CN114833491A - Copper surface selective organic solderability preservative and use method thereof - Google Patents
Copper surface selective organic solderability preservative and use method thereof Download PDFInfo
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- CN114833491A CN114833491A CN202210701011.7A CN202210701011A CN114833491A CN 114833491 A CN114833491 A CN 114833491A CN 202210701011 A CN202210701011 A CN 202210701011A CN 114833491 A CN114833491 A CN 114833491A
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- acid
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- solderability preservative
- organic
- selective organic
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 239000003755 preservative agent Substances 0.000 title claims abstract description 29
- 230000002335 preservative effect Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 12
- FXDLIMJMHVKXAR-UHFFFAOYSA-K iron(III) nitrilotriacetate Chemical compound [Fe+3].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O FXDLIMJMHVKXAR-UHFFFAOYSA-K 0.000 claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 229940120146 EDTMP Drugs 0.000 claims description 6
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 6
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 5
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 5
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- 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 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910000679 solder Inorganic materials 0.000 abstract description 39
- -1 phosphine compound Chemical class 0.000 abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002845 discoloration Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005476 soldering Methods 0.000 description 11
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- COGUOPIIFAMLES-UHFFFAOYSA-N 2-[(4-chlorophenyl)methyl]-1h-benzimidazole Chemical compound C1=CC(Cl)=CC=C1CC1=NC2=CC=CC=C2N1 COGUOPIIFAMLES-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229960002446 octanoic acid Drugs 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- OIHHDYNKEHASLI-UHFFFAOYSA-N 2-[(2,4-dichlorophenyl)methyl]-1h-benzimidazole Chemical compound ClC1=CC(Cl)=CC=C1CC1=NC2=CC=CC=C2N1 OIHHDYNKEHASLI-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 3
- WELZFURMIFFATQ-UHFFFAOYSA-N 5-methyl-2,4-diphenyl-1h-imidazole Chemical compound CC=1NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 WELZFURMIFFATQ-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 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
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- FHHCKYIBYRNHOZ-UHFFFAOYSA-N 2,5-diphenyl-1h-imidazole Chemical compound C=1N=C(C=2C=CC=CC=2)NC=1C1=CC=CC=C1 FHHCKYIBYRNHOZ-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- XPFCXIKQEQOMMW-UHFFFAOYSA-N 2-[(3,4-dichlorophenyl)methyl]-1h-benzimidazole Chemical compound C1=C(Cl)C(Cl)=CC=C1CC1=NC2=CC=CC=C2N1 XPFCXIKQEQOMMW-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- RJRKURJUHLRUPD-UHFFFAOYSA-N 2-heptyl-1h-benzimidazole Chemical compound C1=CC=C2NC(CCCCCCC)=NC2=C1 RJRKURJUHLRUPD-UHFFFAOYSA-N 0.000 description 1
- OYGJENONTDCXGW-UHFFFAOYSA-N 2-pentyl-1h-benzimidazole Chemical compound C1=CC=C2NC(CCCCC)=NC2=C1 OYGJENONTDCXGW-UHFFFAOYSA-N 0.000 description 1
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- YTLQFZVCLXFFRK-UHFFFAOYSA-N bendazol Chemical compound N=1C2=CC=CC=C2NC=1CC1=CC=CC=C1 YTLQFZVCLXFFRK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
Abstract
The invention belongs to the technical field of circuit board processing, and particularly relates to a copper surface selective organic solderability preservative. The copper surface selective organic solderability preservative provided by the invention comprises iron nitrilotriacetate, an organic phosphine compound, an imidazole derivative and an organic acid. The selective organic solder mask provided by the invention selectively forms a compact solder mask with the thickness of 0.15-0.35um on the copper surface of the PCB, and because the selective organic solder mask does not contain copper ions, the solder mask is not formed on the gold surface. In addition, because the selective organic solderability preservative contains the organic phosphine compound and the ferric nitrilotriacetate, the solderability preservative film layer prepared by the selective organic solderability preservative provided by the invention has excellent performances in three aspects of oxidation resistance, heat resistance and solderability.
Description
Technical Field
The invention belongs to the technical field of PCB processing, and particularly relates to a copper surface selective organic solderability preservative and a use method thereof.
Background
An Organic solder mask (OSP) is formed by forming an Organic film layer on a clean bare copper surface in a chemical deposition mode by taking an imidazole derivative as an active component, wherein the film layer can prevent the copper surface from being oxidized and damped, can resist multiple thermal shocks in the subsequent SMT treatment process and keeps good weldability. The development of the OSP technology is driven by the trend of Printed Circuit Boards (PCBs) toward multi-layer, high-density, thin boards, and thinner and shorter electronic components, which leads to the improvement of the requirements of SMT on the heat resistance and solderability of surface treatment, and the conventional tin-spraying process cannot meet the requirements, so the OSP technology is rapidly developed under such circumstances.
In the prior art, the OSP film layer is generally aged quickly in multiple lead-free reflow soldering hot-impact processes, discoloring and blackening are caused, the solderability is deteriorated, and the tin-coating rate is reduced rapidly, and particularly, the tin-coating rate and the tin-coating rate of a through hole are difficult to meet the requirements of plug-in wave soldering performed after 2-3 times of reflow soldering. In addition, the surface of the PCB treated by the nickel-gold and nickel-palladium-gold treatment has a copper surface and a gold surface at the same time, and when the OSP process treatment is carried out, the film can only be selectively formed on the copper surface. If the film is formed on the gold surface, the quality of the binding and routing of the subsequent gold surface is seriously poor. The existing organic solder mask usually contains copper ions, and the copper ions are the main factor causing the film formation of the gold surface.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a copper surface selective organic solder flux and a use method thereof. The organic solder resist contains iron nitrilotriacetate and an organic phosphine compound, and a solder resist layer prepared from the organic solder resist has excellent oxidation resistance, heat resistance and weldability. In order to achieve the purpose, the technical scheme of the invention is as follows:
the copper surface selective organic solderability preservative comprises the following components in percentage by mass:
0.01-1 mass% of iron nitrilotriacetate, 0.01-1 mass% of an organic phosphine compound, 0.1-1 mass% of an imidazole derivative, and 5-30 mass% of an organic acid.
The content of the iron nitrilotriacetate in the copper surface-selective organic solderability preservative is preferably 0.01 to 0.5 mass%, more preferably 0.05 to 0.2 mass%, most preferably 0.08 to 0.12 mass%. When the mass percent of the iron nitrilotriacetate is less than 0.01 mass percent, the thickness of the welding-maintaining film layer is insufficient. When the mass percentage of iron nitrilotriacetate is more than 0.5 mass%, the stability of the solution is lowered, and there is a risk of solid precipitation.
In the copper surface-selective organic solder resist, the organic phosphine compound is preferably at least one selected from the group consisting of aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, ethylenediaminetetramethylidene phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, polyaminopolyetherylmethylenephosphonic acid, bis-1, 6-hexamethylenetriaminepentamethylenephosphonic acid, and sodium salts and potassium salts corresponding to the organic phosphonic acids. More preferably at least one selected from the group consisting of aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid. Most preferably at least one selected from the group consisting of ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid.
The content of the organophosphinic compound in the copper surface-selective organic solder resist is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, most preferably 0.1 to 0.2% by mass. When the mass percentage of the organic phosphine compound is less than 0.01 mass%, the solder resist layer is poor in heat resistance and weldability. When the mass percentage of the organic phosphine compound is more than 1% by mass, no more preferable effect is obtained.
The imidazole derivative in the copper surface selective organic solder resist is not particularly limited, and for example, at least one of 2-pentylbenzimidazole, 2-heptylbenzimidazole, 2-phenylbenzimidazole, 2-benzylbenzimidazole, 2- (4-chlorobenzyl) benzimidazole, 2- (2, 4-dichlorobenzyl) benzimidazole, 2- (3, 4-dichlorobenzyl) benzimidazole, 2, 4-diphenylimidazole, 2, 4-diphenyl-5-methylimidazole, and 2- (2-chlorophenyl) -45-diphenylimidazole can be used.
The imidazole derivative content in the copper surface-selective organic solder resist is preferably 0.05 to 1.5 mass%, more preferably 0.1 to 1 mass%, most preferably 0.3 to 0.7 mass%. When the amount of the imidazole derivative is less than 0.05% by mass, an effective solder mask layer cannot be formed. When the percentage of the imidazole-derived substance is more than 1.5% by mass, the risk of precipitation of the imidazole compound is increased.
The organic acid in the copper surface-selective organic solder resist is not particularly limited, and for example, at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, malic acid, and citric acid can be used.
The content of the organic acid in the copper surface-selective organic solder resist is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, most preferably 10 to 15% by mass. When the organic acid content is less than 1% by mass, the imidazole derivative cannot be completely dissolved. When the organic acid content is more than 30% by mass, there is a risk that the solder resist film layer cannot be formed.
The components of the copper surface selective organic solderability preservative can be dissolved in deionized water, pure water and ultrapure water for preparation.
The use method of the copper surface selective organic solderability preservative adopts a dipping method, wherein the dipping time is 60-90 seconds, and the dipping temperature is 40-45 ℃.
The selectivity of the method for using the copper surface selective organic solderability preservative is that when the PCB surface has copper and gold coexists, the PCB is immersed in the copper surface selective organic solderability preservative, a solderability preservative film is formed only on the copper surface, and a solderability preservative film is not formed on the gold surface.
The thickness of a compact solderability preservative film layer prepared by the selective organic solderability preservative provided by the invention is 0.15-0.35um, and the performances of three aspects of oxidation resistance, heat resistance and solderability are excellent.
Detailed Description
The present invention will be further described below by way of specific embodiments, but the present invention is not limited to only the following examples.
The invention discloses a copper surface selective organic solder mask and a using method thereof, wherein an organic solder mask solution is prepared, and a PCB (printed circuit board) nickel gold plate is selected as a test board. The degreaser and the microetching agent are products of Hafu electronics technology Limited company, and the product names are HAR9010 degreaser and HAR9020 microetching agent respectively.
And comparing whether the gold surface forms a welding protection film layer.
Example 1 the organic solder resist solution of example 1 was prepared by adding 0.3 mass% of ethylenediaminetetramethylenephosphonic acid, 0.1 mass% of iron nitrilotriacetate, 0.5 mass% of 2- (4-chlorobenzyl) benzimidazole, 0.1 mass% of heptanoic acid, and 10 mass% of acetic acid to deionized water.
The organic solderability preservative solution was heated to 40 ℃ and its pH = 3.3 was adjusted. And (3) after the test board is subjected to oil removal, microetching, washing and cold air drying treatment, soaking the test board in the soldering flux protecting solution for 90 seconds, taking out the test board, washing the test board by pure water, and drying the test board by cold air to finish the organic soldering flux protecting film manufacturing process. The gold surface was visually observed to have no discoloration. The gold surface EDS analysis results are shown in table 1.
Comparative example 1 the organic solder resist solution of comparative example 1 was prepared by adding 0.3 mass% of ethylenediaminetetramethylenephosphonic acid, 0.1 mass% of copper chloride, 0.5 mass% of 2- (4-chlorobenzyl) benzimidazole, 0.1 mass% of heptanoic acid, and 10 mass% of acetic acid to deionized water.
The organic solderability preservative solution was heated to 40 ℃ and its pH = 3.3 was adjusted. And (3) after the test board is subjected to oil removal, microetching, washing and cold air drying treatment, soaking the test board in the soldering flux protecting solution for 90 seconds, taking out the test board, washing the test board by pure water, and drying the test board by cold air to finish the organic soldering flux protecting film manufacturing process. The gold surface was visually observed to be distinctly different in color. The gold surface EDS analysis results are shown in table 1.
In addition, one set of test panels was used as a blank panel without any solder mask treatment by degreasing, microetching, washing, and drying with cold air. The gold-faced EDS is shown in table 1.
TABLE 1 gold EDS analysis results
Mass percent of element Au Ni P C O N
Example 196.23% 3.03% 0.30% 0.35% 0.08-
Comparative example 192.26% 2.65% 0.27% 4.20% -0.59
Blank 96.10%, 3.04%, 0.30%, 0.44%, 0.12-
As can be seen from table 1, the EDS analysis results of example 1 and the blank plate are consistent, and it is found that no solder mask was formed on the gold surface of example 1. The EDS analysis result of the comparative example 1 shows that the content of C is obviously increased, and N is detected, which also indicates that the welding-protecting film is formed on the gold surface.
And the oxidation resistance, the heat resistance and the weldability of the welding protection film layer are compared.
Example 2A solder resist solution of example 2 was prepared by adding 0.5 mass% of hydroxyethylidene diphosphonic acid, 0.2 mass% of iron nitrilotriacetate, 0.5 mass% of 2- (2, 4-dichlorobenzyl) benzimidazole, 0.2 mass% of hexanoic acid, and 20 mass% of acetic acid to deionized water.
Example 3A solder resist solution of example 3 was prepared by adding 0.1 mass% of aminotrimethylenephosphonic acid, 0.15 mass% of iron nitrilotriacetate, 0.2 mass% of 2, 4-diphenylimidazole, 10 mass% of acetic acid, 5 mass% of propionic acid, and 0.05 mass% of octanoic acid to deionized water.
Example 4A solder resist solution of example 4 was prepared by adding 0.2 mass% of diethylenetriamine pentamethylenephosphonic acid, 0.3 mass% of iron nitrilotriacetate, 0.35 mass% of 2, 4-diphenyl-5-methylimidazole, 0.1 mass% of octanoic acid, 8 mass% of formic acid, and 2 mass% of propionic acid to deionized water.
Comparative example 2A solder resist solution of comparative example 2 was prepared by adding 0.3 mass% of ethylenediaminetetramethylenephosphonic acid, 0.001 mass% of iron nitrilotriacetate, 0.8 mass% of 2- (4-chlorobenzyl) benzimidazole, 0.1 mass% of heptanoic acid, and 10 mass% of formic acid to deionized water.
Comparative example 3A solder resist solution of comparative example 3 was prepared by adding 0.001 mass% of hydroxyethylidene diphosphonic acid, 0.5 mass% of iron nitrilotriacetate, 0.5 mass% of 2- (2, 4-dichlorobenzyl) benzimidazole, 0.2 mass% of hexanoic acid, and 20 mass% of acetic acid to deionized water.
Comparative example 4A solder resist solution of comparative example 4 was prepared by adding 0.1 mass% of aminotrimethylenephosphonic acid, 0.001 mass% of iron nitrilotriacetate, 0.2 mass% of 2, 4-diphenyl-5-methylimidazole, 10 mass% of acetic acid, 5 mass% of propionic acid, and 0.05 mass% of octanoic acid to deionized water.
The above-mentioned solder resist solutions of examples 2 to 4 and comparative examples 2 to 4 were heated to 40 ℃ and their pH was adjusted to an optimum value. And (3) after the test board is subjected to oil removal, microetching, washing and cold air drying treatment, soaking the test board in the soldering flux protecting solution for 90 seconds, taking out the test board, washing the test board by pure water, and drying the test board by cold air to finish the organic soldering flux protecting film manufacturing process. A group of test boards are not printed with SAC305 solder paste, after 4 times of lead-free reflow soldering heat treatment, the SAC305 solder paste is printed, and then 1 time of lead-free reflow soldering treatment is carried out, the discoloration degree of the film layer is observed, and the tin-coating rate is measured. The test results are shown in Table 2. The other set of test panels was exposed to air at room temperature for 168 hours and the film was observed for discoloration. SAC305 solder paste was printed, and after 1 lead-free reflow treatment, the degree of discoloration of the film layer was observed, and the tin-on property was measured. The test results are shown in Table 3.
TABLE 2 Heat resistance and weldability test results
Group color change and tin coating rate
Example 2 No discoloration of 99%
Example 3 No discoloration of 95%
Example 4 No discoloration of 97%
Comparative example 2 color change 22%
Comparative example 3 discoloration 15%
Comparative example 4 discoloration of 48%
As can be seen from Table 2, the examples of the solder mask prepared by using the copper surface selective organic solder mask provided by the present invention have excellent heat resistance and solderability after being subjected to a plurality of thermal shocks. The comparative example does not contain an organic phosphine compound or iron nitrilotriacetate, or when the content is not reasonable, the heat resistance and weldability of the film layer are deteriorated.
TABLE 3 Oxidation resistance and weldability test results
Group color change and tin coating rate
Example 2 No discoloration 100%
Example 3 No discoloration of 98%
Example 4 No discoloration 97%
Comparative example 2 discoloration 72%
Comparative example 3 discoloration 59%
Comparative example 4 discoloration 77%
As is clear from Table 3, the solder resist obtained by using the copper surface selective organic solder resist of the present invention did not discolor in the examples and was excellent in solderability after being exposed to air at room temperature for 168 hours. The comparative example did not contain an organic phosphine compound or iron nitrilotriacetate, or when the content was not reasonable, the oxidation resistance and weldability of the film layer were decreased.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art will recognize that changes may be made to the embodiments described above without departing from the spirit and scope of the invention. Therefore, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the technical spirit of the present invention are covered by the claims of the present invention. .
Claims (6)
1. A selective organic solderability preservative for copper surfaces comprises ferric nitrilotriacetate, an organophosphine compound, an imidazole derivative and an organic acid.
2. The selective organic solderability preservative of claim 1, wherein the iron nitrilotriacetate is present in an amount of 0.01 to 0.5% by mass, the organophosphinic compound is present in an amount of 0.01 to 1% by mass, the imidazole derivative is present in an amount of 0.05 to 1.5% by mass, and the organic acid is present in an amount of 5 to 30% by mass.
3. The copper surface-selective organic solderability preservative of claim 1 or 2, comprising iron nitrilotriacetate.
4. The copper-surface selective organic flux-shielding material according to claim 1 or 2, wherein the organophosphinic compound is selected from the group consisting of aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, polyaminopolyether methylenephosphonic acid, bis-1, 6-hexylenediaminepentamethylenephosphonic acid, and at least one of the sodium and potassium salts corresponding to the above organophosphinic acids.
5. A method for using a copper surface selective organic solderability preservative, wherein when the surface of a PCB board has copper and gold coexisting, the PCB board is dipped in the copper surface selective organic solderability preservative, a solderability preservative film is formed on the copper surface, and a solderability preservative film is not formed on the gold surface.
6. Wherein the copper surface-selective organic solderability preservative is the copper surface-selective organic solderability preservative of any one of claims 1 to 3.
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| CN202210701011.7A CN114833491B (en) | 2022-06-21 | Copper surface selective organic soldering flux and use method thereof |
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| CN202210701011.7A CN114833491B (en) | 2022-06-21 | Copper surface selective organic soldering flux and use method thereof |
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| CN117655583A (en) * | 2024-01-31 | 2024-03-08 | 梅州鼎泰电路板有限公司 | High-temperature-resistant organic solder resist, organic solder mask layer of PCB and preparation process of organic solder mask layer |
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