CN118002982A - Organic solderability preservative and preparation method and application thereof - Google Patents
Organic solderability preservative and preparation method and application thereof Download PDFInfo
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- CN118002982A CN118002982A CN202410133726.6A CN202410133726A CN118002982A CN 118002982 A CN118002982 A CN 118002982A CN 202410133726 A CN202410133726 A CN 202410133726A CN 118002982 A CN118002982 A CN 118002982A
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- benzimidazole
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- imidazole
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- difluorophenyl
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- 239000003755 preservative agent Substances 0.000 title claims abstract description 66
- 230000002335 preservative effect Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 6
- -1 naphthyl alkyl benzimidazole derivative Chemical class 0.000 claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 30
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 238000004381 surface treatment Methods 0.000 claims abstract description 6
- 239000003223 protective agent Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 26
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 18
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 8
- UJIFCJAKLHISBB-UHFFFAOYSA-N 2-(2-naphthalen-2-ylethyl)-1H-benzimidazole Chemical compound C1=C(C=CC2=CC=CC=C12)CCC=1NC2=C(N1)C=CC=C2 UJIFCJAKLHISBB-UHFFFAOYSA-N 0.000 claims description 8
- 229940074391 gallic acid Drugs 0.000 claims description 8
- 235000004515 gallic acid Nutrition 0.000 claims description 8
- 239000000176 sodium gluconate Substances 0.000 claims description 8
- 235000012207 sodium gluconate Nutrition 0.000 claims description 8
- 229940005574 sodium gluconate Drugs 0.000 claims description 8
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 6
- 230000007928 solubilization Effects 0.000 claims description 6
- 238000005063 solubilization Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 3
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 3
- 229940095100 fulvic acid Drugs 0.000 claims description 3
- 239000002509 fulvic acid Substances 0.000 claims description 3
- RADOGEDDAUTJDB-UHFFFAOYSA-N 2,5-bis(4-fluorophenyl)-1H-imidazole Chemical compound C1=CC(F)=CC=C1C1=CN=C(C=2C=CC(F)=CC=2)N1 RADOGEDDAUTJDB-UHFFFAOYSA-N 0.000 claims description 2
- SHZONHQNGMUIER-UHFFFAOYSA-N 2-(2-naphthalen-1-ylethyl)-1h-benzimidazole Chemical compound C1=CC=C2NC(CCC=3C4=CC=CC=C4C=CC=3)=NC2=C1 SHZONHQNGMUIER-UHFFFAOYSA-N 0.000 claims description 2
- JPPVXZHNQCTVAI-UHFFFAOYSA-N 2-(5-naphthalen-1-ylpentyl)-1H-benzimidazole Chemical compound C1(=CC=CC2=CC=CC=C12)CCCCCC=1NC2=C(N1)C=CC=C2 JPPVXZHNQCTVAI-UHFFFAOYSA-N 0.000 claims description 2
- DZXOCOOLQDKOEU-UHFFFAOYSA-N 2-(5-naphthalen-2-ylpentyl)-1H-benzimidazole Chemical compound C1=C(C=CC2=CC=CC=C12)CCCCCC=1NC2=C(N1)C=CC=C2 DZXOCOOLQDKOEU-UHFFFAOYSA-N 0.000 claims description 2
- VJRPHCDQRJAVSR-UHFFFAOYSA-N 2-(naphthalen-1-ylmethyl)-1h-benzimidazole Chemical compound C1=CC=C2C(CC=3NC4=CC=CC=C4N=3)=CC=CC2=C1 VJRPHCDQRJAVSR-UHFFFAOYSA-N 0.000 claims description 2
- TXUQJAOFDMFKDK-UHFFFAOYSA-N 2-(naphthalen-2-ylmethyl)-1h-benzimidazole Chemical group C1=CC=CC2=CC(CC=3NC4=CC=CC=C4N=3)=CC=C21 TXUQJAOFDMFKDK-UHFFFAOYSA-N 0.000 claims description 2
- DDOCTENLZSXLGX-UHFFFAOYSA-N C1=CC=C2C(=C1)C=CC=C2CCCCCCCC3=NC4=CC=CC=C4N3 Chemical compound C1=CC=C2C(=C1)C=CC=C2CCCCCCCC3=NC4=CC=CC=C4N3 DDOCTENLZSXLGX-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 3
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical class N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 claims 1
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000005476 soldering Methods 0.000 abstract description 20
- 150000003839 salts Chemical class 0.000 abstract description 12
- 239000007921 spray Substances 0.000 abstract description 11
- 238000002474 experimental method Methods 0.000 abstract description 8
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 230000004907 flux Effects 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical group 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001556 benzimidazoles Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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 1
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000004841 phenylimidazoles Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses an organic solderability preservative and a preparation method and application thereof, and relates to the technical field of Printed Circuit Board (PCB) surface treatment. The invention relates to an organic solderability preservative, which comprises the following components: 2.0-4.0g/L of main film forming agent, 150-350g/L of organic solvent, 0.05-1.0g/L of copper ion and 1.7-5.0g/L of auxiliary agent, wherein the main film forming agent comprises naphthyl alkyl benzimidazole derivative and fluoro diphenyl imidazole derivative, and the content of the fluoro diphenyl imidazole derivative is 0.5-1.5 g/L. The OSP film has excellent weldability, bright and full soldering tin, and electrochemical experiments show that the corrosion inhibition rate of the OSP film reaches over 96 percent, and salt spray experiments also show that the OSP film can resist 50 hours without corrosion in salt spray.
Description
Technical Field
The invention relates to the technical field of surface treatment of Printed Circuit Boards (PCBs), in particular to an organic solderability preservative and a preparation method and application thereof.
Background
Organic Solderability Preservative (OSP) is widely used in the surface treatment technology of Printed Circuit Boards (PCBs) due to its advantages such as heat resistance, oxidation resistance, solderability, etc. The Organic Solderability Preservative (OSP) forms a layer of hydrophobic compact metal-organic protective film (OSP film) on the copper surface mainly through coordination and complexation reaction of a main film forming agent and copper ions and self-assembly of Van der Waals force and hydrogen bond among molecules of the main film forming agent, so that the copper surface is prevented from being corroded by oxidation (oxidation resistance), can resist multiple high-temperature reflow soldering without discoloration and decomposition (heat resistance) and can be quickly dissolved by soldering flux, and the copper surface can keep good solderability (solderability). The most typical OSP main film forming agents widely used in the prior art are halogen substituted phenylbenzimidazole derivatives, such as 2- (2, 4-dichlorobenzyl) benzimidazole, 2-p-chlorobenzyl benzimidazole, 2- (3, 4-dichlorobenzyl) benzimidazole and the like, which are further improved in heat resistance of the OSP film by introducing a plurality of halogen substituents such as chlorine, bromine and the like on a benzene ring. However, regulations such as RoHS place clear restrictions on both chlorine and bromine halogens, i.e., cl < 1000ppm, br < 1000ppm, and Cl+Br < 1500ppm. Moreover, when the OSP film containing chlorine and bromine is soldered on tin, halogen in the OSP film is dissolved in the soldering flux, so that the development and use of the halogen-free soldering flux are not significant. It can be seen that such primary film formers have failed to meet the increasingly stringent environmental requirements, and their heat resistance, oxidation resistance and weldability have yet to be further improved to meet industry demands. At present, in order to meet the related requirements, excessive film forming accelerator is usually added, so that an OSP system is unstable and even is precipitated, and the heat resistance, the oxidation resistance and the corrosion resistance are poor.
The prior art discloses a high temperature resistant organic solder resist and an application method thereof, wherein the solder resist comprises the following raw materials: 0.1-10wt% of compound imidazole derivative, 5-35wt% of organic acidic substance, 0.05-1.5wt% of water-soluble metal salt, 10-20wt% of buffer and 100% of deionized water, wherein the compound imidazole derivative is a mixture of phenylimidazole derivative and benzimidazole derivative. However, the high temperature resistant organic solder flux only has high temperature resistance and does not improve the corrosion resistance of the OSP film.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of unstable OSP system and even precipitation and poor corrosion resistance of an OSP film existing in the conventional organic solderable protective agent (OSP), and provides the organic solderable protective agent, which not only solves the problems of easy precipitation of the main film forming agent and unstable OSP solution, but also improves the heat resistance, oxidation resistance and corrosion resistance of the OSP film by compounding the main film forming agent.
Another object of the present invention is to provide a method for preparing an organic solderability preservative.
It is a further object of the present invention to provide the use of an organic solderable protective agent in the surface treatment of printed circuit boards.
The above object of the present invention is achieved by the following technical scheme:
An organic solderability preservative comprising the following components:
2.0 to 4.0g/L of main film forming agent, 150 to 350g/L of organic solvent, 0.05 to 1.0g/L of copper ion and 1.7 to 5.0g/L of auxiliary agent,
Wherein the main film forming agent comprises a naphthyl alkyl benzimidazole derivative and a fluoro diphenyl imidazole derivative, the content of the fluoro diphenyl imidazole derivative is 0.5g/L-1.5g/L,
The structural formula of the naphthyl alkyl benzimidazole derivative is as follows:
wherein n=1-8, m=1-8;
the structural formula of the fluoro diphenyl imidazole derivative is as follows:
Wherein R 1 and R 2 are F, a=0-2, b=0-2, and a and b are different 0.
The OSP film formed by the organic solderability preservative has excellent heat resistance, oxidation resistance and corrosion resistance, can resist reflow soldering for more than 7 times and basically does not change color, and electrochemical experiments show that the corrosion inhibition rate of the OSP film reaches more than 98 percent and salt spray experiments also show that the OSP film can resist 54h of non-corrosion in salt spray. According to the method, by compounding two main film forming agents, on one hand, naphthyl is introduced to greatly improve the decomposition temperature of the OSP film, on the other hand, F atoms are introduced to the benzene ring by the fluoro diphenyl imidazole derivative, and due to the fact that the polarity of a fluorocarbon bond is small, the bond length is short, the van der Waals force among molecules is strong, the hydrophobicity and compactness of the OSP film are enhanced, and therefore the heat resistance, the oxidation resistance and the corrosion resistance of the OSP film are improved.
The OSP solution has good stability and is not easy to separate out. The combination of the naphthyl alkyl benzimidazole derivative with good solubility in the OSP solution and the fluoro diphenyl imidazole derivative with poor solubility in the OSP solution can give consideration to the performance of the OSP film and solve the problem that the OSP solution is easy to separate out. The solvent of the OSP solution is typically water.
The organic soldering protecting agent does not contain two halogens of chlorine and bromine, meets the halogen-free requirement of the printed circuit board industry, overcomes the negative environmental benefits of the two halogens of chlorine and bromine, meets the environmental protection requirement of RoHS, and has environmental protection benefits.
In addition, the organic soldering flux of the patent does not need to add zinc salt to improve heat resistance, avoids pollution of zinc ions to water, and is more green and environment-friendly. In the organic solderability preservative, the main film forming agent is the compound of the naphthyl alkyl benzimidazole derivative and the fluoro diphenyl imidazole derivative, so that the problems that the main film forming agent is easy to separate out and an OSP solution is unstable are solved, and the heat resistance, the oxidation resistance and the corrosion resistance of the OSP film are improved.
In a specific embodiment, the main film forming agent of the present invention may be, for example:
1.8g/L of naphthyl alkyl benzimidazole derivative and 1.2g/L of fluoro diphenyl imidazole derivative;
Or 1.5g/L of naphthylalkylbenzimidazole derivative and 1.5g/L of fluorodiphenylimidazole derivative;
or the content of the naphthyl alkyl benzimidazole derivative is 2.5g/L, and the content of the fluoro diphenyl imidazole derivative is 0.5g/L;
or the content of the naphthyl alkyl benzimidazole derivative is 2.5g/L, and the content of the fluoro diphenyl imidazole derivative is 1.5g/L;
or 1.5g/L of naphthylalkylbenzimidazole derivative and 0.5g/L of fluorodiphenylimidazole derivative.
Preferably, the mass ratio of the naphthyl alkyl benzimidazole derivative to the fluoro diphenyl imidazole derivative in the main film forming agent is 1-2.5:1. for example, 1:1, 1.5:1, 2:1, 2.5:1, etc.
In a specific embodiment, the naphthylalkylbenzimidazole derivative of the present invention is 2- (2-naphthylmethyl) -1H-benzimidazole, 2- (2-naphthylethyl) -1H-benzimidazole, 2- (2-naphthylpentyl) -1H-benzimidazole, 2- (2-naphthyloctyl) -1H-benzimidazole, 2- (2-naphthylheptyl) -1H-benzimidazole, 2- (1-naphthylmethyl) -1H-benzimidazole, 2- (1-naphthylethyl) -1H-benzimidazole, 2- (1-naphthylpentyl) -1H-benzimidazole, 2- (1-naphthyloctyl) -1H-benzimidazole, 2- (1-naphthylheptyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylmethyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylethyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylpentyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthyloctyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylheptyl) -1H-benzimidazole, one or more of 5, 6-difluoro-2- (2-naphthylethyl) -1H-benzimidazole, 5, 6-difluoro-2- (2-naphthylpentyl) -1H-benzimidazole, 5, 6-difluoro-2- (2-naphthyloctyl) -1H-benzimidazole and 5, 6-difluoro-2- (2-naphthylheptyl) -1H-benzimidazole.
In particular embodiments, the fluorodiphenyl imidazole derivatives of the present invention include one or more of 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole, 2- (4-fluorophenyl) -4- (4-fluorophenyl) imidazole, 2- (2, 4-difluorophenyl) -4- (2, 4-difluorophenyl) imidazole, 2-phenyl-4- (2, 4-difluorophenyl) imidazole, 2- (3-fluorophenyl) -4- (3, 5-difluorophenyl) imidazole, 2- (3-fluorophenyl) -4- (3-fluorophenyl) imidazole, 2- (3, 5-difluorophenyl) -4- (3, 5-difluorophenyl) imidazole, 2-phenyl-4- (2, 3-difluorophenyl) imidazole.
Preferably, the auxiliary agent comprises a film forming accelerator and a solubilization corrosion inhibitor, wherein the film forming accelerator is one or more of n-heptanoic acid, gallic acid, 3, 4-dihydroxybenzoic acid and fulvic acid.
The auxiliary agent contains phenolic hydroxyl, hydroxyl or carboxyl, promotes the self-assembly film forming speed of the OSP film through the synergistic effect of the auxiliary agent, strengthens the hydrogen bonding effect so as to make the system more stable, can further improve the stability of an OSP solution, and further improves the oxidation resistance and corrosion resistance of the OSP film.
And through the synergistic effect of the auxiliary agent and the main film forming agent, the self-assembled film forming speed of the OSP film is promoted, and the oxidation resistance and corrosion resistance of the OSP film are further improved. This is because gallic acid, 3, 4-dihydroxybenzoic acid, and fulvic acid in the auxiliary agent have good oxidation resistance.
Preferably, the film forming promoter content in the auxiliary agent is 0.5-2.0g/L, for example, 0.5g/L, 1.0g/L, 1.5g/L, 2.0g/L, etc.
Further preferably, the film forming promoter is n-heptanoic acid and gallic acid, and the content of n-heptanoic acid is not more than 1.0g/L, for example, may be 0.25g/L, 0.7g/L, or 1.0g/L.
Preferably, the content of the solubilization corrosion inhibitor in the auxiliary is 1.2-3.0g/L, for example, 1.2g/L, 1.5g/L, 1.8g/L, 2.2g/L, 2.5g/L, 2.8g/L or 3.0g/L, etc.
In specific embodiments, the solubilization corrosion inhibitor comprises one or more of sodium gluconate, rhamnolipid and dimethylaminoethyl methacrylate quaternary ammonium salt.
The addition of the auxiliary agent, especially rhamnolipid, is used as an environment-friendly biosurfactant, has metal chelating capacity and has obvious solubilization effect on polycyclic aromatic hydrocarbon.
Preferably, the content of sodium gluconate, rhamnolipid and dimethylaminoethyl methacrylate quaternary ammonium salt is 1.0-1.8g/L, 0.1-0.6g/L and 0.1-0.6g/L respectively.
The sodium gluconate, the rhamnolipid and the dimethylaminoethyl methacrylate quaternary ammonium salt are compounded together to have good corrosion inhibition, and the preferable mass ratio of the sodium gluconate to the rhamnolipid to the dimethylaminoethyl methacrylate quaternary ammonium is 3:1:1.
Preferably, the organic solvent is formic acid and acetic acid, wherein the mass ratio of formic acid to acetic acid is (0.1-1): 1, more preferably, the mass ratio of formic acid to acetic acid is 1:9 to 1:4.
In a specific embodiment, the copper ion of the present invention may be one or more of copper chloride, copper formate, and copper acetate.
In a specific embodiment, the pH adjuster of the present invention may be aqueous ammonia.
Preferably, the pH of the organic solderable protective agent is 2.5-4.0, which may be, for example, 2.5, 3.0, 3.5, 4.0, etc., more preferably, the pH of the organic solderable protective agent is 2.8-3.6.
The invention also specifically protects a preparation method of the organic solderability preservative, which comprises the following steps:
dissolving a main film forming agent in an organic solvent, adding an auxiliary agent, and uniformly stirring to obtain a solution A;
Then copper ions are dissolved in water to form a solution B;
Pouring the solution A into the solution B while stirring, continuously stirring uniformly, and finally adding the pH regulator and water.
The invention also specifically protects application of the organic solderability preservative in surface treatment of the printed circuit board.
However, without limitation, the disclosed fluorochemical benzimidazole derivatives of the present invention may also be used as antioxidants in the oxidation resistance of copper or copper alloys and thus may be used in other industries.
The application method of the fluorine-containing benzimidazole derivative organic soldering flux can be specifically referred as follows:
Microetching the PCB or copper plate in microetching liquid for 30-60S, washing with two deionized water, drying, soaking in organic soldering protecting agent (OSP) heated to 40-45deg.C for 40-120S, washing with water, and oven drying.
Compared with the prior art, the invention has the beneficial effects that:
According to the organic weldable protective agent, the naphthyl alkyl benzimidazole derivative with good solubility and the phenyl imidazole with poor solubility are compounded, so that the performance of an OSP film can be considered, the problem that an OSP solution is easy to separate out is solved, the stability of the OSP solution is further improved, on one hand, the naphthyl is introduced to greatly improve the decomposition temperature of the OSP film through compounding the two main film forming agents, on the other hand, the difluoro phenyl imidazole derivative introduces F atoms on a benzene ring, and the polarity of a fluorocarbon bond is smaller, the bond length is shorter, the Van der Waals force among molecules is stronger, and the hydrophobicity and compactness of the OSP film are enhanced, so that the heat resistance, the oxidation resistance and the corrosion resistance of the OSP film are improved.
The OSP film has excellent weldability, and electrochemical experiments show that the corrosion inhibition rate of the OSP film reaches over 96 percent, and salt spray experiments also show that the OSP film can resist 50 hours without corrosion in salt spray.
Drawings
FIG. 1 is a photograph showing the OSP film copper sheets of examples 1-11 subjected to 0-7 reflow soldering
FIG. 2 is a photograph showing comparative examples 1-5 subjected to 0-4 reflow solders.
FIG. 3 shows contact angles of examples 1-11.
Fig. 4 is the contact angle of comparative examples 1-5.
Fig. 5 is a graph of uniformity measurements of a film.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
An organic solderability preservative comprising the following components:
1.8g/L of 2- (2-naphthylethyl) -1H-benzimidazole, 1.2g/L of 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole, 50g/L of formic acid, 200g/L of acetic acid, 1.0g/L of cupric chloride, 0.7g/L of n-heptanoic acid, 0.8g/L of gallic acid, 1.5g/L of sodium gluconate, 0.5g/L of rhamnolipid and 0.5g/L of dimethylaminoethyl methacrylate quaternary ammonium salt and the balance of water.
The pH of the organic solderable protective agent was 3.0.
The preparation method of the organic solderability preservative of example 1 is as follows:
Dissolving 2- (2-naphthylethyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole in organic solvents of formic acid and acetic acid, adding an auxiliary agent, and uniformly stirring to obtain A; dissolving copper chloride in water to obtain B; slowly pouring the A into the B while stirring, and continuously stirring uniformly. Finally, ammonia water is used for adjusting the pH value to 3.0.
The application method of the organic solderability preservative of example 1 can be referred to as follows:
And (3) microetching the copper plate in microetching liquid for 60s, washing and drying the copper plate by two times of deionized water, immersing the copper plate in an organic soldering flux (OSP) heated to 45 ℃ for 90s, washing and drying the copper plate.
Example 2
An organic solderability preservative substantially the same as in example 1 except that:
The content of the main film forming agent 2- (2-naphthylethyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole of the organic welding-assistant protective agent (OSP) is 1.5g/L.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 1 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 1 can be referred to in example 1.
Example 3
An organic solderability preservative substantially the same as in example 1 except that:
the main film forming agents of the organic welding-assisting protective agent (OSP) are 2.5g/L and 0.5g/L respectively, namely 2- (2-naphthylethyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 3 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 3 can be referred to in example 1.
Example 4
An organic solderability preservative substantially the same as in example 1 except that:
The main film forming agents of the organic welding-assisting protective agent (OSP) are 2.5g/L and 1.5g/L respectively, namely 2- (2-naphthylethyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 4 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 4 can be referred to in example 1.
Example 5
An organic solderability preservative substantially the same as in example 1 except that:
The main film forming agents of the organic welding-assisting protective agent (OSP) are 1.5g/L and 0.5g/L respectively, namely 2- (2-naphthylethyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 5 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 5 can be referred to in example 1.
Example 6
An organic solderability preservative substantially the same as in example 1 except that:
The content of the auxiliary agent is 1.7g/L, wherein 0.25g/L of n-heptanoic acid, 0.25g/L of gallic acid, 1.0g/L of sodium gluconate, 0.1g/L of rhamnolipid and 0.1g/L of dimethylaminoethyl methacrylate quaternary ammonium salt.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 6 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 6 can be referred to in example 1.
Example 7
An organic solderability preservative substantially the same as in example 1 except that:
The content of the auxiliary agent is 5.0g/L, wherein 1.0g/L of n-heptanoic acid, 1.0g/L of gallic acid, 1.8g/L of sodium gluconate, 0.6g/L of rhamnolipid and 0.6g/L of dimethylaminoethyl methacrylate quaternary ammonium salt.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 7 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 7 can be referred to in example 1.
Example 8
An organic solderability preservative substantially the same as in example 1 except that:
the organic solvent of formic acid and acetic acid is 0.1:1.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 8 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 8 can be referred to in example 1.
Example 9
An organic solderability preservative substantially the same as in example 1 except that:
the mass ratio of the organic solvent formic acid to the acetic acid is 1:1.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 9 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 9 can be referred to in example 1.
Example 10
An organic solderability preservative substantially the same as in example 1 except that:
The main film forming agent is 1.8g/L of 5-fluoro-2- (2-amyl naphthyl) -1H-benzimidazole and 1.2g/L of 2- (3-fluorophenyl) -4- (3-fluorophenyl) imidazole.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 10 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 10 can be referred to in example 1.
Example 11
An organic solderability preservative substantially the same as in example 1 except that:
The main film forming agent is 1.8g/L of 2- (1-heptyl naphthyl) -1H-benzimidazole and 1.2g/L of 2- (2, 4-fluorophenyl) imidazole.
The pH of the organic solderable protective agent was 3.0.
The organic solderability preservative of example 11 was prepared in the same manner as in example 1.
The application method of the organic solderability preservative of example 11 can be referred to in example 1.
Comparative example 1
An organic solderability preservative substantially the same as in example 1 except that:
The content of the main film forming agents 2- (2-ethylnaphthyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole of the organic soldering protecting agent (OSP) is 0.0g/L.
The organic solderability preservative of comparative example 1 was prepared in the same manner as in example 1.
The method of applying the organic solderability preservative of comparative example 1 can be referred to example 1.
Comparative example 2
An organic solderability preservative substantially the same as in example 1 except that:
the main film forming agents of the organic welding-assisting protective agent (OSP) are 3.0g/L and 0.0g/L respectively, namely 2- (2-ethyl naphthyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The organic solderability preservative of comparative example 2 was prepared in the same manner as in example 1.
The method of applying the organic solderability preservative of comparative example 2 can be referred to example 1.
Comparative example 3
An organic solderability preservative substantially the same as in example 1 except that:
the main film forming agents of the organic welding-assisting protective agent (OSP) are respectively 0.0g/L and 3.0g/L of 2- (2-ethyl naphthyl) -1H-benzimidazole and 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The organic solderability preservative of comparative example 3 was prepared in the same manner as in example 1.
The method of applying the organic solderability preservative of comparative example 3 can be referred to example 1.
Comparative example 4
An organic solderability preservative substantially the same as in example 1 except that:
1.8g/L of 2- (2-ethylnaphthyl) -1H-benzimidazole and 0.4g/L of 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The organic solderability preservative of comparative example 4 was prepared in the same manner as in example 1.
The method of applying the organic solderability preservative of comparative example 4 can be referred to example 1.
Comparative example 5
An organic solderability preservative substantially the same as in example 1 except that:
1.8g/L of 2- (2-ethylnaphthyl) -1H-benzimidazole and 2.2g/L of 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole.
The organic solderability preservative of comparative example 5 was prepared in the same manner as in example 1.
The method of applying the organic solderability preservative of comparative example 5 can be referred to example 1.
Result detection
Performance evaluation was performed on the OSP films of the above examples and comparative examples.
The specific performance evaluation method comprises the following steps:
The test method of the stability of the OSP liquid comprises the following steps: after the OSP solution is left for one week at room temperature, the clear or turbid state of the OSP solution is observed, whether solid precipitation exists or not is observed, if precipitation exists or the solution becomes more turbid, the solution is unstable, and if the solution state is not changed, the solution is stable.
2. The precipitation crystallization test method comprises the following steps: visual inspection was performed.
Osp film thickness and uniformity determination method:
And (3) placing the 4 x 4cm copper clad laminate in 50mL of 5% hydrochloric acid, shaking for 3-5min to dissolve the film completely, measuring an absorbance value at 278nm, and calculating the OSP film thickness according to a film thickness measured by the FIB-SEM and a film thickness calculation formula delta=0.41A established by the corresponding absorbance. The uniformity of the film was observed simultaneously during the focused ion beam scanning electron microscope FIB-SEM test. The results of the uniformity and non-uniformity of the film thickness are shown in FIG. 5.
4. Contact angle measurement method:
Contact angle of copper sheet of OSP film was measured and film-forming water washing was visually examined.
5. The heat resistance measurement method comprises:
the temperature change curve of the reflow soldering process is 170-193 ℃ for 1min;193-242 ℃ for 1min;242-277 ℃,2min,277-239 ℃ for 1min;239-225 ℃ for 1min.
6. Salt spray tolerance determination method:
according to the standard GB/T10125-1997 neutral smoke test method, an OSP film copper plate is placed in a salt spray machine, and a 3.5% sodium chloride solution salt spray is continuously sprayed in a 35 ℃ environment, so that the corrosion condition of the copper plate is observed.
7. The method for measuring the electrochemical corrosion inhibition rate comprises the following steps:
(1) A three-electrode system is adopted, an OSP copper plate is used as a Working Electrode (WE), a platinum electrode is used as an auxiliary electrode (CE), a Saturated Calomel Electrode (SCE) is used as a Reference Electrode (RE), and an electrolyte solution is 3.5wt% NaCl solution. The corrosion current is determined by measuring the polarization curve, and the corrosion inhibition rate is calculated.
8. Method for measuring weldability:
The tin furnace is heated to 260 ℃, the OSP film copper foil subjected to 3 times of reflow soldering is immersed in the soldering flux for 10s, taken out and placed for about 1min, immersed in molten FX-306 lead-free solder for 10s, and the tin plating condition of the copper surface is checked.
The specific results are shown in table 1 below:
TABLE 1
Wherein FIG. 1 is a photograph showing the OSP film copper sheets of examples 1-11 subjected to 0-7 reflow soldering.
FIG. 2 is a photograph showing comparative examples 1-5 subjected to 0-4 reflow solders.
FIG. 3 is a graph showing the contact angle test results of examples 1 to 11.
Fig. 4 is a graph of contact angle test results of comparative examples 1 to 5.
Fig. 5 is a graph of uniformity measurements of a film.
As can be seen from the above Table 1 and FIG. 1, the OSP film formed by applying the organic solderability preservative of the invention has excellent solderability, and after 7 times of reflow soldering, the soldering tin is bright and full, and can resist more than 4-5 times, even 7 times of reflow soldering basically does not change color.
As can be seen from the table 1, the OSP liquid formed by the application of the organic weldable protective agent has good stability and is not easy to separate out, by compounding the two main film forming agents, on one hand, the naphthalene group is introduced to greatly improve the decomposition temperature of the OSP film, on the other hand, the F atom is introduced on the benzene ring, the polarity of the fluorocarbon bond is smaller, the bond length is shorter, the intermolecular van der Waals force is stronger, the hydrophobicity and compactness of the OSP film are enhanced, and compared with the graph in FIG. 3 and FIG. 4, the OSP film has a larger water contact angle, so that the heat resistance and the oxidation resistance and the corrosion resistance of the OSP film are improved, the electrochemical experiment shows that the corrosion inhibition rate of the OSP film reaches over 96 percent, and the salt spray experiment also shows that the OSP film can resist 50h non-corrosion in salt spray.
The results of examples 10 and 11 show that equivalent technical effects can be achieved by compounding other naphthylalkyl benzimidazole derivatives and fluorodiphenyl imidazole derivatives within the scope of the present invention.
Of these, only one of the naphthylalkylbenzimidazole derivatives and fluorodiphenylimidazole derivatives was used in comparative examples 2 and 3, and it was apparent that the corresponding technical effects could not be achieved, and both the hydrophobicity and the corrosion resistance were remarkably lowered.
In comparative examples 4 and 5, the amount of the related fluorodiphenyl imidazole derivative was not within the scope of the present invention, and it was apparent that the corresponding technical effects could not be achieved, and both the hydrophobicity and the corrosion resistance were remarkably reduced.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. An organic solderability preservative, which is characterized by comprising the following components:
2.0 to 4.0g/L of main film forming agent, 150 to 350g/L of organic solvent, 0.05 to 1.0g/L of copper ion and 1.7 to 5.0g/L of auxiliary agent,
Wherein the main film forming agent comprises a naphthyl alkyl benzimidazole derivative and a fluoro diphenyl imidazole derivative, the content of the fluoro diphenyl imidazole derivative is 0.5g/L-1.5g/L,
The structural formula of the naphthyl alkyl benzimidazole derivative is as follows:
wherein n=1-8, m=1-8;
the structural formula of the fluoro diphenyl imidazole derivative is as follows:
Wherein R 1 and R 2 are F, a=0-2, b=0-2, and a and b are different 0.
2. The organic solderable protective agent of claim 1 wherein the mass ratio of naphthyl alkyl benzimidazole derivative to fluorodiphenyl imidazole derivative in the primary film former is 1-2.5:1.
3. The organic solderable protective agent according to claim 1, wherein the naphthylalkyl benzimidazole derivative is 2- (2-naphthylmethyl) -1H-benzimidazole, 2- (2-naphthylethyl) -1H-benzimidazole, 2- (2-naphthylpentyl) -1H-benzimidazole, 2- (2-naphthyloctyl) -1H-benzimidazole, 2- (2-naphthylheptyl) -1H-benzimidazole, 2- (1-naphthylmethyl) -1H-benzimidazole, 2- (1-naphthylethyl) -1H-benzimidazole, 2- (1-naphthylpentyl) -1H-benzimidazole, 2- (1-naphthyloctyl) -1H-benzimidazole, 2- (1-naphthylheptyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylmethyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylethyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylpentyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthyloctyl) -1H-benzimidazole, 5-fluoro-2- (2-naphthylheptyl) -1H-benzimidazole, one or more of 5, 6-difluoro-2- (2-naphthylmethyl) -1H-benzimidazole, 5, 6-difluoro-2- (2-naphthylethyl) -1H-benzimidazole, 5, 6-difluoro-2- (2-naphthylpentyl) -1H-benzimidazole, 5, 6-difluoro-2- (2-naphthyloctyl) -1H-benzimidazole, 5, 6-difluoro-2- (2-naphthylheptyl) -1H-benzimidazole.
4. The organic solderable protective agent according to claim 1, wherein the fluorinated diphenyl imidazole derivative is one or more of 2- (4-fluorophenyl) -4- (2, 4-difluorophenyl) imidazole, 2- (4-fluorophenyl) -4- (4-fluorophenyl) imidazole, 2- (2, 4-difluorophenyl) -4- (2, 4-difluorophenyl) imidazole, 2-phenyl-4- (2, 4-difluorophenyl) imidazole, 2- (3-fluorophenyl) -4- (3, 5-difluorophenyl) imidazole, 2- (3-fluorophenyl) -4- (3-fluorophenyl) imidazole, 2- (3, 5-difluorophenyl) -4- (3, 5-difluorophenyl) imidazole, 2-phenyl-4- (2, 3-difluorophenyl) imidazole.
5. The organic solderability preservative of claim 1 wherein the adjuvant comprises a film formation promoter and a solubilization corrosion inhibitor, the film formation promoter being one or more of n-heptanoic acid, gallic acid, 3, 4-dihydroxybenzoic acid, and fulvic acid.
6. The organic solderability preservative of claim 5 wherein the film formation promoter is n-heptanoic acid and gallic acid and the n-heptanoic acid content is less than or equal to 1.0g/L.
7. The organic solderable preservative of claim 5 wherein the solubilization corrosion inhibitor comprises one or more of sodium gluconate, rhamnolipid and dimethylaminoethyl methacrylate quaternary ammonium salt.
8. The organic solderable protective agent according to any one of claims 1 to 7, wherein the pH of the organic solderable protective agent is 2.5 to 4.0.
9. A method of preparing the organic solderable protective agent of any one of claims 1 to 8, comprising the steps of:
dissolving a main film forming agent in an organic solvent, adding an auxiliary agent, and uniformly stirring to obtain a solution A;
Then copper ions are dissolved in water to form a solution B;
Pouring the solution A into the solution B while stirring, continuously stirring uniformly, and finally adding the pH regulator and water.
10. Use of an organic solderable protective agent as defined in any one of claims 1 to 8 in the surface treatment of printed circuit boards.
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