the solution, and this makes the control of the chemical balance more difficult.
Bruken av mindre mengder forskjellige kjemikalier som er i stand til komplekst å binde kobber(I)-ioner, er også godt kjent i teknikken for å øke stabiliteten av kobberoppløsninger for strømløs plettering. Typiske additiver er cyanider, nitri-ler, uorganiske sulfider og forskjellige, organiske toverdige svovelforbindelser. (Se US-patent nr. 3.095-309 og 3-361.580)..-Vanligvis har også disse additiver flere mangler. Ofte utvider The use of minor amounts of various chemicals capable of complexing copper(I) ions is also well known in the art to increase the stability of copper solutions for electroless plating. Typical additives are cyanides, nitriles, inorganic sulphides and various organic divalent sulfur compounds. (See US patent no. 3,095-309 and 3-361,580)..-Usually these additives also have several deficiencies. Often expands
de kun i liten grad brukslevetiden eller driftsparametrene for oppløsningene, og når stabiliteten sterkt-økes, reduseres vanligvis hastigheten eller kvaliteten av metallavsetningen. Derfor er vanligvis et visst kompromiss mellom stabilitet for beleg-ningsoppløsningen og kvaliteten eller kvantiteten av metallavsetningen nødvendig.. ,.\, they only slightly affect the service life or operating parameters of the solutions, and when stability is greatly increased, the rate or quality of metal deposition is usually reduced. Therefore, some compromise between stability of the coating solution and the quality or quantity of the metal deposit is usually necessary.. ,.\,
Ifølge oppfinnelsen kan den vanlige kobberoppløsning for strømløs plettering stabiliseres innen et visst temperatur-område i ekstremt lange tidsrom uten å gi avkall på kvalitet, farge eller metallavsetningshastighet. Kobberbadene for strøm-løs plettering ifølge oppfinnelsen benyttes kontinuerlig med erstatning av de bestanddeler som tapes ved kjemisk reaksjon eller uttrekking med høy effektivitet. According to the invention, the usual copper solution for electroless plating can be stabilized within a certain temperature range for extremely long periods of time without sacrificing quality, color or metal deposition rate. The copper baths for electroless plating according to the invention are used continuously with replacement of the components that are lost by chemical reaction or extraction with high efficiency.
I tillegg tåler badene som er stabilisert ifølge oppfinnelsen gjentatte oppvarmings- og avkjølingssykler og vil vanligvis kunne benyttes effektivt ved omgivelsestemperaturer. In addition, the baths which are stabilized according to the invention withstand repeated heating and cooling cycles and will usually be able to be used effectively at ambient temperatures.
De resulterende kobberfilmer er lys rosa og består av rent kobber-metall. De har ingen mørke og kornede områder av kobberoksyder, som vanligvis finnes i de til nå kjente filmer. The resulting copper films are light pink and consist of pure copper metal. They have no dark and grainy areas of copper oxides, which are usually found in the films known to date.
Således angår foreliggende oppfinnelse et alkalisk belegningsbad for strømløs kobberbelegning med en pH innen området 10,5 til 14, inneholdende vann, et vannoppløselig kobbersalt, et kompleksdannende middel for kobber(II)-ioner. og formaldehyd, og belegningsbadet karakteriseres ved at det videre inneholder en primær stabilisator med følgende generelle formel: hvor R og R'<1>' er like eller forskjellige og hver er en alkyl-.gruppe med fra 1-12 karbonatomer, en fenyl- eller naftyl-gruppe, X, Y og Z er oksygen eller svovel og R' sammen med Z er en sur gruppe som hydrolyseres i det alkaliske bad, og der badet videre eventuelt inneholder en sekundær stabilisator med den generelle formel: Thus, the present invention concerns an alkaline coating bath for electroless copper coating with a pH within the range 10.5 to 14, containing water, a water-soluble copper salt, a complexing agent for copper (II) ions. and formaldehyde, and the coating bath is characterized by the fact that it also contains a primary stabilizer with the following general formula: where R and R'<1>' are the same or different and each is an alkyl group with from 1-12 carbon atoms, a phenyl or naphthyl group, X, Y and Z are oxygen or sulfur and R' together with Z is an acidic group which is hydrolysed in the alkaline bath, and where the bath further optionally contains a secondary stabilizer with the general formula:
hvor R'' er en alkylgruppe med fra 1-12 karbonatomer, en fenyl- eller naftylgruppe eller en substituert fenyl- eller naftylgruppe, X' er en tio-, sulfoksyd-, sulfonyl-, oksy-, karbonyl- eller iminogruppe, n er 1, 2 eller 3, eller hvor R''X' er et imid'eller en heterocyklisk ring med nitrogen og karbon med eller uten oksygen. where R'' is an alkyl group with from 1-12 carbon atoms, a phenyl or naphthyl group or a substituted phenyl or naphthyl group, X' is a thio, sulfoxide, sulfonyl, oxy, carbonyl or imino group, n is 1, 2 or 3, or where R''X' is an imide or a heterocyclic ring of nitrogen and carbon with or without oxygen.
I alle tilfeller bør i den primære stabilisator bindingene i R'''X og R'''-Y være stabile i det alkaliske bad, In all cases, in the primary stabilizer the bonds in R'''X and R'''-Y should be stable in the alkaline bath,
og de bør motstå hydrolyse. X, Y og Z kan være oksygen og svovel, helst er X og Y oksygen. R' kan bety et stort område av kjemiske grupper. Hovedkriteriet ved valget av R' er at den sammen med Z danner en sur gruppe som langsomt hydrolyserer i det alkaliske belegningsbad, slik at det fremkommer en R(X)R(Y)P(S)-(Z)~ del. En hvilken som helst struktur hvor karbo-net som er bundet til Z er bundet til en del forskjellig fra en alkylgruppe, er egnet. Mer spesielt kan R' være hydrogen, en substituert alkyl- eller arylgruppe, hvori substituenten er en eller flere av de følgende: halogen (f.eks. klorid, bromid eller jodid), hydroksyl, amino eller lavere alkyl- eller alkanol-amino, amido, nitro, karbalkoksy, alkyltio, alkoksy eller aryl-oksygruppe eller pyrimidyl. Alkylgruppene kan ha 1 - 12 karbonatomer, men:helst 1-4. Arylgruppen kan være fenyl eller naftyl'. Slike grupper er: én paranitrofenylgruppe, en etyltio-gruppe, en N-metylkarbamoylmetylgruppe, en trikloretylgruppe, en l,2-di(etoksykarbonyl)etyltiogruppe. Imidlertid kan ikke mer enn en av de tre R-grupper være hydrogen. and they should resist hydrolysis. X, Y and Z can be oxygen and sulphur, preferably X and Y are oxygen. R' can mean a wide range of chemical groups. The main criterion for the selection of R' is that together with Z it forms an acidic group which slowly hydrolyses in the alkaline coating bath, so that an R(X)R(Y)P(S)-(Z)~ part appears. Any structure in which the carbon attached to Z is attached to a moiety other than an alkyl group is suitable. More particularly, R' may be hydrogen, a substituted alkyl or aryl group, wherein the substituent is one or more of the following: halogen (eg chloride, bromide or iodide), hydroxyl, amino or lower alkyl or alkanol amino, amido, nitro, carbaloxy, alkylthio, alkoxy or aryloxy group or pyrimidyl. The alkyl groups can have 1-12 carbon atoms, but preferably 1-4. The aryl group can be phenyl or naphthyl'. Such groups are: one paranitrophenyl group, one ethylthio group, one N-methylcarbamoylmethyl group, one trichloroethyl group, one 1,2-di(ethoxycarbonyl)ethylthio group. However, no more than one of the three R groups can be hydrogen.
I den sekundære stabilisator er X' helst en nitrogen-gruppe og R'' og n sammen en ftalimid- eller ftalimidoksygruppe; således er forbindelsen av propargyltypen en propargylftalimid eller en propargyloksyf talimid .' In the secondary stabilizer X' is preferably a nitrogen group and R'' and n together a phthalimide or phthalimidoxy group; thus the compound of the propargyl type is a propargylphthalimide or a propargyloxyphthalimide.'
Representative primære stabilisatorer er: dietyl-p-nitrofenylfosfat, dietyl-p-nitrofenyltionofosfat (Parathion), dimetyl-S-2-etyltioetyltiolofosfat, monometylamid av 0,0-dimetyl-ditiofosforyleddiksyre, dietylester av 0,O-dimetylditiofosforyl-ravsyre (malathion), dimetylhydroksy-2,2,2-trikloretylfosfonat og dietyl-2-isopropyl-4-metylpyrimid-6-yl-tionofosfat. Representative primary stabilizers are: diethyl-p-nitrophenyl phosphate, diethyl-p-nitrophenylthionophosphate (Parathion), dimethyl-S-2-ethylthioethylthiolophosphate, 0,0-dimethyldithiophosphorylacetic acid monomethylamide, 0,O-dimethyldithiophosphorylsuccinic acid diethyl ester (malathion) , dimethylhydroxy-2,2,2-trichloroethylphosphonate and diethyl-2-isopropyl-4-methylpyrimid-6-yl-thionophosphate.
Mest foretrukket av disse forbindelser er dietyl-p-nitrof enyltionof osf at og dietylesteren av 0,O-dimetylditio-fosforylravsyre, kjent under trivialnavnene Parathion, henholds-vis Malathion. Most preferred of these compounds are diethyl-p-nitrof enylthiophate and the diethyl ester of 0,0-dimethyldithio-phosphorylsuccinic acid, known under the trivial names Parathion, respectively Malathion.
Beregnet på antall mol kobber(II)-salt som benyttes, tilsettes fra 0,0001 til 0,001 mol av den organiske fosfat-stabilisator til den ikke-elektriske belegningsoppløsning. Calculated on the number of moles of copper (II) salt used, from 0.0001 to 0.001 mole of the organic phosphate stabilizer is added to the non-electric coating solution.
Helst benyttes fra 0,0002 til 0,0004 mol. Preferably from 0.0002 to 0.0004 mol is used.
Eksempler på sekundære stabilisatorer som kan benyttes omfatter: N-propargylmaleimid, N-propargylravsyreimid, N-alkyl-N-propargylamider, N,N-dialkyl-N-propargylaminer, aryl-og alkyl-propargyletere, aryl- og alkyl-propargyltioetere, aryl-og alkyl-propargylketoner og aryl- og alkyl-propargylsulfoner. Examples of secondary stabilizers that can be used include: N-propargyl maleimide, N-propargyl succinimide, N-alkyl-N-propargyl amides, N,N-dialkyl-N-propargyl amines, aryl and alkyl propargyl ethers, aryl and alkyl propargyl thioethers, aryl -and alkyl propargyl ketones and aryl and alkyl propargyl sulfones.
Mengden av sekundær stabilisator som kan benyttes uttrykkes helst ved kobber(II)-saltet i 1 liter av det ikke-elektriske kobberbelegningsbad. Vanligvis benyttes. 0,0001 til 0,001 mol, helst 0,0002 til 0,0004 mol. The amount of secondary stabilizer that can be used is preferably expressed by the copper (II) salt in 1 liter of the non-electrical copper plating bath. Usually used. 0.0001 to 0.001 mol, preferably 0.0002 to 0.0004 mol.
Kobberbelegningsoppløsningene ifølge oppfinnelsen er alkaliske vandige oppløsninger som inneholder en kilde for kobber(II)-ioner, minst ett kompleksdannende middel for kobber-(II)-ioner og et aktivt reduserende middel. Alkaliteten kan fremkomme ved natrium- eller kaliumhydroksyder, karbonater eller fosfater eller andre baser. Ifølge oppfinnelsen er det foretrukkede alkali en blanding av et alkalimetallhydroksyd og karbonat. Denne blanding er økonomisk og tillater lett regulering av pH-Vérdien. Natriumsaltene er vanligvis foretrukket på grunn av disses lave omkostninger. The copper coating solutions according to the invention are alkaline aqueous solutions containing a source of copper (II) ions, at least one complexing agent for copper (II) ions and an active reducing agent. The alkalinity can arise from sodium or potassium hydroxides, carbonates or phosphates or other bases. According to the invention, the preferred alkali is a mixture of an alkali metal hydroxide and carbonate. This mixture is economical and allows easy regulation of the pH value. The sodium salts are usually preferred because of their low cost.
Egnede kilder for kobber(II)-ioner er vannoppløselige kobbersalter slik som kobber(II)sulfat, kobber(II)nitrat, kobber(II)klorid og kobber(II)acetat. Ifølge oppfinnelsen er kobber(II)sulfat foretrukket på grunn av den lave pris og den lette oppnåelighet. Suitable sources for copper (II) ions are water-soluble copper salts such as copper (II) sulphate, copper (II) nitrate, copper (II) chloride and copper (II) acetate. According to the invention, copper (II) sulfate is preferred because of its low price and easy availability.
Egnede kompleksdannende midler for kobber(II)-ioner er trietanolamin, tetrakis-N-N-N-N-hydroksypropyletylendiamin, salter av nitrilotrieddiksyre, salter av etylendiaminacetater og salter av hydroksykarboksylsyrer slik som glukonsyre, sitron-syre og vinsyre. Blandinger av salter av etylendiamintetraeddiksyre og vinsyre er de foretrukkede kompleksdannende midler, og disse gir optimal stabilitet og avsetningsegenskaper i for-bindelse med de foretrukkede additiver ifølge oppfinnelsen. Egnede reduserende midler er formaldehyd og formaldehyd-kilder, inkludert vandig'formaldehyd, paraformaldehyd og derivater derav. Vandig formaldehyd er foretrukket på grunn av lave omkostninger, oppnåelighet og lett anvendelighet. Suitable complexing agents for copper (II) ions are triethanolamine, tetrakis-N-N-N-N-hydroxypropylethylenediamine, salts of nitrilotriacetic acid, salts of ethylenediamine acetates and salts of hydroxycarboxylic acids such as gluconic acid, citric acid and tartaric acid. Mixtures of salts of ethylenediaminetetraacetic acid and tartaric acid are the preferred complexing agents, and these provide optimal stability and deposition properties in connection with the preferred additives according to the invention. Suitable reducing agents are formaldehyde and formaldehyde sources, including aqueous formaldehyde, paraformaldehyde and derivatives thereof. Aqueous formaldehyde is preferred due to low cost, availability and ease of use.
Fagmannen vil forstå at andre additiver, slik som overflateaktive midler, kan benyttes, for å øke effektiviteten av en kobberbelegningsoppløsning for strømløs plettering. Those skilled in the art will appreciate that other additives, such as surfactants, can be used to increase the effectiveness of a copper coating solution for electroless plating.
Generelt sagt kan mengden av kobbersulfat pr. liter belegningsoppløsning være 0,002 til 0,15 mol, helst 0,002 til 0,04. Tilstrekkelig alkali bør være tilstede til å gi en pH-verdi på 10,5 til 14, helst 13j0 til 13>5- Mengden av formalde-hyd eller ekvivalent dertil kan være 0,06 til 1,3 mol, helst 0,25 til 0,50. Molantallet for det kompleksdannende middel bør være 1-4 ganger moltallet for kobber, helst omkring 2-2,5 ganger dette. Generally speaking, the amount of copper sulphate per liter of coating solution be 0.002 to 0.15 mol, preferably 0.002 to 0.04. Sufficient alkali should be present to give a pH of 10.5 to 14, preferably 13.0 to 13.5. The amount of formaldehyde or equivalent may be 0.06 to 1.3 moles, preferably 0.25 to 0.50. The molar number for the complexing agent should be 1-4 times the molar number for copper, preferably around 2-2.5 times this.
Slik som nevnt tidligere er de ikke-elektriske kobberbelegningsoppløsninger ifølge oppfinnelsen stabile i utstrakte tidsrom ved omgivelsestemperaturer. Videre kan de motstå temperaturer opp til 48,9°C og i enkelte tilfeller også koking, uten ugunstige virkninger. As mentioned earlier, the non-electrical copper coating solutions according to the invention are stable for extended periods of time at ambient temperatures. Furthermore, they can withstand temperatures up to 48.9°C and in some cases also boiling, without adverse effects.
Belegningsoppløsningene ifølge oppfinnelsen holdes helst på en spesifik vekt på 1,04 til 1,05 og en temperatur på 23,9 til 26,7°C. Under disse betingelser kan det oppnås en avsetningshastighet på 2,54 x 10<->^ cm/min. Ved høyere temperaturer økes avsetningshastigheten. The coating solutions according to the invention are preferably maintained at a specific gravity of 1.04 to 1.05 and a temperature of 23.9 to 26.7°C. Under these conditions, a deposition rate of 2.54 x 10<->^ cm/min can be achieved. At higher temperatures, the deposition rate is increased.
I praksis oppbevares kobberbelegningsoppløsningen ifølge oppfinnelsen i plasttanker eller plastforede metalltanker ved 21,1 til 37,8°C, helst under mekanisk omrøring. Stykkene som skal belegges renses, og hvis nødvendig, gjøres de følsomme ved fremgangsmåter som er vel kjent for fagmannen. Neddypping In practice, the copper coating solution according to the invention is stored in plastic tanks or plastic-lined metal tanks at 21.1 to 37.8°C, preferably with mechanical stirring. The pieces to be coated are cleaned and, if necessary, sensitized by methods well known to those skilled in the art. Immersion
av gjenstanden som skal belegges i 10 - 30 min. er vanligvis tilstrekkelig til å gi den ønskede beleggtykkelse. Etterføl-gende avsetning av ytterligere metallbelegg på elektrolytisk måte kan deretter lett gjennomføres hvis ønskelig. of the object to be coated for 10 - 30 min. is usually sufficient to give the desired coating thickness. Subsequent deposition of additional metal coatings electrolytically can then be easily carried out if desired.
Overflaten som skal belegges må være fri for fett og andre forurensende stoffer. Der en ikke-metallisk overflate skal belegges, bør overflatearealene som skal motta avsetningen, først som ved vanlige prosesser, behandles med vanlige sensitiver-ende og podende oppløsninger, slik som tinn(II)-klorid (SnC^K fulgt av behandling med en fortynnet- oppløsning av palladium- The surface to be coated must be free of grease and other contaminants. Where a non-metallic surface is to be coated, the surface areas to receive the deposit should first, as in normal processes, be treated with common sensitizing and grafting solutions, such as tin(II) chloride (SnC^K followed by treatment with a diluted - dissolution of palladium-
(PdClg). Der en metalloverflate, slik .som rustfritt stål, skal behandles, bør den avfettes og deretter behandles med syre, f.eks. saltsyre eller fosforsyre for å befri overflaten for tilstedeværende oksyd. Hvis strømløs avsetning skal skje på et plastunderlag eller et keramisk underlag som er impregnert med kobber(I)oksyd (CUgO), neddyppes den rensede gjenstand i belegningsbadet og tillates å forbli der inntil avsetningen er tilstrekkelig tykk. (PdClg). Where a metal surface, such as stainless steel, is to be treated, it should be degreased and then treated with acid, e.g. hydrochloric acid or phosphoric acid to free the surface from the oxide present. If electroless deposition is to take place on a plastic substrate or a ceramic substrate impregnated with copper (I) oxide (CUgO), the cleaned object is immersed in the coating bath and allowed to remain there until the deposition is sufficiently thick.
De følgende illustrerende eksempler skal belyse oppfinnelsen nærmere. The following illustrative examples shall illuminate the invention in more detail.
Eksempel 1 Example 1
Ifølge oppfinnelsen prepareres 7 kobber-belegnings-oppløsninger for strømløs belegning. Sammensetningen av oppløs-ningene er som følger: Til omtrent \ liter vann tilsettes i den rekkefølge som er angitt i tabellen, de forskjellige angitte forbindelser. Før tilsetningen oppløseliggjøres stabilisatorene med et medoppløsningsmiddel slik som en glykoleter, slik det lett vil være klart for fagmannen. Etter at alle bestanddelene er tilsatt, tilsettes tilstrekkelig vann til at det hele utgjør 1 liter. Hver av oppløsningene inneholder 9,25 g CuSC^ 5H2O, According to the invention, 7 copper coating solutions are prepared for electroless coating. The composition of the solutions is as follows: To approximately \ liter of water, in the order indicated in the table, the various indicated compounds are added. Before the addition, the stabilizers are solubilized with a co-solvent such as a glycol ether, as will be readily apparent to the person skilled in the art. After all the ingredients have been added, sufficient water is added so that the whole amounts to 1 litre. Each of the solutions contains 9.25 g CuSC^ 5H2O,
16 g NaOH, 5 g Na2C03 og 30 g 37 5&ig formaldehyd. 16 g NaOH, 5 g Na2C03 and 30 g 37 5&ig formaldehyde.
Den følgende tabell angir de andre bestanddeler som er tilstede i kobberbelegningsoppløsningene ifølge oppfinnelsen: The following table indicates the other components present in the copper coating solutions according to the invention:
Aksellererte stabilitetsprøver gjennomføres ved for-segling av de ovenfor angitte oppløsninger i glassampuller og lagring av disse ved 54,4<0>C opp til 12 dager. Den følgende tabell beskriver det prosentuale tap av kobber(II)-ioner ved forskjellige tidsrom for lagringen. Accelerated stability tests are carried out by sealing the above-mentioned solutions in glass ampoules and storing these at 54.4<0>C for up to 12 days. The following table describes the percentage loss of copper (II) ions at different times of storage.
Den ovenfor angitte tabell viser den markert forbed-rede stabilitet for oppløsningene ifølge oppfinnelsen sammenlignet med kontrollen. En oppløsning identisk med oppløsning nr. 1, bortsett fra at malathion ble utelatt, hadde en i det vesentlige samme stabilitet som kontrollen, selv om 0,005 ..g av ftalimidet er tilstede. Por å vise effektiviteten av kobberbelegningsoppløs-' ningene ifølge oppfinnelsen ble hver av de 7 oppløsninger benyttet til å belegge epoksyplastpaneler. Panelene ble skrubbet og gjort følsomme ifølge fremgangsmåter som er vel kjente i teknikkens stand. De følsomgjorte paneler ble deretter neddyppet i separate begerglass, hvert inneholdende en av de ovenfor angitte oppløsninger, ved 23,9°C, og en pH-verdi på 13,3 i 10 min. Den følgende tabell viser tykkelsen av det strømløst utfelte kobberbelegg som ble notert for hver av oppløsningene. The above table shows the markedly improved stability of the solutions according to the invention compared to the control. A solution identical to solution No. 1, except that malathion was omitted, had substantially the same stability as the control, even though 0.005 g of the phthalimide is present. In order to show the effectiveness of the copper coating solutions according to the invention, each of the 7 solutions was used to coat epoxy plastic panels. The panels were scrubbed and sensitized according to methods well known in the art. The sensitized panels were then immersed in separate beakers, each containing one of the above solutions, at 23.9°C, and a pH of 13.3 for 10 min. The following table shows the thickness of the electroless deposited copper coating noted for each of the solutions.
I hvert tilfelle, bortsett fra kontrollen, hadde det belagte materiale et kobberb'elegg méd en tykkelse på omtrent 254 x 10 ■ mm. Dette tilsvarer en belegningshastighet på 25,4 x 10 ^ mm pr. min. Kobberbelegget hadde en utmerket kvalitet, en rosa farge, og var fritt for urenheter. En spesielt god kvalitet oppnås der det er tilsatt sekundær stabilisator. In each case, except the control, the coated material had a copper coating having a thickness of about 254 x 10 ■ mm. This corresponds to a coating rate of 25.4 x 10 ^ mm per my. The copper coating was of excellent quality, a pink color, and free from impurities. A particularly good quality is achieved where a secondary stabilizer has been added.
Mens belegningshastighetén for kontrollen er noe høyere, er det oppnådde kobberbelegg ikke av høy kvalitet og det inneholder dekomponeringsprodukter som opptrer som' mørke og grå-aktige områder på platen. While the plating speed of the control is somewhat higher, the copper plating obtained is not of high quality and contains decomposition products that appear as dark and greyish areas on the plate.
Denne sammenligning viser tydelig at kobberbelegnings-oppløsningene ifølge oppfinnelsen er stabile, gir høyverdig kobberbelegg og har tilfredsstillende avsetningshastigheter. Fagmannen vil lett forstå at den optimale mengde stabilisatorer kan variere for spesielle belegningsbad, for spesielle substrater og for spesielle belegningsbetingelser. Ved rutineforsøk kan man oppnå den beste balanse mellom avsetningshastighet, stabilitet og beleggkvalitet. This comparison clearly shows that the copper coating solutions according to the invention are stable, provide high quality copper coating and have satisfactory deposition rates. The person skilled in the art will easily understand that the optimal amount of stabilizers can vary for particular coating baths, for particular substrates and for particular coating conditions. With routine tests, the best balance can be achieved between deposition rate, stability and coating quality.
Eksempel 2 Example 2
For å vise bruken av andre stabilisatorer innenfor rammen av oppfinnelsen, ble det fremstilt ytterligere oppløsnin-ger. Disse oppløsninger er i det vesentlige de samme som opp-løsning nr. 5 i eksempel 1, bortsett fra at stabilisatorene var 0,005 g av forskjellige dialkylmerkaptotionofosfater og at de benyttes istedenfor malathion. Ved bruk av de samme prøver som vist i eksempel 1, ble det oppnådd følgende stabiliteter og belegningshastighetén In order to demonstrate the use of other stabilizers within the scope of the invention, additional solutions were prepared. These solutions are essentially the same as solution no. 5 in example 1, except that the stabilizers were 0.005 g of various dialkyl mercaptothionophosphates and that they are used instead of malathion. Using the same samples as shown in example 1, the following stabilities and coating rates were obtained
I hvert av disse forsøk hadde kobberbelegget en utmerket kvalitet, rosa farge, og det var fritt for urenheter. In each of these trials, the copper coating was of excellent quality, pink in color, and free from impurities.
Eksempel 5 Example 5
Ved bruk av den samme fremgangsmåte som beskrevet i eksempel 1, ble det fremstilt en oppløsning identisk med oppløsning nr. 1, bortsett fra at 0}005 g N-propargyloksyftalimid ble benyttet istedet for N-propargylftalimid. Resultatene tilsvarte de som ble oppnådd for oppløsning nr. 1. Using the same method as described in Example 1, a solution identical to solution No. 1 was prepared, except that 0}005 g of N-propargyloxyphthalimide was used instead of N-propargylphthalimide. The results were similar to those obtained for solution #1.
De stabiliserte kobberbelegningsoppløsninger som er beskrevet i de ovenfor angitte eksempler, er stabile i lange tidsrom ved omgivelsestemperaturer og ved forhøyede temperaturer opp til 48,9°C sammenlignet med kontrolloppløsninger uten stabilisatorene ifølge oppfinnelsen. The stabilized copper coating solutions described in the examples given above are stable for long periods of time at ambient temperatures and at elevated temperatures up to 48.9°C compared to control solutions without the stabilizers according to the invention.
Claims (8)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US21845972A | 1972-01-17 | 1972-01-17 |
Publications (2)
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NO135188B true NO135188B (en) | 1976-11-15 |
NO135188C NO135188C (en) | 1977-02-23 |
Family
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Family Applications (1)
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NO123/73A NO135188C (en) | 1972-01-17 | 1973-01-11 |
Country Status (23)
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US (1) | US3790392A (en) |
JP (1) | JPS5519983B2 (en) |
AT (1) | AT320372B (en) |
AU (1) | AU464729B2 (en) |
BE (1) | BE794048A (en) |
CH (1) | CH599981A5 (en) |
DD (1) | DD107490A5 (en) |
DE (1) | DE2300748C3 (en) |
DK (1) | DK143948C (en) |
ES (1) | ES410652A1 (en) |
FI (1) | FI54500C (en) |
FR (1) | FR2168364B1 (en) |
GB (1) | GB1414896A (en) |
HK (1) | HK65076A (en) |
IL (1) | IL41331A (en) |
IT (1) | IT980460B (en) |
LU (1) | LU66834A1 (en) |
NL (1) | NL177330C (en) |
NO (1) | NO135188C (en) |
PL (1) | PL94000B1 (en) |
RO (1) | RO69172A (en) |
SE (1) | SE387664B (en) |
ZA (1) | ZA73328B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL164906C (en) * | 1975-08-19 | 1981-02-16 | Philips Nv | PROCESS FOR PREPARING AN AQUEOUS ALKALINE SELLER BATH. |
JPS60159328U (en) * | 1984-03-31 | 1985-10-23 | 株式会社 高津製作所 | Oil level gauge with drain alarm |
US4666858A (en) * | 1984-10-22 | 1987-05-19 | International Business Machines Corporation | Determination of amount of anionic material in a liquid sample |
US5626736A (en) | 1996-01-19 | 1997-05-06 | Shipley Company, L.L.C. | Electroplating process |
EP2639335B1 (en) | 2012-03-14 | 2015-09-16 | Atotech Deutschland GmbH | Alkaline plating bath for electroless deposition of cobalt alloys |
CN103225092A (en) * | 2013-05-22 | 2013-07-31 | 南通鑫平制衣有限公司 | Plated copper for plastics |
JP6176841B2 (en) * | 2013-07-19 | 2017-08-09 | ローム・アンド・ハース電子材料株式会社 | Electroless copper plating solution |
US10060034B2 (en) | 2017-01-23 | 2018-08-28 | Rohm And Haas Electronic Materials Llc | Electroless copper plating compositions |
US10655227B2 (en) | 2017-10-06 | 2020-05-19 | Rohm And Haas Electronic Materials Llc | Stable electroless copper plating compositions and methods for electroless plating copper on substrates |
US10294569B2 (en) | 2017-10-06 | 2019-05-21 | Rohm And Haas Electronic Materials Llc | Stable electroless copper plating compositions and methods for electroless plating copper on substrates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1192021B (en) * | 1963-01-12 | 1965-04-29 | Dehydag Gmbh | Galvanic baths |
US3457089A (en) * | 1967-04-07 | 1969-07-22 | Shipley Co | Electroless copperplating |
US3635758A (en) * | 1969-08-04 | 1972-01-18 | Photocircuits Corp | Electroless metal deposition |
-
0
- BE BE794048D patent/BE794048A/en not_active IP Right Cessation
-
1972
- 1972-01-17 US US00218459A patent/US3790392A/en not_active Expired - Lifetime
-
1973
- 1973-01-05 AU AU50768/73A patent/AU464729B2/en not_active Expired
- 1973-01-08 DE DE2300748A patent/DE2300748C3/en not_active Expired
- 1973-01-08 AT AT13573A patent/AT320372B/en not_active IP Right Cessation
- 1973-01-11 NO NO123/73A patent/NO135188C/no unknown
- 1973-01-12 SE SE7300440A patent/SE387664B/en unknown
- 1973-01-15 CH CH52373A patent/CH599981A5/xx not_active IP Right Cessation
- 1973-01-15 GB GB207373A patent/GB1414896A/en not_active Expired
- 1973-01-15 FR FR7301315A patent/FR2168364B1/fr not_active Expired
- 1973-01-15 LU LU66834A patent/LU66834A1/xx unknown
- 1973-01-16 ZA ZA730328A patent/ZA73328B/en unknown
- 1973-01-16 IT IT67057/73A patent/IT980460B/en active
- 1973-01-16 DK DK23573A patent/DK143948C/en not_active IP Right Cessation
- 1973-01-16 DD DD168260A patent/DD107490A5/xx unknown
- 1973-01-16 FI FI117/73A patent/FI54500C/en active
- 1973-01-16 ES ES410652A patent/ES410652A1/en not_active Expired
- 1973-01-16 NL NLAANVRAGE7300599,A patent/NL177330C/en not_active IP Right Cessation
- 1973-01-17 JP JP774073A patent/JPS5519983B2/ja not_active Expired
- 1973-01-17 RO RO7373524A patent/RO69172A/en unknown
- 1973-01-17 IL IL41331A patent/IL41331A/en unknown
- 1973-01-17 PL PL1973160307A patent/PL94000B1/pl unknown
-
1976
- 1976-10-14 HK HK650/76*UA patent/HK65076A/en unknown
Also Published As
Publication number | Publication date |
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DD107490A5 (en) | 1974-08-05 |
DE2300748A1 (en) | 1973-07-26 |
ES410652A1 (en) | 1976-01-01 |
LU66834A1 (en) | 1973-03-19 |
FI54500B (en) | 1978-08-31 |
BE794048A (en) | 1973-07-16 |
PL94000B1 (en) | 1977-07-30 |
FI54500C (en) | 1978-12-11 |
IL41331A (en) | 1975-11-25 |
IT980460B (en) | 1974-09-30 |
NL7300599A (en) | 1973-07-19 |
DK143948C (en) | 1982-04-19 |
NO135188C (en) | 1977-02-23 |
CH599981A5 (en) | 1978-06-15 |
JPS5519983B2 (en) | 1980-05-30 |
US3790392A (en) | 1974-02-05 |
FR2168364B1 (en) | 1975-03-28 |
DE2300748C3 (en) | 1975-10-30 |
NL177330B (en) | 1985-04-01 |
DK143948B (en) | 1981-11-02 |
ZA73328B (en) | 1973-10-31 |
NL177330C (en) | 1985-09-02 |
GB1414896A (en) | 1975-11-19 |
IL41331A0 (en) | 1973-03-30 |
FR2168364A1 (en) | 1973-08-31 |
AT320372B (en) | 1975-02-10 |
HK65076A (en) | 1976-10-22 |
JPS4999934A (en) | 1974-09-20 |
AU464729B2 (en) | 1975-09-04 |
AU5076873A (en) | 1974-07-11 |
SE387664B (en) | 1976-09-13 |
DE2300748B2 (en) | 1975-03-13 |
RO69172A (en) | 1980-01-15 |
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