CN108396325A - A kind of solderable nickel protective agent of water solubility - Google Patents
A kind of solderable nickel protective agent of water solubility Download PDFInfo
- Publication number
- CN108396325A CN108396325A CN201810161376.9A CN201810161376A CN108396325A CN 108396325 A CN108396325 A CN 108396325A CN 201810161376 A CN201810161376 A CN 201810161376A CN 108396325 A CN108396325 A CN 108396325A
- Authority
- CN
- China
- Prior art keywords
- nickel
- alcohol
- carboxylic acid
- quinoline
- fatty alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C22/58—Treatment of other metallic material
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention discloses a kind of solderable nickel protective agent of water solubility.The solderable nickel protective agent of the water solubility contains fatty alcohol and quinoline carboxylic acid, wherein the molar ratio of fatty alcohol and quinoline carboxylic acid are 1:1~3:1.The present invention uses protective agent of the combination of fatty alcohol and quinoline carboxylic acid as solderable nickel for the first time; on the one hand; quinoline carboxylic acid can divest the oxidation film layer of nickel; another aspect quinoline carboxylic acid occurs esterification with fatty alcohol and is complexed to form fine and close protective film on nickel layer surface; block the oxidation of nickel; meanwhile nickel oxide can be reduced to elemental nickel by the protective film, accelerated oxidation film layer divests.The protective agent fusion inhibition anti-corrosion of the present invention and reduction help and are welded in one, realize the synchronization process for divesting oxidation film and shielding restitutive protection's film, noresidue Corrosion Potential, real Non-water washing, and protective film automatic classifying when scolding tin ensure that being smoothed out for scolding tin.
Description
Technical field
The invention belongs to electronic component technical field of surface, more particularly to a kind of solderable nickel protection of water solubility
Agent.
Background technology
As electronic product is portable and the market demand of multifunction, peace (group) dress technology and wiring board (PCB) are necessary
Constantly move towards densification.Since the pad of PCB is copper, copper surface is easy to form oxide layer, and not only resistance is big
It even insulate, and not solderable.Therefore, upper surface painting (plating) layer must be applied/plated on the copper pad of PCB to be protected.
In electronic product, nickel coating is a kind of coat of metal generally used.It is plated using solderable nickel on electronic component
Layer, there is following effect：So that non-, can have in weldering base material can face of weld layer；Prevent base material from penetrating into the barrier layer of melting tin-lead solder；
Inhibit to generate the intermetallic compound that unwanted substrate alloy is formed with surface finishing metal.However due to the pole of nickel coating
Easily quickly self-passivation, nickel coating will start self-passivation for several seconds and generate fine and close oxidation film in air, cause nickel plating first
Phenomena such as it is poor that solderability occurs in part, rosin joint, sagging, becomes larger or short circuit so as to cause welding position resistance, seriously affects electronics production
The use of product.
Currently, industry mainly improves the solderability of nickel coating by following a few class techniques：
1 improvement plating solution composition
When chemical nickel plating, the phosphorus content in coating can influence the solderability of nickel coating.Low-phosphorous solderability of nickel coatings is preferable,
Middle and high phosphorus solderability of nickel coatings is poor.But low-phosphorous nickel coating is with the continuity of time, the phosphorus content in coating can gradually increase from
And deteriorated weldability.It is molten that the invention of the patent No. 201010603610.2 provides a kind of chemical plating nickel-phosphorus alloy of high solderability
Liquid makes chemical Ni-P coating be provided with better solderability, and phosphorus content is not restricted in by coating.
2 surface metallization protective layers
Surface is armor coated mainly using there is inert metal, is carried out to fresh nickel surface for example, by using gold, palladium
Covering protection prevents nickel coating from aoxidizing, and ensures the good solderability of nickel coating.
Chemical nickel plating/leaching gold process (Electroless Nickel and Immersion Gold；ENIG) from 1996
Since, at home and abroad promoted rapidly.In order to improve the solderability of chemical nickel coating, by method of cementation by nickel coating table
Face deposited gold coating.But the price of gold is expensive, can voluntarily be dissolved in brazing process, reaches certain concentration just by broken
It is bad；And since nickel coating crystalline texture porosity (related with phosphorus content, roughness etc.), internal stress are big, brittleness is larger etc. asks
Topic, in addition phosphorus rich layer is between nickel layer and gold (very thin) layer, be easily etched with embrittlement etc., it increases chemical Ni-plating layer and produces
The possibility of raw black disk.
Chemical nickel plating/chemical palladium-plating/leaching gold (Electroless Nickel Electroless Palladium
Immersion Gold, ENEPIG) come across in the 1970s, but since PCB density requirements at that time are not high, the originals such as cost is big
Cause there is no popularization.Currently, with the requirement of PCB densifications, ENEPIG technologies start to be taken seriously.Although ENEPIG
Be not in black disk phenomenon, but palladium, gold are precious metal, the pressure of production cost should not be underestimated.
Chinese patent (the patent No.：200580023897.9) disclose it is a kind of by acid palladium solution into line replacement
It precipitates and deposits a thin layer palladium on nickel coating to improve the solderability of nickel coating.Palladium salt needed for this method does not have special want
It asks, acid uses sulfuric acid, phosphoric acid, palladium etching acid, acetic acid and oxalic acid, facilitates purchase.And nickel plating is deposited on by method of replacing
The palladium coating of layer surface is very thin, 0.008-0.016 μm, and the performance for not interfering with nickel plays.The method simple process is applicable in simultaneously
In the matt nickel of plating and chemical nickel plating, but production cost is improved, increases production pressure.
Also have by solving the problems, such as that solderability is poor in nickel surface deposition tin or tin alloy.But by covering on the surface
The coating, the wherein thickness of sedimentary can influence some advantageous properties (such as hardness, wearability, combinable of nickel at 2-5 μm
Property).And the method is only applicable to electronickelling, cannot achieve the metal pattern of coating surface.
3 plating posttreatments
Su He and woods Zhang Hua has developed a kind of anti-passivator MP of nickel coating, and main component is containing-N- ,-S- ,-P- containing orphan
Organic compound such as triazole to electronics etc and additive H are a little.It should be noted that the anti-passivator must be
It keeps under the activated state of nickel using just effective.Before Passivation Treatment, need to throw nickel coating by essence the oxide layer for removing surface,
Then the PCB of nickel plating is placed on dip-coating certain time in the aqueous solution of MP, first with originally washing after dip-coating, then it is clear with deionized water
It washes.The time of dip-coating must execute in strict accordance with process stipulation, and extending the time can be unfavorable to scolding tin.
Cheng Yonghong adds Solder additives to improve solderability in nickel-plating liquid, and further uses CYH-W protections
Agent post-processes.CYH-W can form one layer of scintilla film as a kind of water soluble antioxidant, dip-coating in coating surface, prevent
Coating is contacted with air.The collaboration of Solder additives and CYH-W antioxidants uses, and can keep the solderable of product for a long time
Property.But only the CYH-W with anti-oxidation function is only applicable to fresh nickel layer surface, and the Solderable Bright Nickel Plating
Anode can only use electrolytic nickel, cannot use high-sulfur nickel.
The patent of invention of the patent No. 200880020640.1 discloses a kind of for improving metal or metal alloy surface, spy
Not Shi Yongyu tin and its solderability of alloy surface and the solution and method of corrosion resistance, including phosphorus compound and increase solderability
The solution of compound.However when applied to metallic nickel, the enrichment of nickel layer surface phosphorus basement membrane has hidden danger to its solderability.
In practical application, due to the quick self-passivation of nickel, the prior art do not allow for industry to be long placed in nickel coating after again
Scolding tin is carried out, but scolding tin is carried out immediately after carrying out solderability processing to fresh nickel face.The most common way of industry is using dilute
After hydrochloric acid, dust technology etch or electrochemical etching slough the oxidation film layer of nickel coating, washes through 2-3 pure water, and then carry out
Scolding tin.This method goes oxide film dissolving, multiple washing residual to need to carry out step by step, and indispensable, technique burden is cumbersome；And not
Any anti-passivation anti-oxidation protection can be provided to nickel face, nickel face after processing need to carry out scolding tin immediately, and be long placed in preservation can
Weldering property can not ensure；In addition, the acid group of hydrochloric acid and nitric acid is strong acid radical ion, it is easy residual and further corruption is caused to nickel layer
Erosion, influences solderability, when washing, causes serious electrochemistry if remaining acid ion enters with water inside nickel coating micropore
Corrosion.For the nickel face being long placed in, since nickel oxide film layer is blocked up, strong acid treatment is needed to divest the oxidation film time longer, corrosion
Hidden danger is more, and industry will not use this method.
Invention content
It is impregnated for poor, the traditional diluted acid of solution solderability caused by nickel coating self-passivation and is confined to fresh nickel face, work
The problems such as skill is cumbersome, acid ion easily remains corrosion, the present invention provides a kind of solderable nickel protective agents of water solubility, by once soaking
Bubble technique realizes the synchronization process for divesting oxidation film and shielding protection film, while the weak acid radical ion of reproducibility also has general
Nickel oxide is reduced to the function of nickel simple substance, noresidue Corrosion Potential, real Non-water washing.When scolding tin, which then can be in scolding tin
At a high temperature of (245~260 DEG C) automatic classifying, ensure that being smoothed out for scolding tin.
The above-mentioned purpose of the present invention is realized by following technological means.
On the one hand, the present invention provides a kind of solderable nickel protective agent of water solubility, the solderable nickel of water solubility of the present invention is protected
Shield agent contains fatty alcohol and quinoline carboxylic acid.
Quinoline carboxylic acid is a kind of important pesticide, medicine and medicine intermediate, can be used for synthesizing the imidazoline of the ring containing quinoline
Type herbicides, it can also be used to synthetic antibiotic and important drugs intermediate.Many drugs containing quinoline ring have anti-swollen
The multiple biological activities such as tumor, antibacterial, anti-inflammatory, enhancing memory, antidepression and anti-hypertension.
Quinoline carboxylic acid and fatty alcohol collective effect are protected field by the present invention in the solderability of nickel coating for the first time.On the one hand profit
The oxidation film layer of nickel is divested with the weak acid radical ion of quinoline carboxylic acid, after with fatty alcohol esterification occurs for one side quinoline carboxylic acid,
It is complexed to form fine and close semi-hard dryness protective film on nickel layer surface, completely cuts off corrosive medium, blocked the oxidation of nickel.Meanwhile it should
Protection film layer has reproducibility, can nickel oxide be reduced to elemental nickel, further speed up divesting for oxidation film layer, more fully
Protect the solderability of nickel.When scolding tin, the film layer then can at a high temperature of scolding tin (245~260 DEG C) automatic classifying, ensure that weldering
Tin is smoothed out.
Quinoline carboxylic acid of the present invention is the mixture of quinolinecarboxylic acid or quinoline acetic acid or the two.It is preferred that quinoline -2-
Carboxylic acid, 2- quinoline-acetic acid, quinoline-3-carboxylic acid, 3- quinoline-acetic acid, Cinchonic Acid, one kind in 4- quinoline-acetic acid or
Several mixtures.One or several kinds of mixing in more preferable quinaldic acid, quinoline-3-carboxylic acid, Cinchonic Acid
Object.Most preferably -2 carboxylic acid of quinoline.
The fatty alcohol that the present invention uses is structural formula for CnH2n+1The fatty alcohol of-OH.When carbon atom number is identical, straight chain fatty
Alcohol length is maximum, and institute is at hydrophobic film thickness with respect to highest；Branched fatty alcohol is in film forming because of space structure influence, film layer consistency
The performance of aspect can existing defects.However, not straight-chain fatty alcohol carbon atom number more long length is longer, hydrophobic film thickness is thicker,
Protect weldering property can be better.Unexpectedly, inventor herein has found by test repeatedly, straight-chain fatty alcohol carbon atom
During number increases to 22 by 6, the trend slowly reduced after significantly raising can be presented first in protective agent weldering property.Carbon atom number by
6 when increasing to 18, and thicknesses of layers gradually increases, and protective agent system helps weldering ability to increase；Carbon atom number continues to increase to 22 by 18
When, filming function steric interference increases, and film forming matter weakens with metal surface binding force, protective agent weldering property can slightly under
Drop.Therefore, straight-chain fatty alcohol of the preferred carbon atom number of fatty alcohol of the present invention between 8-20, further preferred carbon atom
Straight-chain fatty alcohol of the number between 12-18.As one embodiment of the present invention, the straight-chain fatty alcohol of optional (but not limited to)
Including：1- octanols (eight alcohol), Decanol (ten carbon alcohol), laruyl alcohol (lauryl alcohol), tridecanol, tetradecyl alchohol, hexadecanol, heptadecanol,
Stearyl alcohol (octadecyl alcolol), eicosanol etc..
The molar ratio of fatty alcohol and quinoline carboxylic acid are 1 in the present invention:1~3:1.Inventor herein sends out by repetition test
It is existing, when the molar ratio of the two is less than 1:When 1, the hydrophily of entire water-soluble solderable nickel protective agent system can be caused too strong and hydrophobic
Property it is inadequate, the thickness of superficial film, compactness reduce, and protective agent helps weldering function reduction；And when the molar ratio of the two is more than 3:1 it
Afterwards, and the poorly water-soluble of whole system can be led to, and the steric hindrance for being formed by molecular structure is big, causes filming function tired
Difficulty, the binding force between flim forming molecule and the coat of metal are also weakened, and superficial film is difficult to reach complete fine and close degree, helps weldering work(
It can decline.The molar ratio of fatty alcohol and quinoline carboxylic acid are 2:When 1, all at binding force of membrane, the compactness of film and hydrophilic and hydrophobic
It has obtained taking into account well, protective agent weldering property can be best.Therefore, the molar ratio of final preferred fat alcohol and quinoline carboxylic acid are 2:
1。
Scheme as a further preference, the solderable nickel protective agent of water solubility of the present invention also contain corrosion inhibiter, compound
Surfactant system, chelating agent and builder.
The corrosion inhibiter is by nitrogen azole compounds, glyoxaline compound, thiol compound, thiazole compound and long-chain
One or several kinds of compounds composition in aromatic sulfonic acid and its salt etc..
The complexed surfactant system contains one or more kinds of hc-surfactants, includes at least simultaneously
One or more of fluorinated surfactant and biosurfactant；Wherein, fluorinated surfactant be nonionic and it is cloudy from
It is one or more in subtype；Biosurfactant is the one or more of rhamnolipid, sophorolipid and polysaccharide, preferably mouse
Lee's glycolipid.And most preferred surfactant system is to contain hc-surfactant, biosurfactant and fluorine table simultaneously
The complexed surfactant system of face activating agent.
The chelating agent is hydramine type organic, preferably diethanol amine, triethanolamine.
The builder includes the mixture of heterocyclic alcohol, alcohol ether or the two.The preferred tetrahydrofurfuryl alcohol of heterocyclic alcohol；Alcohol ether is preferred
Ethylene glycol monobutyl ether, the double butyl ether of ethylene glycol, at least one of propylene glycol monobutyl ether and the double butyl ether of propylene glycol etc..
In addition to above-mentioned component, water is also contained in component of the invention, the parts by weight of the water can be according to difference
The case where adjust, when such as preparing product, for the ease of transport and preservation, at this point it is possible to do not add water or add a small amount of water, with
Improve the concentration of fatty alcohol and quinoline carboxylic acid；It is diluted, is adjusted to suitable use concentration in use, can then add water.
Certainly, using same or similar concentration when being also not excluded for transport, storage and using.
As a preferred embodiment, in the present invention, water-soluble solderable nickel protective agent is in use, fatty alcohol and quinoline
A concentration of 0.3%~1.4% (mass concentration) of carboxylic acid.As a preferred embodiment, the water solubility of the present invention is solderable
Nickel protective agent, when transporting with preservation, a concentration of 10%~20% (mass concentration) of fatty alcohol and quinoline carboxylic acid.As a kind of excellent
The embodiment of choosing, it is when as hole sealing agent concentrate, then water-free, be also when using certainly by using concentration to be diluted,
Because concentrate excessive concentration is possible to that bad order can be caused.
As a preferred embodiment, the solderable nickel protective agent of water solubility provided by the present invention, contains following weight
The component of number：Fatty alcohol and 10-15 parts of quinoline carboxylic acid, 4-10 parts of corrosion inhibiter, 10-20 parts of complexed surfactant system, chela
15-25 parts of mixture, 10-20 parts of builder.The specific ingredient of each auxiliary agent is seen above.In use, first 3% is diluted to pure water~
7% (mass ratio), it is proposed that concentration 5% (mass ratio).
It should be pointed out that common various corrosion inhibiter, surfactant, chelating agent, builder, may be used to this hair
The water-soluble solderable nickel protective agent of bright preparation, and do not influence or help quickly to divest the oxide skin(coating) of nickel while generating reproducibility
Protective film.This is because core of the invention point is to provide a kind of solderable nickel protective agent of water solubility, by quickly divesting nickel
Oxide skin(coating) generates restitutive protection's film mask erosion medium, noresidue Corrosion Potential, Non-water washing, final raising electronics member simultaneously
The solderability of device nickel coating.This purpose is used as major function component to realize by fatty alcohol with quinoline carboxylic acid；And
The effect of above-mentioned corrosion inhibiter, hc-surfactant, chelating agent, builder etc. is to assist major function component, to metal
The micropore of coating surface and coating and lopsided crystal defect implement high-efficiency cleaning and tentatively reduce coated metal corrosion activity etc.
Effect reacts the integrated protection performance after forming a film to enhance fatty alcohol with quinoline carboxylic acid.Therefore, although the present invention lists preferably
Corrosion inhibiter, surfactant, chelating agent, builder etc., but the adoptable corrosion inhibiter of the present invention, surfactant, chelating agent,
Builder etc., is not limited by mentioned kind, as long as in the prior art, can not influence or help quickly to divest nickel
Oxide skin(coating) generates the auxiliary agent of restitutive protection's film simultaneously can be with.
On the other hand, invention also provides the application methods of the solderable nickel protective agent：Using simple soaking technology.
Specifically, nickel plating component is immersed in solderable nickel protective agent and is handled, treatment temperature is 50~55 DEG C, processing time
It is 5~90 seconds, then takes out hot blast drying.Due to the easily quick self-passivation of nickel coating, fresh nickel coating is exposed at sky
It will start within 1~2 second in gas self-passivation and generate fine and close oxidation film.After placing a period of time, it is contemplated that the oxidation film layer in nickel face
Blocked up, preferably catholyte assists soaking technology, to accelerate stripping or reduction of the present invention to nickel oxidation film layer, i.e.,：Workpiece
As cathode, stainless steel is as anode, 5~8V of control voltage.
The beneficial effects of the present invention are：
1, the present invention is merged inhibition anti-corrosion and reduction helps and is welded in one, realized and divest oxidation by simply immersing technique
The synchronization process of film and shielding restitutive protection's film, noresidue Corrosion Potential, real Non-water washing, protective film divides automatically when scolding tin
Solution, ensure that being smoothed out for scolding tin.
2, the present invention is suitable for any plating, obtain fresh of chemical plating process or is long placed in nickel coating, and nickel coating is through this
After invention processing, 255 DEG C of wicking 5s, upper tin area is more than 95%, good weldability.
3, the iron material nickel coating salt spray resistance of the invention handled 8~12 hours, copper material nickel coating salt spray resistance 48~72 hours,
Meet industry working standard.
4, the nickel coating that the present invention is handled, exposed placement are up to half a year in air, and solderability is still good.
Description of the drawings
Fig. 1 is the wicking picture of nickel coating after present invention processing, as can be seen from Figure, solderable nickel protective agent of the invention nursing
Afterwards, it is full to climb tin, is completely covered, does not reveal nickel, leakage tin phenomenon, good weldability.
Specific implementation mode
Below by way of the technical solution that specific embodiment further illustrates the present invention, specific embodiment does not represent to this hair
The limitation of bright protection domain.Other people still fall within this hair according to some nonessential modifications and adjustment that theory of the present invention is made
Bright protection domain.
1 solderable nickel protective agent of embodiment
Table 1
Table 2
Concentrate is prepared respectively by 8 formulas of Tables 1 and 2, and being diluted to 5% concentration with pure water is made working solution.
2 scolding tin performance test of embodiment
Purpose：Utilize scolding tin that is fresh, being long placed in nickel coating after the general simple wicking method test different formulations processing of industry
Performance.
Test piece sample：
Sample 1：Fresh nickel face.Copper material nickel plating leg, electroplating technology, 1.0~2 μm of nickel layer film thickness (40~80 μ ").
Sample 2：It is long placed in nickel face.Copper material nickel plating leg, electroplating technology, 1.0~2 μm of nickel layer film thickness (40~80 μ ").It opens wide
It places 3 months in air.
Solderability protects treatment conditions：
To 50 DEG C, fresh nickel face is immersed directly in 8 formula working solutions 8 formula working solutions in heating embodiment 1
Hot blast drying is taken out in processing 5 seconds；It is long placed in nickel face and uses catholyte auxiliary process, using workpiece as cathode, stainless steel is anode,
Voltage 7V is controlled, is immersed in 8 formula working solutions and handles 30 seconds, take out hot blast drying.
Simple wicking test：After processing, 255 DEG C of wickings 5 seconds are virtually free from leakage tin, dew nickel phenomenon to workpiece, i.e., on
Tin area >=95%, then solderability is qualified.
Test result：After the processing of 8 formulas, fresh nickel face and it is long placed in the upper tin area in nickel face >=95%, solderability is good
It is good.
The corrosion-resistant test of 3 nickel coating of embodiment
Purpose：Nickel coating is tested through different formulations treated corrosion-resistant oxidation resistance using neutral salt spray test.
Test piece sample：
Sample 1：Copper material chemical nickel plating, 2 μm of nickel layer film thickness (80 μ ").
Sample 2：Iron material electronickelling, 2.5 μm of nickel layer film thickness (100 μ ").
Solderability protects treatment conditions：For 8 formula working solutions in heating embodiment 1 to 55 DEG C, sample 1 and sample 2 are equal
Immersion treatment 10 seconds takes out hot blast drying.
Blank control group is set simultaneously, i.e., is handled without solderability protection.
By test piece sample rear progress neutral salt spray test processed by the invention, specific test method is with reference to GB/T
10125-2012《Artificial atmosphere corrosion test-salt spray test》Testing standard.Resisting salt fog corrosion requirement of the industry for nickel coating
Different because of base material, Copper base material nickel plating generally requires salt spray resistance 24~48 hours；Iron-based material nickel plating, it is general since iron is more active compared with copper
All over requiring salt spray resistance 8 hours.The salt spray test period of this experiment based on industry working standard, is specifically shown in Table 3.Experiment
As a result according to GB/T6461-2002《Metal and sample and test specimen of other inorganic cover layers after corrosion test on metallic matrix
Grading》Rating scale is evaluated.Appearance and coating breakage rating result are shown in Table 4 and table 5.
3 different formulations of table and sample neutral salt spray test period
| Number | 1,2,3,4 formula | 5,6,7,8 formula |
| 1 copper material nickel plating of sample | 48h | 72h |
| 2 iron material nickel plating of sample | 8h | 12h |
Table 4 is formulated the neutral salt spray test comparing result of 1-4
| Number | Sample explanation | Appearance is graded | Coating breakage is graded |
| Sample 1 | Copper material nickel plating, blank, salt fog 48h | 1 grade | H grades |
| Sample 1 | Copper material nickel plating, solderability protection, salt fog 48h | 10 grades | A grades |
| Sample 2 | Iron material nickel plating, blank, salt fog 8h | 1 grade | H grades |
| Sample 2 | Iron material nickel plating, solderability protection, salt fog 8h | 10 grades | A grades |
Table 5 is formulated the neutral salt spray test comparing result of 5-8
| Number | Sample explanation | Appearance is graded | Coating breakage is graded |
| Sample 1 | Copper material nickel plating, blank, salt fog 72h | 1 grade | H grades |
| Sample 1 | Copper material nickel plating, solderability protection, salt fog 72h | 10 grades | A grades |
| Sample 2 | Iron material nickel plating, blank, salt fog 12h | 1 grade | H grades |
| Sample 2 | Iron material nickel plating, solderability protection, salt fog 12h | 10 grades | A grades |
Note：Class-A surfaces appearance is unchanged；H grades of corrosion of coating crackings.
It summarizes：By table 4 and table 5 it is found that using the sample of the solderable nickel protective agent processing of the present invention after salt spray test, coating
Appearance is unchanged, corrosion-free defect, and appearance can be kept to grade 10 grades and graded A grades with coating breakage；Solderability protection is not made
After salt spray test, coating is corroded the sample of processing by large area, cracking.Contain only the solderable of fatty alcohol and quinoline carboxylic acid
Nickel protective agent (formula 1-4) has fully met salt spray resistance requirement of the industry for nickel coating；Relative to containing only fatty alcohol
With the solderable nickel protective agent of quinoline carboxylic acid (formula 1-4), at the solderable nickel protective agent (formula 5-8) also containing other auxiliary agents
For the sample of reason after salt air corrosion, the corrosion resistant time is longer.Illustrate that other auxiliary agents have the function of certain improving performance.
Embodiment 4 stores solderability test
Purpose：Lasting protective capability of the test present invention for solderability of nickel coatings.
Test piece sample：
Fresh nickel face.Copper material nickel plating leg, 1.0~2 μm of electroless nickel layer film thickness (40~80 μ ").
Solderability protects treatment conditions：8 in heating embodiment 1 formula working solutions are to 55 DEG C, sample immersion treatment 80
Second, take out hot blast drying.
2 months (25 DEG C of mean temperature, relative humidity are placed by being opened wide indoors by the sample of 1,2,3,4 formula processing
RH be 60%) after, carry out solderability test, test method is the same as embodiment 2.
6 months (25 DEG C of mean temperature, relative humidity are placed by being opened wide indoors by the sample of 5,6,7,8 formula processing
RH be 60%) after, carry out solderability test, test method is the same as embodiment 2.
The results show that after processed sample is long placed in 2~6 months, nickel coating surface is without apparent corrosion and oxidative phenomena, leaching
Tin test wetted area reaches 95% or more, still has good solderability.
Claims (11)
1. a kind of composition, it is characterised in that containing fatty alcohol and quinoline carboxylic acid, the molar ratio of the fatty alcohol and quinoline carboxylic acid
It is 1:1~3:1.
2. composition according to claim 1, it is characterised in that also contain corrosion inhibiter, complexed surfactant system, chela
Mixture and builder.
3. composition according to claim 1, which is characterized in that the fatty alcohol is that structural formula is CnH2n+1The fat of-OH
Alcohol.
4. composition according to claim 3, which is characterized in that the fatty alcohol CnH2n+1- OH is C atomicities n in 8-20
Between straight-chain fatty alcohol；
Preferably, the fatty alcohol CnH2n+1- OH is straight-chain fatty alcohols of the C atomicities n between 12-18.
5. composition according to claim 1, which is characterized in that the quinoline carboxylic acid be quinolinecarboxylic acid or quinoline acetic acid or
The mixture of the two；It is preferred that quinaldic acid, 2- quinoline-acetic acid, quinoline-3-carboxylic acid, 3- quinoline-acetic acid, Cinchonic Acid,
One or several kinds of mixtures in 4- quinoline-acetic acid；More preferable quinaldic acid, quinoline-3-carboxylic acid, Cinchonic Acid
In one or several kinds of mixtures；Most preferably -2 carboxylic acid of quinoline.
6. composition according to claim 1, which is characterized in that the molar ratio of the fatty alcohol and quinoline carboxylic acid are 2:1.
7. composition according to claim 2, it is characterised in that：The corrosion inhibiter is by nitrogen azole compounds, imidazoles
One or several kinds of compound groups in conjunction object, thiol compound, thiazole compound and long-Chain aromatic hydrocarbon sulfonate or its salt
At；Preferably, the complexed surfactant system at least contains a kind of hc-surfactant, while including at least fluorine surface
One kind in activating agent and biosurfactant；It is highly preferred that the fluorinated surfactant is nonionic and anion
It is one or more in type；It is highly preferred that the biosurfactant is one kind of rhamnolipid, sophorolipid and polysaccharide
Or it is a variety of；Even more preferably from rhamnolipid；Most preferably, the surfactant system simultaneously contain hc-surfactant,
Biosurfactant and fluorinated surfactant；Preferably, the chelating agent is hydramine type organic；It is highly preferred that described
Hydramine type organic is diethanol amine and/or triethanolamine；Preferably, the builder is heterocyclic alcohol and/or alcohol ether；More preferably
Ground, the heterocyclic alcohol are tetrahydrofurfuryl alcohol；It is highly preferred that the alcohol ether is ethylene glycol monobutyl ether, the double butyl ether of ethylene glycol, the third two
One or more of alcohol monobutyl ether and the double butyl ether of propylene glycol.
8. composition according to claim 2, it is characterised in that the ingredient containing following parts by weight：
Fatty alcohol and quinoline carboxylic acid are 10-15 parts total；
4-10 parts of corrosion inhibiter；
10-20 parts of complexed surfactant system；
15-25 parts of chelating agent；
10-20 parts of builder；
Preferably, the corrosion inhibiter by nitrogen azole compounds, glyoxaline compound, thiol compound, thiazole compound and
One or several kinds of compounds composition in long-Chain aromatic hydrocarbon sulfonate or its salt；Preferably, the complexed surfactant system
At least contain a kind of hc-surfactant, while including at least one kind in fluorinated surfactant and biosurfactant；
It is highly preferred that the fluorinated surfactant is one or more in nonionic and anionic；It is highly preferred that described
Biosurfactant is the one or more of rhamnolipid, sophorolipid and polysaccharide；Even more preferably from rhamnolipid；Most preferably
Ground, the surfactant system contain hc-surfactant, biosurfactant and fluorinated surfactant simultaneously；It is excellent
Selection of land, the chelating agent are hydramine type organic；It is highly preferred that the hydramine type organic is diethanol amine and/or three second
Hydramine；Preferably, the builder is heterocyclic alcohol and/or alcohol ether；It is highly preferred that the heterocyclic alcohol is tetrahydrofurfuryl alcohol；It is more excellent
Selection of land, the alcohol ether are one kind in ethylene glycol monobutyl ether, the double butyl ether of ethylene glycol, propylene glycol monobutyl ether and the double butyl ether of propylene glycol
Or it is several.
9. the solderable nickel protective agent of water solubility according to claim 8, which is characterized in that also contain in the composition
Water.
10. according to any compositions of claim 1-9, it is characterized in that, the composition is as water-soluble solderable nickel protection
Agent.
11. the application method of the composition described in claim 1-10, which is characterized in that using water-soluble solderable nickel protective agent pair
Nickel plating workpiece carries out immersion treatment, and temperature is 50~55 DEG C, and the time is 5~90 seconds, and hot blast drying is taken out after immersion treatment；It is preferred that
Ground, using workpiece as cathode, stainless steel assists soaking technology as anode, using catholyte, and control voltage is in 5~8V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810161376.9A CN108396325B (en) | 2018-02-27 | 2018-02-27 | Water-soluble weldable nickel protective agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810161376.9A CN108396325B (en) | 2018-02-27 | 2018-02-27 | Water-soluble weldable nickel protective agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108396325A true CN108396325A (en) | 2018-08-14 |
| CN108396325B CN108396325B (en) | 2020-07-03 |
Family
ID=63095640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810161376.9A Active CN108396325B (en) | 2018-02-27 | 2018-02-27 | Water-soluble weldable nickel protective agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108396325B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176442A (en) * | 2019-05-30 | 2019-08-27 | 苏州浪潮智能科技有限公司 | A kind of chip pin of anti-bridge joint |
| CN114807943A (en) * | 2022-06-27 | 2022-07-29 | 深圳市板明科技股份有限公司 | Micro-etching solution for 5G high-frequency line production process, micro-etching method and application of micro-etching solution |
| CN115044895A (en) * | 2022-05-12 | 2022-09-13 | 华南理工大学 | Corrosion-resistant phosphating solution using enalapril maleate and preparation method and application thereof |
| CN115433929A (en) * | 2022-09-14 | 2022-12-06 | 深圳市豪龙新材料技术有限公司 | Organic weldable copper surface protective agent and preparation method thereof |
| CN117835585A (en) * | 2024-03-06 | 2024-04-05 | 梅州鼎泰电路板有限公司 | Surface treatment method of circuit board and circuit board manufactured by same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102559358A (en) * | 2012-01-11 | 2012-07-11 | 广州天至环保科技有限公司 | Water-soluble electric contact lubricating protective agent improving pluggable resistance of electronic element and use method thereof |
| CN103668147A (en) * | 2012-09-26 | 2014-03-26 | 广州天至环保科技有限公司 | Chrome-free water-based protective agent capable of improving overall performance of tin and tin alloy clad layers |
-
2018
- 2018-02-27 CN CN201810161376.9A patent/CN108396325B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102559358A (en) * | 2012-01-11 | 2012-07-11 | 广州天至环保科技有限公司 | Water-soluble electric contact lubricating protective agent improving pluggable resistance of electronic element and use method thereof |
| CN103668147A (en) * | 2012-09-26 | 2014-03-26 | 广州天至环保科技有限公司 | Chrome-free water-based protective agent capable of improving overall performance of tin and tin alloy clad layers |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176442A (en) * | 2019-05-30 | 2019-08-27 | 苏州浪潮智能科技有限公司 | A kind of chip pin of anti-bridge joint |
| CN115044895A (en) * | 2022-05-12 | 2022-09-13 | 华南理工大学 | Corrosion-resistant phosphating solution using enalapril maleate and preparation method and application thereof |
| CN115044895B (en) * | 2022-05-12 | 2023-07-18 | 华南理工大学 | Corrosion-resistant phosphating solution using enalapril maleate and preparation method and application thereof |
| CN114807943A (en) * | 2022-06-27 | 2022-07-29 | 深圳市板明科技股份有限公司 | Micro-etching solution for 5G high-frequency line production process, micro-etching method and application of micro-etching solution |
| CN115433929A (en) * | 2022-09-14 | 2022-12-06 | 深圳市豪龙新材料技术有限公司 | Organic weldable copper surface protective agent and preparation method thereof |
| CN115433929B (en) * | 2022-09-14 | 2023-08-08 | 深圳市豪龙新材料技术有限公司 | Organic solderability copper surface protective agent and preparation method thereof |
| CN117835585A (en) * | 2024-03-06 | 2024-04-05 | 梅州鼎泰电路板有限公司 | Surface treatment method of circuit board and circuit board manufactured by same |
| CN117835585B (en) * | 2024-03-06 | 2024-05-03 | 梅州鼎泰电路板有限公司 | Surface treatment method of circuit board and circuit board manufactured by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108396325B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108396325A (en) | A kind of solderable nickel protective agent of water solubility | |
| CA2004796C (en) | Inhibited composition and method for stripping tin, lead or tin-lead alloy from copper surfaces | |
| JP5707135B2 (en) | Self-assembled molecules on immersion silver coatings | |
| US6200451B1 (en) | Method for enhancing the solderability of a surface | |
| USRE45881E1 (en) | Method for enhancing the solderability of a surface | |
| KR101270770B1 (en) | Electroplating method for printed circuit board | |
| CN112126929A (en) | Local gold plating process for surface of aluminum material | |
| US6905587B2 (en) | Method for enhancing the solderability of a surface | |
| US8961678B2 (en) | Organic solderability preservative and method | |
| CN111434801B (en) | Water-based copper protective agent | |
| JP6192181B2 (en) | Electronic component and manufacturing method thereof | |
| TWI746583B (en) | A water-based composition for post-treatment of metal surfaces | |
| EP2180081B1 (en) | Post-treatment composition for increasing corrosion resistance of metal or metal alloy surfaces | |
| EP2878702B1 (en) | Organic disulfide-containing surface treatment solution for gold or gold alloy plating and method thereof | |
| TWI593687B (en) | Method for forming organic coating on nickel surface | |
| CN112410838B (en) | Water-based electroplated nickel sealing agent and preparation method thereof | |
| CN113038734B (en) | Organic metal solderability preservative, preparation method and application of organic metal solderability preservative film | |
| US7267259B2 (en) | Method for enhancing the solderability of a surface | |
| EP0750549B1 (en) | Bismuth coating protection for copper | |
| Li Fang et al. | The advantages of mildly alkaline immersion silver as a final finish for solderability | |
| EP1029944A2 (en) | Method for enhancing the solderability of a surface | |
| KR102622751B1 (en) | Composition for cleaning mask and method for cleaning mask using the same | |
| CN106227004B (en) | A kind of copper or copper alloy wiring water system photoresist stripper | |
| KR20150084264A (en) | A composition of the corrosion inhibitors of the copper surface of the magnesium alloy is applied to the communucations rf filter and a treating method using the composition | |
| CN115044894A (en) | Water-based protective agent shared by gold and tin coatings and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |