CN116463621B - Browning liquid for high-frequency high-speed circuit board and preparation method thereof - Google Patents
Browning liquid for high-frequency high-speed circuit board and preparation method thereof Download PDFInfo
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- CN116463621B CN116463621B CN202310488289.5A CN202310488289A CN116463621B CN 116463621 B CN116463621 B CN 116463621B CN 202310488289 A CN202310488289 A CN 202310488289A CN 116463621 B CN116463621 B CN 116463621B
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- circuit board
- speed circuit
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- corrosion inhibitor
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- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 230000007797 corrosion Effects 0.000 claims abstract description 59
- 238000005260 corrosion Methods 0.000 claims abstract description 59
- 239000003112 inhibitor Substances 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 21
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 30
- 235000018417 cysteine Nutrition 0.000 claims description 21
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- 229920000570 polyether Polymers 0.000 claims description 20
- 229920002545 silicone oil Polymers 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 13
- 239000012964 benzotriazole Substances 0.000 claims description 13
- ULGGZAVAARQJCS-UHFFFAOYSA-N 11-sulfanylundecan-1-ol Chemical compound OCCCCCCCCCCCS ULGGZAVAARQJCS-UHFFFAOYSA-N 0.000 claims description 12
- XOKHYMSSRGJTKI-UHFFFAOYSA-N 2H-benzotriazole propane Chemical compound CCC.C1=CC2=NNN=C2C=C1 XOKHYMSSRGJTKI-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- ISXHHOJTMQGRHS-UHFFFAOYSA-N 1-[3-(benzotriazol-1-yl)propyl]benzotriazole Chemical compound N1=NC2=CC=CC=C2N1CCCN1C2=CC=CC=C2N=N1 ISXHHOJTMQGRHS-UHFFFAOYSA-N 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052802 copper Inorganic materials 0.000 abstract description 47
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 230000005764 inhibitory process Effects 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- -1 sulfhydryl compound Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- FWQHRZXEQNUCSY-UHFFFAOYSA-N tert-butyl N-[2-(ethoxycarbonylamino)-5-[(4-fluorophenyl)methyl-prop-2-ynylamino]phenyl]carbamate Chemical compound CCOC(=O)NC1=C(C=C(C=C1)N(CC#C)CC2=CC=C(C=C2)F)NC(=O)OC(C)(C)C FWQHRZXEQNUCSY-UHFFFAOYSA-N 0.000 description 4
- 238000006087 Brown hydroboration reaction Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MWYMHZINPCTWSB-UHFFFAOYSA-N dimethylsilyloxy-dimethyl-trimethylsilyloxysilane Chemical class C[SiH](C)O[Si](C)(C)O[Si](C)(C)C MWYMHZINPCTWSB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0315—Oxidising metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a brown oxide liquid for a high-frequency high-speed circuit board and a preparation method thereof, wherein the brown oxide liquid comprises the following components: 80-120g/L of 98wt% concentrated sulfuric acid, 10-20g/L of 30wt% hydrogen peroxide, 8-15g/L of compound corrosion inhibitor, 20-50g/L of silane coupling agent, 40-70g/L of copper sulfate, 5-15g/L of impregnating compound, 5-8g/L of dispersing agent and the balance of deionized water. The brown chemical solution utilizes the combined action of the corrosion inhibitor and the impregnating compound to form lower roughness on the copper surface, and simultaneously forms good binding force between the corrosion inhibition film and the copper surface as well as between the corrosion inhibition film and the resin, thereby solving the problem of reduced binding strength between the copper and the resin caused by reduced roughness of the copper surface, and leading the brown copper plate to have wide application prospect on a high-frequency high-speed circuit board.
Description
Technical Field
The invention belongs to the technical field of circuit board treatment agents, and particularly relates to a brown oxide liquid for a high-frequency high-speed circuit board and a preparation method thereof.
Background
The printed circuit industry has gradually developed from weak to complete industrial chain, and the product has developed from the low end to the middle end and the high end.
With the development of electronic technology, the emerging application fields of 5G communication technology, internet of things, internet of vehicles and the like, high-frequency high-speed signal high-quality transmission becomes a characteristic which is necessary for a new generation of printed circuit boards, and communication PCBs develop towards low roughness, high-density interconnection, high signal integrity (quality of signals on a transmission path) and the like of circuits, so that higher requirements are provided for special materials-copper surface treatment technology for manufacturing printed circuit board electronic circuits. Due to the skin effect, it is known that when the frequency reaches 1GHz, the transmission depth of the signal on the surface of the wire is 2.1mm, and at this time, if the roughness of the surface of the wire is 3 to 5mm, the signal is transmitted in the thickness range of the roughness. Therefore, when the signal reaches a high frequency band above 10GHz, the signal transmission depth is only 0.7mm, and the signal is still transmitted in the range of the roughness thickness. When the signal is transmitted only in a rough thickness range, standing waves and reflection are enhanced, a signal transmission path is lengthened, loss is increased, and the signal is lost or even distorted. Therefore, roughness of the line surface becomes an important factor affecting the high frequency signal integrity. In summary, high-frequency high-speed signal high-quality transmission needs to meet requirements of interlayer bonding force and thermal shock resistance and reduce surface roughness of copper in a multilayer printed circuit board, so that copper surface treatment is already a current research hot spot.
The brown oxidation solution mainly comprises sulfuric acid, hydrogen peroxide and specific organic matters, an organic copper film layer is formed on the copper surface after brown oxidation treatment, wherein the corrosion inhibitor plays a role in controlling the rapid corrosion of the copper surface, and the oxidant oxidizes Cu to form Cu 2 After O, under the combined action of cross-linking agent, plasticizer, corrosion inhibitor and the like, the catalyst reacts with Cu by chemical bonding 2 O forms a rough organic copper oxide layer with honeycomb appearance on the surface of copper; in the lamination process, the organic copper oxide film layer and the resin undergo curing and crosslinking reaction, so that better interface bonding force can be provided.
Chinese patent application No. 201110437314.4 discloses a browning treatment fluid containing sulfhydryl compound, which is used for improving the bonding force between the inner copper surface and a prepreg in the production process of a Printed Circuit Board (PCB) multilayer board. The copper-carrying amount of the browning treatment liquid can be up to 50g/L, black brown precipitation can not be generated in the solution, the reaction activity of the solution can be maintained even under the condition of discontinuous production, and the replacement of a new solution is not needed. In addition, the brown oxide treatment liquid has copper ion concentration of 1-50 g/L, copper surface with uniform honeycomb structure observed by Scanning Electron Microscope (SEM), and peel strength maintained above 4.0lb/in all the time, and qualified thermal shock resistance. Chinese patent application No. 200410026849.2 discloses a browning treatment fluid for improving adhesion between an inner copper surface of a circuit board and a polymeric material, wherein the browning treatment fluid contains sulfuric acid, hydrogen peroxide, halogen ions, water-soluble polymers, corrosion inhibitors such as indoles, triazolylmethanes, 1-substituted benzotriazoles, 4-substituted benzotriazoles or 5-methyl-1-substituted benzotriazoles, or a combination of the above corrosion inhibitor compounds. The above patents all improve the interfacial bonding force between copper and resin, but the roughness of the copper surface is also improved, thereby affecting the integrity of the transmission signal, and the method is not suitable for the browning treatment on a high-frequency high-speed circuit board.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the brown oxide liquid for the high-frequency high-speed circuit board and the preparation method thereof, wherein the brown oxide liquid has low microetching amount, the copper surface treated by the brown oxide liquid has low roughness, and meanwhile, the bonding strength between the copper plate and resin is not influenced, so that the brown oxide liquid has wide application value in the preparation of the 5G high-frequency high-speed circuit board.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the brown oxide liquid for the high-frequency high-speed circuit board comprises the following components:
80-120g/L of 98wt% concentrated sulfuric acid, 10-20g/L of 30wt% hydrogen peroxide, 8-15g/L of compound corrosion inhibitor, 20-50g/L of silane coupling agent, 40-70g/L of copper sulfate, 5-15g/L of impregnating compound, 5-8g/L of dispersing agent and the balance of deionized water.
Preferably, the brown oxide liquid for the high-frequency high-speed circuit board comprises the following components:
90-110g/L of 98wt% concentrated sulfuric acid, 12-16g/L of 30wt% hydrogen peroxide, 10-13g/L of compound corrosion inhibitor, 30-40g/L of silane coupling agent, 50-60g/L of copper sulfate, 8-12g/L of impregnating compound, 6-7g/L of dispersing agent and the balance of deionized water.
Preferably, the preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing cysteine solution, then adding 11-mercapto-undecanol, adding dilute hydrochloric acid to adjust the pH to 3-4, and uniformly stirring to obtain mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol, stirring uniformly to obtain a solution A, adding the solution A into the mixed emulsion obtained in the step (1), adding benzotriazole, and mixing uniformly to obtain the compound corrosion inhibitor.
Preferably, in the step (1), the mass concentration of the cysteine solution is 10-20%, the mass ratio of the cysteine solution to the 11-mercapto-undecanol is 100:10-20, and the mass concentration of the dilute hydrochloric acid is 5%.
Preferably, the temperature of stirring in the step (1) is 70-80 ℃ and the stirring time is 5-8h.
Preferably, the mass concentration of 1, 3-bis (1H-benzotriazole) propane in the solution A in the step (2) is 5-10%; the mass ratio of the mixed emulsion to the solution A to the benzotriazole is 110-120:40-60:5-10.
Preferably, the silane coupling agent is one or more of KH550, KH560 and KH 570.
Preferably, the impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:1-2.
Preferably, the dispersing agent is polyethylene glycol monomethyl ether.
The invention also provides a preparation method of the brown oxide liquid for the high-frequency high-speed circuit board, which comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and a dispersing agent into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the brown oxidation liquid for the high-frequency high-speed circuit board, cysteine and 11-mercapto-undecanol are compounded firstly, and then benzotriazole and 1, 3-bis (1H-benzotriazole) propane are added to form a compound corrosion inhibitor, compared with a single-component corrosion inhibitor, the added 1, 3-bis (1H-benzotriazole) propane has the advantages that as one alkyl group is added in a molecule, the increased alkyl chain can increase the electron cloud density on an N atom, the coordination capacity with copper atoms is enhanced, and when the compound corrosion inhibitor is compounded with benzotriazole, the combined adsorption between the compound corrosion inhibitor and the surface of a substrate can improve the interaction between the corrosion inhibitor and the surface of the substrate, change the interaction force property between adsorption particles and improve the adsorption coverage and the stability of an adsorption film; the compound corrosion inhibitor contains a large number of lone pair electrons of heteroatoms such as N, O, S and large pi bonds of benzene rings, can be combined with empty orbits of copper atoms, is easy to adsorb on the surface of copper, forms coordination bonds, and improves the bonding force between a corrosion inhibition film and a copper interface; meanwhile, the nitrogen azole forms intermolecular hydrogen bonds with amino acids and alkanol corrosion inhibitors through hydrogen atoms contained in molecules, so that the adsorption layer can be more stable, and the formed protective film is more compact, so that the brown copper surface has lower roughness, the loss of signals on a circuit board is reduced, and the method is suitable for brown copper plates on high-frequency and high-speed circuit boards.
(2) The brown oxide liquid for the high-frequency high-speed circuit board provided by the invention has the advantages that the surface of copper is easier to infiltrate by adding the composite impregnating compound, the brown oxide liquid is enabled to be contacted with the surface of copper more uniformly after the surface of copper is infiltrated, the roughness of the surface of copper is further reduced, meanwhile, the good surface wettability is the premise that copper and an organic corrosion inhibition film form close combination, and an ethoxy chain link contained in polyether silicone oil has electronegativity and has electric absorption property, the polarity of molecules is increased, the binding force between the corrosion inhibition film and the organic resin is increased, and the binding strength between a copper plate and the resin caused by the reduction of the roughness is reduced.
(3) The brown oxide liquid for the high-frequency high-speed circuit board provided by the invention utilizes the combined action of the corrosion inhibitor and the impregnating compound to enable the copper surface to form lower roughness, and simultaneously enables the corrosion inhibition film to form good bonding force with the copper surface and the resin, thereby solving the problem of reduced bonding strength between copper and the resin caused by reduced copper surface roughness, and enabling the brown oxide copper plate to have wide application prospect on the high-frequency high-speed circuit board.
Drawings
FIG. 1 is a SEM image of the copper surface after browning of a copper plate using the browning liquid prepared in example 1;
FIG. 2 is an SEM image of the copper surface after browning of a copper plate using the browning liquid prepared in comparative example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The 1, 3-bis (1H-benzotriazole) propane is prepared according to the literature of synthesis of benzotriazole and its alkyl derivatives, liu Qiaoru and the like, andrographon of the university of flat top mountain, 10 months in 2013, and is specifically as follows:
2.62g of benzotriazole is weighed and placed in a three-necked bottle, 250mL of DMF is added for dissolution, 0.58g of LiOH is rapidly added, ultrasonic oscillation is carried out for 5min, 50mL of methanol solution in which 2.02g of 1, 3-dibromopropane is dissolved is dropwise added, stirring and heating reflux are carried out for 12H at 120 ℃, after the reaction is completed, cooling to room temperature, 400mL of distilled water is poured into the reaction mixture to generate floccules, standing is carried out overnight, suction filtration is carried out to obtain a crude product, and then mixed solvent of methanol-water is used for recrystallization to obtain white needle-like crystals, namely 1, 3-bis (1H-benzotriazole) propane.
The polyether silicone oil is purchased from Shandong Xin Runjin chemical industry Co., ltd and is polyether modified heptamethyltrisiloxane; the fatty alcohol polyoxyethylene ether sodium sulfate is purchased from the company of the chemical group of Morse Co., ltd, and the CAS number is 9004-82-4.
Example 1
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
98wt% concentrated sulfuric acid 100g/L, 30wt% hydrogen peroxide 15g/L, compound corrosion inhibitor 12g/L, KH55035g/L, copper sulfate 55g/L, impregnating compound 10g/L, polyethylene glycol monomethyl ether 7g/L and deionized water balance.
The preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing a cysteine solution with the mass concentration of 15%, then adding 15g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 3, uniformly stirring, wherein the stirring temperature is 70 ℃, and the stirring time is 8 hours, so as to obtain a mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol to prepare a solution A with the mass concentration of 5%, then adding 50g of the solution A into 115g of the mixed emulsion in the step (1), adding 7g of benzotriazole, and uniformly mixing to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:1.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Example 2
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
110g/L of 98wt% concentrated sulfuric acid, 15g/L of 30wt% hydrogen peroxide, 10g/L, KH56040g/L of compound corrosion inhibitor, 60g/L of copper sulfate, 12g/L of impregnating compound, 7g/L of polyethylene glycol monomethyl ether and the balance of deionized water.
The preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing a cysteine solution with the mass concentration of 20%, then adding 20g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 3, uniformly stirring, wherein the stirring temperature is 75 ℃, and the stirring time is 7 hours, so as to obtain a mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol to prepare solution A with the mass concentration of 8%, then adding 40g of solution A into 120g of mixed emulsion in the step (1), adding 8g of benzotriazole, and uniformly mixing to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:2.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Example 3
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
80g/L of 98wt% concentrated sulfuric acid, 10g/L of 30wt% hydrogen peroxide, 8g/L, KH57020-50g/L of compound corrosion inhibitor, 40g/L of copper sulfate, 5g/L of impregnating compound, 5g/L of polyethylene glycol monomethyl ether and the balance of deionized water.
The preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing a cysteine solution with the mass concentration of 10%, then adding 10g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 4, uniformly stirring, wherein the stirring temperature is 75 ℃, and the stirring time is 6 hours, so as to obtain a mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol to prepare solution A with the mass concentration of 10%, then adding 40g of solution A into 110g of mixed emulsion in the step (1), adding 5g of benzotriazole, and uniformly mixing to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:1.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Example 4
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
120g/L of 98wt% concentrated sulfuric acid, 20g/L of 30wt% hydrogen peroxide, 15g/L, KH55020-50g/L of compound corrosion inhibitor, 70g/L of copper sulfate, 15g/L of impregnating compound, 8g/L of polyethylene glycol monomethyl ether and the balance of deionized water.
The preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing a cysteine solution with the mass concentration of 20%, then adding 20g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 4, uniformly stirring, wherein the stirring temperature is 80 ℃, and the stirring time is 5 hours, so as to obtain a mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol to prepare a solution A with the mass concentration of 5%, then adding 60g of the solution A into 120g of the mixed emulsion in the step (1), adding 10g of benzotriazole, and uniformly mixing to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:2.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Comparative example 1
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
98wt% concentrated sulfuric acid 100g/L, 30wt% hydrogen peroxide 15g/L, compound corrosion inhibitor 12g/L, KH55035g/L, copper sulfate 55g/L, impregnating compound 10g/L, polyethylene glycol monomethyl ether 7g/L and deionized water balance.
The preparation method of the compound corrosion inhibitor comprises the following steps:
preparing a cysteine solution with the mass concentration of 15%, then adding 15g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 3, uniformly stirring, wherein the stirring temperature is 70 ℃, and the stirring time is 8 hours, so as to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:1.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Comparative example 2
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
98wt% concentrated sulfuric acid 100g/L, 30wt% hydrogen peroxide 15g/L, compound corrosion inhibitor 12g/L, KH55035g/L, copper sulfate 55g/L, impregnating compound 10g/L, polyethylene glycol monomethyl ether 7g/L and deionized water balance.
The preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing a cysteine solution with the mass concentration of 15%, then adding 15g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 3, uniformly stirring, wherein the stirring temperature is 70 ℃, and the stirring time is 8 hours, so as to obtain a mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol to prepare a solution A with the mass concentration of 5%, then adding 50g of the solution A into 115g of the mixed emulsion in the step (1), and uniformly mixing to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:1.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
Comparative example 3
The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
98wt% concentrated sulfuric acid 100g/L, 30wt% hydrogen peroxide 15g/L, compound corrosion inhibitor 12g/L, KH55035g/L, copper sulfate 55g/L, impregnating compound 10g/L, polyethylene glycol monomethyl ether 7g/L and deionized water balance.
The preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing a cysteine solution with the mass concentration of 15%, then adding 15g of 11-mercapto-undecanol into 100g of the cysteine solution, adding dilute hydrochloric acid to adjust the pH to 3, uniformly stirring, wherein the stirring temperature is 70 ℃, and the stirring time is 8 hours, so as to obtain a mixed emulsion;
(2) And (3) adding 7g of benzotriazole into 115g of the mixed emulsion in the step (1), and uniformly mixing to obtain the compound corrosion inhibitor.
The impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the polyether silicone oil is 1:1.
A preparation method of brown oxide liquid for a high-frequency high-speed circuit board comprises the following steps: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and polyethylene glycol monomethyl ether into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
The brown liquid prepared in the examples 1-4 and the comparative examples 1-3 is respectively subjected to brown treatment on a copper plate, the brown temperature is 35 ℃, the brown time is 60s, then the copper plate is washed and dried, the roughness of the surface of the copper plate is tested, and the dried copper plate and the epoxy prepreg are pressed at the pressing temperature of 180 ℃ and the pressing pressure of 150N/cm 2 And pressing under the condition of 40min of pressing time to obtain a finished PCB, and measuring the peel strength by referring to a standard method IPC-TM-650No.2.4.8 test method, wherein the test result is shown in the following table 1:
TABLE 1
Remarks: rz represents the average value of the height differences between five peaks and valleys on the section to be measured, ra represents the arithmetic average value of the distances from each point on the section to be measured to the zero reference line, and Sdr represents the specific surface area increase rate before and after the browning of the copper plate.
As can be seen from table 1 above, the brown oxide liquid prepared by the invention is used for brown oxide of copper, the microetching amount of the copper surface is low, and the values of Ra, rz and Sdr are low according to the test data of the surface roughness, which indicates that the roughness of the copper surface is low and the surface is uniform, and the peel strength of copper and resin is not obviously reduced, thus the brown oxide liquid has good application prospect in the preparation of 5G high-frequency high-speed circuit boards.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The brown oxide liquid for the high-frequency high-speed circuit board is characterized by comprising the following components:
80-120g/L of 98wt% concentrated sulfuric acid, 10-20g/L of 30wt% hydrogen peroxide, 8-15g/L of compound corrosion inhibitor, 20-50g/L of silane coupling agent, 40-70g/L of copper sulfate, 5-15g/L of impregnating compound, 5-8g/L of dispersing agent and the balance of deionized water;
the preparation method of the compound corrosion inhibitor comprises the following steps:
(1) Preparing cysteine solution, then adding 11-mercapto-undecanol, adding dilute hydrochloric acid to adjust the pH to 3-4, and uniformly stirring to obtain mixed emulsion;
(2) Adding 1, 3-bis (1H-benzotriazole) propane into absolute ethyl alcohol, stirring uniformly to obtain a solution A, adding the solution A into the mixed emulsion obtained in the step (1), adding benzotriazole, and mixing uniformly to obtain the compound corrosion inhibitor;
the impregnating compound is a mixture of fatty alcohol polyoxyethylene ether sodium sulfate and polyether silicone oil, and the mass ratio of the impregnating compound to the mixture is 1:1-2.
2. The browning liquid for use on high-frequency and high-speed circuit boards according to claim 1, comprising the following components:
90-110g/L of 98wt% concentrated sulfuric acid, 12-16g/L of 30wt% hydrogen peroxide, 10-13g/L of compound corrosion inhibitor, 30-40g/L of silane coupling agent, 50-60g/L of copper sulfate, 8-12g/L of impregnating compound, 6-7g/L of dispersing agent and the balance of deionized water.
3. The browning liquid for high-frequency and high-speed circuit board according to claim 1, wherein the mass concentration of the cysteine solution in the step (1) is 10-20%, the mass ratio of the cysteine solution to 11-mercapto-undecanol is 100:10-20, and the mass concentration of the dilute hydrochloric acid is 5%.
4. The browning liquid for use on a high-frequency, high-speed circuit board according to claim 1, wherein the temperature of stirring in step (1) is 70-80 ℃ and the stirring time is 5-8h.
5. The browning liquid for use on high-frequency high-speed circuit boards according to claim 1, wherein the mass concentration of 1, 3-bis (1H-benzotriazolyl) propane in said solution a in step (2) is 5 to 10%; the mass ratio of the mixed emulsion to the solution A to the benzotriazole is 110-120:40-60:5-10.
6. The browning liquid for high-frequency and high-speed circuit board according to claim 1, wherein the silane coupling agent is one or more of KH550, KH560 and KH 570.
7. The browning liquid for use on a high-frequency and high-speed circuit board according to claim 1, wherein said dispersant is polyethylene glycol monomethyl ether.
8. A method for preparing the browning liquid for use on a high-frequency high-speed circuit board according to any one of claims 1 to 7, comprising the steps of: adding 98wt% of concentrated sulfuric acid, 30wt% of hydrogen peroxide, a compound corrosion inhibitor, a silane coupling agent, copper sulfate, a sizing agent and a dispersing agent into water according to a formula, and uniformly mixing to obtain the brown oxide liquid for the high-frequency high-speed circuit board.
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