CN102713007A - Agent for treatment of metal surface - Google Patents
Agent for treatment of metal surface Download PDFInfo
- Publication number
- CN102713007A CN102713007A CN2011800062619A CN201180006261A CN102713007A CN 102713007 A CN102713007 A CN 102713007A CN 2011800062619 A CN2011800062619 A CN 2011800062619A CN 201180006261 A CN201180006261 A CN 201180006261A CN 102713007 A CN102713007 A CN 102713007A
- Authority
- CN
- China
- Prior art keywords
- surface treatment
- treatment agent
- metal
- silver
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- YXIWHUQXZSMYRE-UHFFFAOYSA-N benzothiazolyl mercaptan Natural products C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012964 benzotriazole Substances 0.000 claims abstract description 7
- 239000012756 surface treatment agent Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 31
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 239000002512 suppressor factor Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 12
- 229910052728 basic metal Inorganic materials 0.000 claims description 10
- 150000003818 basic metals Chemical class 0.000 claims description 10
- 238000007669 thermal treatment Methods 0.000 claims description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 15
- 238000002310 reflectometry Methods 0.000 abstract description 15
- 238000004381 surface treatment Methods 0.000 abstract description 14
- -1 benzotriazole compound Chemical class 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 13
- 238000003466 welding Methods 0.000 description 10
- 229910000679 solder Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- 210000000981 epithelium Anatomy 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000006174 pH buffer Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- HXQHRUJXQJEGER-UHFFFAOYSA-N 1-methylbenzotriazole Chemical compound C1=CC=C2N(C)N=NC2=C1 HXQHRUJXQJEGER-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GPJPBLLWYCLERP-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-n-octyloctan-1-amine Chemical compound C1=CC=C2N(CN(CCCCCCCC)CCCCCCCC)N=NC2=C1 GPJPBLLWYCLERP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Led Device Packages (AREA)
Abstract
Disclosed is an agent for treating a metal surface, which can exhibit a high discoloration-preventing effect even when exposed to a heat treatment during a production process thereof or high temperature environments during use, has excellent wire bonding properties, and does not cause the deterioration in reflectivity when subjected to a surface treatment. The agent for treating a metal surface is characterized by being produced by dissolving or dispersing, as an inhibitor, at least specific compound selected from the group consisting of a benzotriazole compound represented by general formula (1), a mercaptobenzothiazole compound represented by general formula (2) and a triazine compound represented by general formula (3) in water and adjusting the pH value of the solution or dispersion to 4 to 7.
Description
Technical field
The present invention relates to the surface treatment agent of metal, particularly silver or silver alloys.
Background technology
As the junctor of electronics with interconnecting piece, a large amount of substrates of using copper facing on the surface of brass, phosphor bronze, nickel, and and then in this substrate silver plated material.Because silver is the good conductor of electricity and heat, so the silver coating that is used as junctor, lead frame etc. as described above uses.But the silvering material is variable color easily in air, is particularly containing under the atmosphere of sulphur and can be corroded, and it is black-and-blue to become dark brown, has the problem that electrically contacts variation.
As one of method that addresses this problem, surface preparation is arranged.Promptly, with treatment solution Processing Ag coating surface, cause appearance degradation and contact resistance to improve to prevent variable color.As the surface preparation in the past of silvering material, for example have shown in the patent documentation 1 such, the method for Processing Ag coating material in containing the solution of suppressor factor.Although utilize this method can see that really the saprophage that prevents because of silvering causes the effect that prevents of variable color, this prevents that effect is incomplete, and is different according to environment, still has the problem of local variable color.
In addition, put down in writing in the patent documentation 2 and prevented the silvering material, and then given surface treatment liquid and the surface treatment method of coating surface with oilness because of the saprophage variable color.In this surface treatment liquid as suppressor factor contain be selected from specific benzotriazole based compound, mercaptobenzothiazole based compound and the triazine based compound more than a kind or 2 kinds, and then contain lubricant and emulsifying agent.This surface treatment liquid is owing to carry out the pH value and adjusted, so can think in pH8.8 ~ 8.9 time to carry out surface treatment.When being used for junctor, though in anti-variable color, give oilness, should prevent that color changeable effect was insufficient, thermotolerance can not be said so fully in addition.
On the other hand, photodiode (LED) device is through semi-conductive pn knot is circulated along directional current; At engaging zones electronics and hole are combined once more; Thereby carry out luminous diode, since simple in structure, electric energy is directly become luminous energy; So conversion efficiency, safety height are by extensive practicability.
In recent years, from the viewpoint of energy-conservation even environment protection, as replacement present incandescent light, the new light sources of luminescent lamp, lighting fixtures, the utilization of white color light emitting diode receives that people pay close attention to.
This LED device is designed to: process the pedestal of lead frame, carry led chip in position that reflecting part fences up, the illuminating reflecting part of led chip is efficiently taken out.In addition, as required, with the resin package of said led chip with epoxy resin etc.
This LED device, though as light source by practicability, the problem that exists all needs to improve.The problem that the first, existence improve the reflectivity of reflecting part.
As the elite clone of present luminous reflectance factor, known that the epithelium of silver, aluminium or gold is useful materials (patent documentation 3,4).Wherein, the glossiness of silver, reflectivity height are used as most preferred material as reflecting material and are known by the people.
But silver has activity, and the surface of argenteum makes its performance reduction easily through oxidation etc. and variable color is influential to the light reflective of argenteum.Variable color under the hot environment of particularly have heat treated variable color, being given in use because of LED manufacturing process, the problem that causes light reflective properties to reduce.
But the countermeasure that reduces about the improvement of the light reflective properties of argenteum or the light reflective properties that causes owing to the variable color under oxidation stain, the particularly hot environment; Still do not develop otherwise effective technique; Particularly be used as the white light source that needs high brightness of use in vehicle mounted, illumination are used etc., need carry out above-mentioned improvement in order to promote.
Even promptly, need be in the heat treated in the LED manufacturing process etc., or be exposed under the hot environment surface treatment agent that anti-color changeable effect is high, the metal wire welding characteristic is excellent, surface treatment does not make the reflectivity deterioration in use.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 5-311492 communique
Patent documentation 2: japanese kokai publication hei 9-249977 communique
Patent documentation 3: TOHKEMY 2005-56941 communique
Patent documentation 4: japanese kokai publication hei 9-293904 communique
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide a kind of in the heat treated in the LED manufacturing process etc., even perhaps be exposed in use under the hot environment, the surface treatment agent that anti-color changeable effect is high, the metal wire welding characteristic is excellent, surface treatment does not make the reflectivity deterioration.
Solve the means of problem
In order to address the above problem, the inventor studies, the surface treatment agent shown in below the result has invented.
Promptly the present invention includes following technical scheme.
(1). a kind of metallic surface treatment agent; It is characterized in that; Through will being selected from the compound dissolution more than a kind or 2 kinds in the triazine based compound shown in mercaptobenzothiazole based compound shown in the benzotriazole based compound shown in the formula (1), the formula (2) and the formula (3) or being dispersed in the water as suppressor factor; It is 4 ~ 7 that the pH value is adjusted to, thereby obtains
In the formula, R
1Represent hydrogen, replacement or do not have substituted alkyl, R
2Represent basic metal, hydrogen, replacement or do not have substituted alkyl,
In the formula, R
3Expression basic metal or hydrogen,
In the formula, R
4Expression-SH, by alkyl, alkenyl or aryl substiuted amino or alkyl substituted imidazole base alkyl, R
5, R
6Expression-NH
2,-SH or-SM, M representes basic metal.
(2). like above-mentioned (1) described metallic surface treatment agent, it is characterized in that, also contain tensio-active agent.
(3). like above-mentioned (1) or (2) described metallic surface treatment agent, it is characterized in that said metal is silver or silver alloys.
(4). each the described metallic surface treatment agent like above-mentioned (1) ~ (3), it is characterized in that, be used for the LED reflecting material that the surface has silver or silver alloys.
(5). a kind of surface has the base material of metal, it is characterized in that, uses each described metallic surface treatment agent of above-mentioned (1) ~ (3) to handle.
(6). have the base material of metal like above-mentioned (5) described surface; It is characterized in that; The metallic surface that it uses said surface treatment agent to handle, even after carrying out 10 minutes thermal treatment under 200 ℃ and then carrying out 6 hours thermal treatment under 120 ℃, anti-discolouration is also excellent.
(7). have the base material of metal like above-mentioned (5) or (6) described surface, it is characterized in that said base material is the LED reflecting material that the surface has silver or silver alloys.
The invention effect
Through the metallic surface that surface treatment agent of the present invention was handled, the metachroic deterioration that prevents that effect is high, the metal wire welding characteristic is excellent, surface treatment can not cause reflectivity of heat treated.In addition, surface treatment agent of the present invention is water-soluble, does not contain organic solvent, heavy metal, so excellent in safety does not produce and handles bad order uneven, spot.In addition, contact resistance is low, and solder wetting property is good.
Embodiment
The suppressor factor that contains in the surface treatment agent of the present invention be selected from the compound shown in following, be in benzotriazole based compound, mercaptobenzothiazole based compound, the triazine based compound more than a kind or 2 kinds.These suppressor factor are through generating very thin protection epithelium in the metallic surface with metal reaction, and through this epithelium metal inside is protected, and the erosion resistance of metallic surface (discoloration-resistant) improves as a result.
The benzotriazole based compound that uses among the present invention is with general formula (1) expression,
(in the formula, R
1Represent hydrogen, replacement or do not have substituted alkyl, R
2Represent basic metal, hydrogen, replacement or do not have substituted alkyl.)。
As the R in the general formula (1)
1Represented replacement or do not have substituted alkyl, the alkyl of preferred carbonatoms 1 ~ 24, and, as R
2The replacement of expression or do not have substituted alkyl, the alkyl of also preferred carbonatoms 1 ~ 24.In addition, as said substituting group, be preferably amino, sulfydryl, hydroxyl etc.Said amino can also be by carbonatoms 1 ~ 24 alkyl substituted.
If enumerate the preference in the compound shown in this general formula (1), then for example can enumerate, benzotriazole (R
1, R
2Be hydrogen), 1-Methylbenzotriazole (R
1Be hydrogen, R
2Be methyl), azimido-toluene (R
1Be methyl, R
2Be hydrogen), 1-(N, N-dioctyl amino methyl) benzotriazole (R
1Be hydrogen, R
2Be N, N-dioctyl amino methyl) etc.
The mercaptobenzothiazole based compound that uses among the present invention is represented with general formula (2).
(in the formula, R
3Expression basic metal or hydrogen.)
If enumerate the preference in the compound shown in this general formula (2), then can enumerate the sodium salt of for example mercaptobenzothiazole, mercaptobenzothiazole, the sylvite of mercaptobenzothiazole etc.R in the general formula (2)
3During for basic metal, the mercaptobenzothiazole based compound is dissolved in the water easily.
The triazine based compound is represented with general formula (3).
(in the formula, R
4Expression-SH, by alkyl, alkenyl or aryl substiuted amino or alkyl substituted imidazole base alkyl, R
5, R
6Expression-NH
2,-SH or-SM (M representes basic metal).〕
As the R in the general formula (3)
4Substituent, the said alkyl or the alkenyl of represented amino, alkyl, the alkenyl of preferred carbonatoms 1 ~ 24 are as the preferred phenyl of aryl.If enumerate the preference of the compound shown in this general formula (3), can enumerate out for example following compound.
Perhaps, be an alkali metal salt of their Na or K etc.R in the general formula (3)
5, R
6The dissolving of triazine based compound in water becomes easy during for-SM.
Suppressor factor is dissolved or be dispersed in the water.The addition of suppressor factor is in the scope of 0.001 ~ 1 weight %, more preferably 0.001 ~ 0.1 weight %.When being lower than 0.001 weight %, can't see treatment effect, when more than 1 weight %, finding has detrimentally affect to contact resistance.
Water preferably uses pure water, after making the suppressor factor dissolving or disperseing, the pH value is adjusted to 4 ~ 7.As the pH regulator agent, preferably use organic acids such as phosphoric acid, acetate, Hydrocerol A, tartrate, oxalic acid, oxysuccinic acid, succsinic acid etc.
When the pH value was low, anti-color changeable effect uprised, but the bad stability of liquid.In addition, also variation of the solvability of suppressor factor.Otherwise when the pH value uprised, the stability of liquid improved, but anti-color changeable effect step-down.Based on the stability of anti-color changeable effect and liquid, more preferably the pH value is 4 ~ 7, and then preferred pH value is 5 ~ 6.
And then, surface treatment agent of the present invention, can from make suppressor factor in the aqueous solution, dissolve, improve the metallic surface wettability, make solution soak into, make clean etc. the purpose in metallic surface easily, and contain tensio-active agent.In addition, surface treatment agent of the present invention from suppressor factor dissolved purpose in the aqueous solution, can contain dissolution aids.
As tensio-active agent, natural alcohol is that tensio-active agent is because biological degradability is excellent, few and preferred to the environment detrimentally affect.Can preferably use alkylphenol ethylene oxide adduct, the higher alcohols ethylene oxide adduct of decomposition of little under acid, alkali effect.
As dissolution aids, preferably using terepthaloyl moietie such as Ethylene Glycol Methyl ether, terepthaloyl moietie isopropyl ether, ethylene glycol butyl ether is propylene glycol system of ether, propylene glycol monomethyl ether, propylene glycol propyl ether, Ucar 35 butyl ether etc. etc.
In addition, as the composition that can also contain, can enumerate out the pH buffer reagent.
The pH buffer reagent has the effect that the pH value that makes solution is fixing, control the adsorptivity of suppressor factor.As the pH buffer reagent, can enumerate out sodium hydrogen phosphate, acetate, sodium acetate, Hydrocerol A, Trisodium Citrate, tartrate, sodium tartrate etc.From considerations such as cost, use difficulty or ease property, optimization citric acid, sodium acetate etc.
Surface treatment agent of the present invention does not contain lubricant.The situation of the surface treatment agent that in as the junctor purposes of electronics, uses with interconnecting piece; Need give oilness to the metallic surface; So contain lubricant, but be not in the junctor purposes but the surface treatment agent of the present invention that in LED reflecting material etc., uses need not given oilness; Perhaps give oilness and bring detrimentally affect might for the metal wire welding characteristic, so do not contain lubricant.
As treatment process, can utilize treated material is immersed in the surface treatment agent, or surface treatment agent is sprayed or arbitrary method of coating etc., but preferred dipping.As immersion condition, flood more than 5 seconds down, got final product in about for example 5 seconds ~ 1 minute 15 ~ 60 ℃ of temperature, then washing, drying.
Through washing, handle bad orders such as inequality, spot and disappear.
As treated material, be the base material that the surface has metal, as metal, can enumerate out silver, silver alloys, copper, brass, phosphor bronze, iron etc.Preferably use as the silver of variable color especially easily and the surface treatment agent of silver alloys.As silver alloys, can enumerate out the alloy of silver and, gold, platinum, copper, palladium, indium, tin, zinc, ruthenium, rhodium, bismuth etc.
Come treat surface to have the base material of metal through such use surface treatment agent of the present invention, form the epithelium that forms by surface treatment agent in the metallic surface.
Surface treatment agent of the present invention is the aqueous solution, does not contain organic solvent, heavy metal, so excellent in safety.In addition; Handle metallic surface that obtain, that have the epithelium that forms by surface treatment agent through surface treatment agent of the present invention; Even for example carrying out 10 minutes thermal treatment under 200 ℃, under 120 ℃, carrying out 6 hours thermal treatment; Anti-discolouration is also excellent, and contact resistance is low, solder wetting property is good, the deterioration that the metal wire welding characteristic is excellent, surface treatment does not produce reflectivity yet.
Therefore, metallic surface treatment agent of the present invention preferably uses as the surface treatment agent of reflecting material that the surface has a LED of silver or silver alloys.
Embodiment
Enumerate embodiment below and specify the present invention.
Embodiment 1
As being processed base material, use the substrate that on pure Cu substrate, plates the thick silver layer of 4 μ m, it is immersed in 30 seconds in the surface treatment agent of following composition under 40 ℃, washing then, through blower with the warm braw drying, thereby carry out surface treatment.
Surface treatment agent is formed
Suppressor factor: triazine-2,4,6-three mercaptan 0.01 weight %
Tensio-active agent: oleyl alcohol ethoxylate 0.01 weight %
Dissolution aids: Ucar 35 butyl ether 1 weight %
PH buffer reagent: sodium hydrogen phosphate 1 weight %
Use phosphoric acid as the pH regulator agent, the pH value is adjusted to 5.5.
To the base material after the surface treatment of embodiment 1; Under the situation of not heat-treating, carry out hydrogen sulfide test (concentration of hydrogen sulfide: 3ppm, temperature: 40 ℃, humidity: 80%RH, test period: 4 hours), carry out the visual inspection of outward appearance based on JISH8502.In addition; Carry out 200 ℃ of following heat treated of 10 minutes with the heated air circulation type drying machine after; And then under 120 ℃, carry out 6 hours heat treated, and the base material after the heat treated is carried out the hydrogen sulfide test same with the situation of not heat-treating, carry out the visual inspection of outward appearance.
Metewand
Zero: detect by an unaided eye, find that coating surface does not have variable color;
△: detect by an unaided eye, find that coating surface becomes light blueness,
*: detect by an unaided eye, it is darker black-and-blue to find that coating surface becomes.
Result such as table 1 expression.
Embodiment 2 ~ 8, comparative example 1 ~ 8
Suppressor factor among the embodiment 1 and pH buffer reagent are become the compound and the concentration of record in the table 1, the pH value is become the value shown in the table 1 with phosphoric acid, in addition, be processed the surface treatment of base material equally, estimate equally with embodiment 1 with embodiment 1.
The result is as shown in table 1.
[table 1]
Base material after the surface treatment of use embodiment 1,2,7 and comparative example 1 carries out the evaluation of contact resistance, solder wetting property, metal wire welding characteristic, reflectivity with following mode.The result is as shown in table 2.
(1) contact resistance
Contact resistance is measured under direct current 7.4mA, open voltage 20mV, load 2.5 ~ 50g.The judgment standard of contact resistance is following.
Zero: contact resistance is less than 0.02 Ω;
*: contact resistance is more than 0.02 Ω
(2) solder wetting property
Solder wetting property is through the sample before and after heat of immersion is handled in the solder trough of 265 ℃ tin-silver-copper alloy, measures buoyancy and becomes for 0 needed time, thereby estimate.Thermal treatment is under 200 ℃, to carry out 10 minutes, and then under 120 ℃, carries out 6 hours.The judgment standard of solder wetting property is following.
Zero: buoyancy became for 0 needed time and is less than 0.2 second;
*: it is more than 0.2 second that buoyancy became for 0 needed time
(3) metal wire welding characteristic
The metal wire welding characteristic is through after engaging metal wire, and metal wire is stretched, pulls apart with 500 μ m/ second, pulls apart with line that the position estimates.The judgment standard of metal wire welding characteristic is following.
Zero: line is for pulling apart
*: peel off at online place, junction surface with sample
(4) reflectivity
Reflectivity is through the reflectivity under 450 ~ 900nm of the sample that uses ultraviolet-visual spectrometer mensuration thermal treatment front and back, thereby estimate.In addition, thermal treatment is after carrying out 10 minutes under 200 ℃ and then under 120 ℃, to carry out 6 hours.The judgment standard of reflectivity is following.
Zero: be more than 90% in 450 ~ 900nm internal reflection rate.
*: in 450 ~ 900nm, exist reflectivity to be lower than 90% wavelength.
[table 2]
Among the embodiment 1,2,7, the deterioration of the rising of contact resistance, the deterioration of solder wetting property, reflectivity all do not see, hence one can see that road, and anti-variable color is handled does not have detrimentally affect to contact resistance, solder wetting property, reflectivity.In addition, among the embodiment 1,2,7, do not find that the junction surface of metal wire and sample is peeled off, hence one can see that, and anti-variable color is handled does not have detrimentally affect to the metal wire welding characteristic.
Claims (7)
1. metallic surface treatment agent; It is characterized in that; Through will being selected from the compound dissolution more than a kind or 2 kinds in the triazine based compound shown in mercaptobenzothiazole based compound shown in the benzotriazole based compound shown in the formula (1), the formula (2) and the formula (3) or being dispersed in the water as suppressor factor; It is 4 ~ 7 that the pH value is adjusted to, thereby obtains
In the formula, R
1Represent hydrogen, replacement or do not have substituted alkyl, R
2Represent basic metal, hydrogen, replacement or do not have substituted alkyl,
In the formula, R
3Expression basic metal or hydrogen,
In the formula, R
4Expression-SH, by alkyl, alkenyl or aryl substiuted amino or alkyl substituted imidazole base alkyl, R
5, R
6Expression-NH
2,-SH or-SM, M representes basic metal.
2. metallic surface treatment agent as claimed in claim 1 is characterized in that, also contains tensio-active agent.
3. according to claim 1 or claim 2 metallic surface treatment agent is characterized in that said metal is silver or silver alloys.
4. like each described metallic surface treatment agent of claim 1 ~ 3, it is characterized in that, be used for the LED reflecting material that the surface has silver or silver alloys.
5. a surface has the base material of metal, it is characterized in that, uses each described metallic surface treatment agent of claim 1 ~ 3 to handle.
6. surface as claimed in claim 5 has the base material of metal; It is characterized in that; The metallic surface that it uses said surface treatment agent to handle, even after carrying out 10 minutes thermal treatment under 200 ℃ and then carrying out 6 hours thermal treatment under 120 ℃, anti-discolouration is also excellent.
7. have the base material of metal like claim 5 or 6 described surfaces, it is characterized in that said base material is the LED reflecting material that the surface has silver or silver alloys.
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| CN113403652A (en) * | 2021-06-17 | 2021-09-17 | 深圳市联合蓝海黄金材料科技股份有限公司 | Protective film electrolyte, gold-plated silver ornament and preparation method thereof |
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| JP6209996B2 (en) * | 2014-03-11 | 2017-10-11 | 住友金属鉱山株式会社 | Metal surface treatment method |
| JP6149811B2 (en) * | 2014-06-27 | 2017-06-21 | 住友金属鉱山株式会社 | Method for manufacturing metal member for LED package |
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| JP2007266343A (en) * | 2006-03-29 | 2007-10-11 | Toyoda Gosei Co Ltd | Light emitting device |
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| JPS6043493A (en) * | 1983-08-19 | 1985-03-08 | Chiyoda Kagaku Kenkyusho:Kk | Discoloration inhibitor for copper |
| JP2550436B2 (en) * | 1990-10-23 | 1996-11-06 | 株式会社ジャパンエナジー | Anti-tarnish solution for copper |
| JP2008045215A (en) * | 1999-01-25 | 2008-02-28 | Chemical Denshi:Kk | Metal surface treatment agent, and surface treatment method for metallic layer |
| JP4740754B2 (en) * | 2006-01-27 | 2011-08-03 | 株式会社大和化成研究所 | Anti-discoloration composition |
| JP2007266349A (en) * | 2006-03-29 | 2007-10-11 | Matsushita Electric Ind Co Ltd | Conductive member for semiconductor device, package for semiconductor device, and manufacturing method of them |
| JP2009120437A (en) * | 2007-11-14 | 2009-06-04 | Niigata Univ | Siloxane-grafted silica, highly transparent silicone composition, and light-emitting semiconductor device sealed with the composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09249977A (en) * | 1996-03-13 | 1997-09-22 | Nikko Kinzoku Kk | Surface treatment liquid for silver plated material and surface treatment using the same |
| CN1520468A (en) * | 2001-06-26 | 2004-08-11 | �ձ�������ʽ���� | Surface treatment agent for metal, process for surface treatment of metallic substances and surface-treated metallic substances |
| JP2004169157A (en) * | 2002-11-22 | 2004-06-17 | Mitsubishi Paper Mills Ltd | Process and liquid for treating silver-plated layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113403652A (en) * | 2021-06-17 | 2021-09-17 | 深圳市联合蓝海黄金材料科技股份有限公司 | Protective film electrolyte, gold-plated silver ornament and preparation method thereof |
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| CN103789772B (en) | 2016-04-27 |
| CN103789772A (en) | 2014-05-14 |
| TW201134982A (en) | 2011-10-16 |
| TWI537422B (en) | 2016-06-11 |
| WO2011089943A1 (en) | 2011-07-28 |
| JP5995305B2 (en) | 2016-09-21 |
| JPWO2011089943A1 (en) | 2013-05-23 |
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