Background technology
Electroless copper is a kind of technique in circuit board fabrication.Metal copper ion is made to exist by reducing agent appropriate in solutionThe metal copper deposition process of progress, also referred to as electroless copper facing or self-catalysis copper facing are restored under the autocatalysis of matrix surface, is changedThe process that copper facing process nature is redox reaction is learned, belonging to has electronics transfer, the chemical deposition process without external power.
Electroless copper stability is high, and operating temperature and the solution concentration scope of application are wider, and layers of copper is fine and close, there is splendid combinationPower, these are all the advantages of electroless copper.Electroless copper is widely used in all trades and professions, such as：Electronic apparatus, five gold process,The fields such as craftwork, furniture decoration.Electroless copper have it is easy to operate, large-size pipeline is operable, unaccommodated semiworksCan operate, not need to be powered, and environmental protection, without cyanogen, the advantages that applying generally to all metals and nonmetallic surface copper facing.
Chemical bronze plating liquid is a kind of dedicated liquid for electroless copper industry, has heavy copper at a high speed, stability is high, workThe features such as temperature and the wider solution concentration scope of application.Most popular in the electronics industry at present is using formaldehyde as reductionAgent, EDTA and sodium potassium tartrate tetrahydrate are independent or mixing complexing agent system.Formaldehyde is used not only to have for the electroless copper of reducing agentThere is a relatively low production cost, and can obtain that purity is higher, the preferable copper coating of electric conductivity in catalytic matrix surface, thereforeIt has been widely used in the industrial production.For example, the metallization of through-hole and blind hole on plastic electroplating, printed circuit board,Preparation of conductive treatment and electromagnetic shielding box of ceramics etc., generally all uses the electroless copper using formaldehyde as reducing agent to beatBottom.
But by formaldehyde be used as reducing agent chemical bronze plating liquid, due to itself have toxicity, can cause human body and fromThe pollution of right environment.Chemical copper plating solution using formaldehyde as reducing agent must could occur effectively to react in high alkalinity, so as toEasily cause the corrosion of plating piece body.In addition, also there is the defects of plating speed is relatively low, bath stability is poor in the technique, industriallyUsing limited.
Therefore, developing a kind of chemical bronze plating liquid that can solve above-mentioned performance issue is highly desirable.
Invention content
Present invention mainly solves the technical issues of, for current chemical bronze plating liquid mostly using formaldehyde as reducing agent, toxicityGreatly, the chemical copper plating solution using formaldehyde as reducing agent must could occur effectively to react in high alkalinity, easily cause plating piece machineThe defects of corrosion of body, provides a kind of preparation method of environmental friendly, anti-corrosive erosion chemical bronze plating liquid.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of environmental friendly, anti-corrosive erosion chemical bronze plating liquid, it is characterised in that specifically preparation process is：
（1）By 200~250mL Mian Jiang liquid be put into the reaction kettle with air valve, reaction kettle is sealed, by air valve to reaction kettleCarbon dioxide gas is inside passed through, breather valve, heat temperature raising are closed after ventilation, insulation reaction obtains reaction mass；
（2）Above-mentioned reaction mass is mixed with quick lime, heat temperature raising resolution causticity obtains the causticity slurries that disappear, the causticity that will disappear slurryLiquid is separated by filtration collection filter residue, and filter residue is placed in oven and dried, and obtains hydro-thermal coke；
（3）200~250mL liquor potassic permanganates are prepared, concentrated sulfuric acid solution is added in liquor potassic permanganate, adjust potassium permanganatePH value of solution obtains acid permanganate soln, and acid permanganate soln is poured into water-bath, heat temperature raising, take 80~100g polyurethane foams are put into water-bath and polyurethane foam are made to be completely immersed in acid permanganate soln, impregnate, obtainIt is roughened polyurethane foam；
（4）Roughening polyurethane foam is put into equipped with being impregnated in 150~200mL oxalic acid solutions, stirred with glass bar and is squeezed is thickChange polyurethane foam, take out roughening polyurethane foam, washed 2~3 times with clear water, obtain polyurethane base-material, prepare 100~120mTin chloride solution adds 5~7g glass puttys, 30~40mL hydrochloric acid into tin chloride solution, obtains sensitizing solution, polyurethane base-material is put intoIt is impregnated in sensitizing solution, obtains sensitization polyurethane base-material；
（5）Palladium chloride solution and hydrochloric acid are mixed to get solution glue in equal volume, by above-mentioned sensitization polyurethane base-material immerse 120~In 150mL solution glues, after dispergation processing, take out, by dispergation, treated that polyurethane base-material is put into 200~220mL ammonium hypophosphitesIn solution, impregnate, obtain activated urethanes glue；
（6）Count in parts by weight, by 40~50 parts of copper sulphate, 20~30 parts of hydro-thermal coke, 15~20 parts of glyoxalic acids, 60~70 partsSodium tartrate, 40~50 parts of activated urethanes glues and 20~25 parts of sodium carbonate, which are put into 400~500 parts of deionized waters, to be disperseed,It is mixed, obtains environmental friendly, anti-corrosive erosion chemical bronze plating liquid.
Step（1）The Mian Jiang liquid solid masses content for 25%, Ventilation Rate is 40~50mL/min, ventilationDuration is 10~15min, and temperature is 200~220 DEG C after heat temperature raising, and the insulation reaction time is 7~8h.
Step（2）The mass ratio that the reaction mass is mixed with quick lime is 10 ︰ 1, after heat temperature raising temperature for 80~90 DEG C, digestion time is 4~5min, and set temperature is 100~110 DEG C, and drying time is 4~10h.
Step（3）The mass concentration of the liquor potassic permanganate is 7~10g/mL, and the mass fraction of concentrated sulfuric acid solution is85%, liquor potassic permanganate pH to 2~3 is adjusted, temperature is 45~50 DEG C after heat temperature raising, and soaking time is 3~4min.
Step（4）The mass fraction is 5%, squeezes the roughening polyurethane foam time as 5~7min, tin chloride solutionMass fraction for 5%, the mass fraction of hydrochloric acid is 10%, and polyurethane base-material is put into 5~8min of soaking time in sensitizing solution.
Step（5）The mass concentration of the palladium chloride solution is 0.5g/L, and the mass fraction of hydrochloric acid solution is 5%, dispergationProcessing time is 4~5min, and the mass fraction of ammonium hypophosphite solution is 45%, and soaking time is 5~10min.
Step（6）The mixing time is 20~25min.
The beneficial effects of the invention are as follows：
（1）The present invention by Mian Jiang liquid be put into reaction kettle, be passed through heating and thermal insulation after carbon dioxide gas and react, obtain reactantReaction mass quick lime is cleared up causticity, is separated by filtration rear re-dry and obtains hydro-thermal coke, using polyurethane foam as original by materialMaterial is roughened to obtain roughening polyurethane foam, then immersing roughening polyurethane foam into oxalic acid solution through acid permanganate soln,Take out, it is washed be put into sensitizing solution impregnate obtain sensitization polyurethane base-material, sensitization polyurethane base-material after dispergation is handled, impregnateIn ammonium hypophosphite solution, its surface active is obtained into activated urethanes glue, by activated urethanes glue, copper sulphate, hydro-thermalThe substances such as coke and sodium tartrate are scattered in deionized water, obtain environmental friendly, anti-corrosive erosion chemical bronze plating liquid, of the invention by hydro-thermalCoke aoxidizes in the chemical bronze plating liquid of high-temperature heating, generation reducibility gas-carbonoxide and hydrogen is reacted with water, from platingCopper ion is aoxidized electrolysis on metallic matrix by the reducibility gas slowly released in liquid, and in addition polyurethane base-material is as metalOrganic coating of matrix, contributes to copper to be uniformly dispersed in metal body surface, forms smooth copper coating, wherein polyurethane is thickDuring change, the binding force of polyurethane surface and copper metal coating can be increased, open simultaneously blind hole and the inside of foam base plateChannel, on the surface of polyurethane foam generation there is hydrophilic group, make surface roughening, be conducive to the coat of metal from havingMachine coating surface grows out, and increases the copper facing area of metallic matrix, and reducing agent used in copper facing is mainly hydro-thermal coke, in addition alsoContaining a small amount of glyoxalic acid and ammonium hypophosphite, copper ion can be restored, the binding force of organic coating and the coat of metal can also be madeIncrease, the noxious materials such as corrosive substances and formaldehyde such as strong acid and strong base, thus the chemical plating of the present invention are free of in chemical bronze plating liquidCopper liquid is safe and environmentally friendly；
（2）Chemical bronze plating liquid is in a high temperauture environment in electroplating process in the present invention, the electronics phase on metal copper ion and cathodeWith reference to generation copper metal atom, the constantly crystallization of copper metal atom forms continuous metal deposition layer in matrix surface, and copper metal is brilliantFormation of the body on cathode can be roughly divided into the generation of metal crystal nuclei and two processes of growth of metal grain, organic in electroplate liquidCoating can inhibit the growth of crystal grain, and the speed of growth of crystal grain is caused to be less than the formation speed of nucleus, forms more tiny metalCrystal grain, the accumulation for making copper coating is more fine and close, and copper coating surface is not likely to produce protrusion, and copper coating skeleton surface is damaged when being washed awaySmaller, the crystal grain of gained metal copper coating is more and tiny, and metallic copper first deposits and forms coating afterwards, the nickel chloride in chemical bronze plating liquidStart to restore on cathode, plate last layer nickel film in copper coating surface, metallic nickel has good corrosion resistance, can be rightCopper coating plays preferable protective effect, and copper coating is avoided to be aoxidized, and organic coating can be filled the hole of copper coating, copperCoating is improved the corrosion resistance of inorganic acid highly basic, so as to make coating more perfect to the protection of metallic matrix, chemistryThe Corrosion Protection of copper plating bath improves, and has a extensive future.
Specific embodiment
By Mian Jiang that 200~250mL solid masses content is 25% liquid be put into the reaction kettle with air valve, sealing is anti-Kettle to be answered, with the Ventilation Rate of 40~50mL/min, carbon dioxide gas is passed through into reaction kettle by air valve, ventilation continues 10~15min closes breather valve, is heated to 200~220 DEG C, 7~8h of insulation reaction obtains reaction mass；By above-mentioned reactantMaterial is mixed with quick lime for 10 ︰ 1 in mass ratio, is heated to 80~90 DEG C, is cleared up 4~5min, is obtained the causticity slurries that disappear, willThe causticity that disappears slurries are separated by filtration collection filter residue, filter residue are put into the baking oven that set temperature is 100~110 DEG C, dry 4~10h,Obtain hydro-thermal coke；The liquor potassic permanganate that 200~250mL mass concentrations are 7~10g/mL is prepared, is 85% by mass fractionConcentrated sulfuric acid solution add in liquor potassic permanganate in, adjust liquor potassic permanganate pH to 2~3, obtain acid permanganate soln,Acid permanganate soln is poured into water-bath, is heated to 45~50 DEG C, 80~100g polyurethane foams is taken to be put into waterIn bath and polyurethane foam is made to be completely immersed in acid permanganate soln, impregnate 3~4min, obtain roughening polyurethane foamFoam；Polyurethane foam will be roughened to be put into equipped with impregnating in the oxalic acid solution that 150~200mL mass fractions are 5%, stirred with glass barIt mixes and squeezes roughening 5~7min of polyurethane foam, take out roughening polyurethane foam, washed 2~3 times with clear water, obtain polyurethaneBase-material prepares the tin chloride solution that 100~120mL mass fractions are 5%, into tin chloride solution plus 5~7g glass puttys, 30~40mL mass fractions are 10% hydrochloric acid, obtain sensitizing solution, and polyurethane base-material is put into 5~8min of immersion in sensitizing solution, is obtained quickChange polyurethane base-material；The hydrochloric acid that palladium chloride solution and mass fraction that mass concentration is 0.5g/L are 5% is mixed to get in equal volumeGlue is solved, above-mentioned sensitization polyurethane base-material is immersed in 120~150mL solution glues, after dispergation handles 4~5min, takes out, will solveTreated that polyurethane base-material is put into that 200~220mL mass fractions are in 45% ammonium hypophosphite solution for glue, impregnates 5~10min,Obtain activated urethanes glue；It counts in parts by weight, by 40~50 parts of copper sulphate, 20~30 parts of hydro-thermal coke, 15~20 parts of secondAldehydic acid, 60~70 parts of sodium tartrates, 40~50 parts of activated urethanes glues and 20~25 parts of sodium carbonate are put into 400~500 parts and goDisperse in ionized water, 20~25min is mixed, obtain environmental friendly, anti-corrosive erosion chemical bronze plating liquid.
Example 1
By 200mL solid masses content be 25% Mian Jiang liquid be put into the reaction kettle with air valve, seal reaction kettle, withThe Ventilation Rate of 40mL/min is passed through carbon dioxide gas into reaction kettle by air valve, ventilates and continue 10min, closes ventilationValve, is heated to 200 DEG C, and insulation reaction 7h obtains reaction mass；It is in mass ratio with quick lime by above-mentioned reaction mass10 ︰ 1 are mixed, and are heated to 80 DEG C, are cleared up 4min, are obtained the causticity slurries that disappear, and the causticity that will disappear slurries are separated by filtration collection filter residue,Filter residue is put into the baking oven that set temperature is 100 DEG C, dry 4h obtains hydro-thermal coke；It is 7g/ to prepare 200mL mass concentrationsThe concentrated sulfuric acid solution that mass fraction is 85% is added in liquor potassic permanganate, it is molten to adjust potassium permanganate by the liquor potassic permanganate of mLLiquid pH to 2, obtains acid permanganate soln, and acid permanganate soln is poured into water-bath, is heated to 45 DEG C, takes80g polyurethane foams are put into water-bath and polyurethane foam are made to be completely immersed in acid permanganate soln, impregnate 3min, obtainTo roughening polyurethane foam；Polyurethane foam will be roughened to be put into equipped with impregnating in the oxalic acid solution that 150mL mass fractions are 5%, usedGlass bar stirs and squeezes roughening polyurethane foam 5min, takes out roughening polyurethane foam, is washed 2 times with clear water, obtain poly- ammoniaEater base stocks prepare the tin chloride solution that 100mL mass fractions are 5%, 5g glass puttys, 30mL mass fractions are added into tin chloride solutionFor 10% hydrochloric acid, sensitizing solution is obtained, polyurethane base-material is put into sensitizing solution and impregnates 5min, obtains sensitization polyurethane base-material；It willThe hydrochloric acid that the palladium chloride solution and mass fraction that mass concentration is 0.5g/L are 5% is mixed to get solution glue in equal volume, will be above-mentioned quickChange polyurethane base-material to immerse in 120mL solution glues, after dispergation processing 4min, take out, treated that polyurethane base-material is put by dispergationEnter in the ammonium hypophosphite solution that 200mL mass fractions are 45%, impregnate 5min, obtain activated urethanes glue；In parts by weightMeter, by 40 parts of copper sulphate, 20 parts of hydro-thermal coke, 15 parts of glyoxalic acids, 60 parts of sodium tartrates, 40 parts of activated urethanes glues and 20 partsSodium carbonate, which is put into 400 parts of deionized waters, to be disperseed, and 20min is mixed, and obtains environmental friendly, anti-corrosive erosion chemical bronze plating liquid.
Example 2
By 225mL solid masses content be 25% Mian Jiang liquid be put into the reaction kettle with air valve, seal reaction kettle, withThe Ventilation Rate of 45mL/min is passed through carbon dioxide gas into reaction kettle by air valve, ventilates and continue 13min, closes ventilationValve, is heated to 210 DEG C, and insulation reaction 7.5h obtains reaction mass；It is in mass ratio with quick lime by above-mentioned reaction mass10 ︰ 1 are mixed, and are heated to 85 DEG C, are cleared up 4.5min, are obtained the causticity slurries that disappear, and the causticity that will disappear slurries are separated by filtration collection filterFilter residue is put into the baking oven that set temperature is 105 DEG C by slag, and dry 7h obtains hydro-thermal coke；Preparing 225mL mass concentrations isThe concentrated sulfuric acid solution that mass fraction is 85% is added in liquor potassic permanganate, adjusts permanganic acid by the liquor potassic permanganate of 8g/mLPotassium solution pH to 2.5, obtains acid permanganate soln, and acid permanganate soln is poured into water-bath, is heated to48 DEG C, 90g polyurethane foams is taken to be put into water-bath and polyurethane foam is made to be completely immersed in acid permanganate soln, impregnated3.5min obtains roughening polyurethane foam；Polyurethane foam will be roughened to be put into equipped with the oxalic acid solution that 175mL mass fractions are 5%Middle immersion is stirred with glass bar and squeezes roughening polyurethane foam 6min, taken out roughening polyurethane foam, washed 2 times with clear water,Polyurethane base-material is obtained, the tin chloride solution that 110mL mass fractions are 5% is prepared, 6g glass puttys, 35mL is added into tin chloride solutionMass fraction is 10% hydrochloric acid, obtains sensitizing solution, polyurethane base-material is put into sensitizing solution and impregnates 7min, obtain being sensitized poly- ammoniaEater base stocks；The hydrochloric acid that palladium chloride solution and mass fraction that mass concentration is 0.5g/L are 5% is mixed to get dispergation in equal volumeLiquid immerses above-mentioned sensitization polyurethane base-material in 135mL solution glues, after dispergation processing 4.5min, takes out, by dispergation, treatedPolyurethane base-material is put into the ammonium hypophosphite solution that 2100mL mass fractions are 45%, is impregnated 7min, is obtained activated urethanes glueLiquid；It counts in parts by weight, 45 parts of copper sulphate, 25 parts of hydro-thermal coke, 17 parts of glyoxalic acids, 65 parts of sodium tartrates, 45 parts of activation are poly-Urethane glue and 23 parts of sodium carbonate, which are put into 450 parts of deionized waters, to be disperseed, and 23min is mixed, obtains environmental friendly, anti-corrosive lossLearn copper plating bath.
Example 3
By 250mL solid masses content be 25% Mian Jiang liquid be put into the reaction kettle with air valve, seal reaction kettle, withThe Ventilation Rate of 50mL/min is passed through carbon dioxide gas into reaction kettle by air valve, ventilates and continue 15min, closes ventilationValve, is heated to 220 DEG C, and insulation reaction 8h obtains reaction mass；It is in mass ratio with quick lime by above-mentioned reaction mass10 ︰ 1 are mixed, and are heated to 90 DEG C, are cleared up 5min, are obtained the causticity slurries that disappear, and the causticity that will disappear slurries are separated by filtration collection filter residue,Filter residue is put into the baking oven that set temperature is 110 DEG C, dry 10h obtains hydro-thermal coke；Preparing 250mL mass concentrations isThe concentrated sulfuric acid solution that mass fraction is 85% is added in liquor potassic permanganate, adjusts permanganic acid by the liquor potassic permanganate of 10g/mLPotassium solution pH to 3, obtains acid permanganate soln, and acid permanganate soln is poured into water-bath, is heated to 50DEG C, 100g polyurethane foams is taken to be put into water-bath and polyurethane foam is made to be completely immersed in acid permanganate soln, are impregnated4min obtains roughening polyurethane foam；Polyurethane foam will be roughened to be put into the oxalic acid solution for being 5% equipped with 200mL mass fractionsIt impregnates, stirred with glass bar and squeezes roughening polyurethane foam 7min, take out roughening polyurethane foam, washed 3 times, obtained with clear waterTo polyurethane base-material, the tin chloride solution that 120mL mass fractions are 5% is prepared, 7g glass puttys, 40mL matter are added into tin chloride solutionThe hydrochloric acid that score is 10% is measured, sensitizing solution is obtained, polyurethane base-material is put into sensitizing solution and impregnates 8min, obtains sensitization polyurethaneBase-material；The hydrochloric acid that palladium chloride solution and mass fraction that mass concentration is 0.5g/L are 5% is mixed to get solution glue in equal volume,Above-mentioned sensitization polyurethane base-material is immersed in 150mL solution glues, after dispergation processing 5min, is taken out, by dispergation treated poly- ammoniaEater base stocks are put into the ammonium hypophosphite solution that 220mL mass fractions are 45%, are impregnated 10min, are obtained activated urethanes glue；It pressesParts by weight meter, by 50 parts of copper sulphate, 30 parts of hydro-thermal coke, 20 parts of glyoxalic acids, 70 parts of sodium tartrates, 50 parts of activated urethanes glueLiquid and 25 parts of sodium carbonate, which are put into 500 parts of deionized waters, to be disperseed, and 25min is mixed, and obtains environmental friendly, anti-corrosive erosion electroless copperLiquid.
Comparative example
With the chemical bronze plating liquid of company of Shenzhen production as a comparison case
The chemical bronze plating liquid in chemical bronze plating liquid and comparative example is lost to environmental friendly, anti-corrosive produced by the present invention to be detected, detection knotFruit is as shown in table 1：
As sample, the clean workpiece that will be plated is put into heated example 1~3 and comparative example product prepared by the present inventionIt into the sample of relevant temperature, is taken out after plating 2h, dries up, tested.
1st, reaction process
As sample, the clean workpiece that will be plated is put into heated example 1~3 and comparative example product prepared by the present inventionInto the sample of relevant temperature, unplated piece surface starts to generate the time of bubble, is denoted as starting reaction time T1.
The time that unplated piece surface is covered completely by copper, it is denoted as complete Plating times T2.
2nd, appearance
Visually observe the surface condition of each plating piece.
3rd, binding force is tested：
With ethyl alcohol（95%）100 grids are cut in wipe samples surface with cross-cut tester（Per grid size 1mm × 1mm）, use adhesive tapeIt is polished again with cotton after being adjacent to, stands 2min, vertically pulled with 90 ° in moment（It is required that it is：The range that comes off is less than test zone5%）.
4th, peel stress is tested：
Viscosity is evaluated with the cohesive force of base resin and plated film.After sintering, the plated copper film of acquisition is cut into size with cutterFor the test specimen of 2cm × 2cm × 2cm, according to printed circuit board test method JISC5012 Instron5564 testers measure withThe load capacity when rate of extension of an angle of 90 degrees and 50mm/min are removed.Test is repeated 4 times, and is averaged.
5th, workpiece corrosion is tested：
It after workpiece is dipped into the stipulated time, takes out, is first rinsed with tap water, then corrosion product is removed with hairbrush.After cleaning, useCoarse filter paper suck dry moisture, is placed in the plate for being lined with filter paper, is put into 50 DEG C of incubators, and dry 1h is gripped with tweezers, in smart on balanceReally weigh.Calculate rate of corrosion（R values）.
1 performance measurement result of table
From the data in table 1, it can be seen that when environmental friendly, anti-corrosive erosion chemical bronze plating liquid produced by the present invention carries out electroless copper, it is greatly improvedElectroless copper plating speed, so as to faster, stably obtain copper coating, and quality of coating is good, binding force is tough, to plating pieceCorrosivity is small.Without the noxious materials such as corrosive substances and formaldehyde such as strong acid and strong base, Ke Yiyou in the chemical bronze plating liquid of the present inventionEffect improves plating solution pollution problem.It is substantially better than comparative example product.Therefore, there is wide prospect of the application.