CN106609385A - High-filling acidic copper copper-plated brightener for electrocoppering - Google Patents
High-filling acidic copper copper-plated brightener for electrocoppering Download PDFInfo
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- CN106609385A CN106609385A CN201710146980.XA CN201710146980A CN106609385A CN 106609385 A CN106609385 A CN 106609385A CN 201710146980 A CN201710146980 A CN 201710146980A CN 106609385 A CN106609385 A CN 106609385A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
A high-filling copper-plated brightener for electrocoppering comprises at least the following materials by weight: 7 to 8 parts of dye compound, 3.4 to 3.6 parts of bis-(sodium sulfopropyl)-disulfide, 4.2 to 4.4 parts of tetra-sulfo-terephthalic acid salt, 1.8 to 2 parts of 1,4-butyne diol, 5.6 to 5.8 parts of thiomorpholine, 12 to 15 parts of tetrahydrofuran, and 85 to 88 parts of water.
Description
Technical field
The present invention relates to electroplating technology, more particularly to a kind of electro-coppering height fills and leads up brightening agent for acid copper electroplating.
Background technology
Plating is closely related with electrochemistry, organic chemistry, surface chemistry, crystallography, kinetics etc., is one comprehensive
Application technology.The main purpose of plating is to provide overcoat for part or material surface or change the surface characteristic of matrix material.
Change the surface characteristic of solid material by electroplating, outward appearance can be improved and improve corrosion resisting property, wear-resistant, antifriction increases hard
Degree, there is provided the surface characteristic such as special magnetic, electrical, optical, heat and other physical properties etc., it might even be possible to match somebody with somebody for improving machinery
Close, repair part that worn-out and processing is scrapped etc., thus industrially obtain a wide range of applications.Plating is actually one kind
Metal electrodeposition process, exactly obtains on a solid surface the process of metal deposition layer by electrolytic method.
Copper coating pinkiness, uniform, careful, the copper coating tone that different process is plated out is different.Copper coating master
To be used for doing prime coat, intermediate deposit, it is also possible to do overlay coating.Typically require that copper plate has good adhesion with matrix,
Coating is bright, smooth, careful, thickness uniform, and has good flexibility and ductility.
The copper-plating technique for using at present mainly has cyanide copper plating, hydrosulphate copper facing and pyrophosphate copper plating etc., often
Planting technique respectively has feature.Basic demand to copper plating bath is：Plating solution has good dispersibility and covering power and light
And leveling ability, electric current density use range width, stablize, it is easy to maintenance, it is high to the tolerance of impurity.Acidiccopper plating extensively should
For the bottom that Protective-deeorative plating, plastic electroplating, electroforming and printed wiring board hole metallization thicken plating and graphic plating
Coating, but can not on zinc, iron-based body Direct Electroplating.
Effect according to additive can be divided into following four class：The first kind is polysulfide organic sulfonate, such as poly- two sulfur of phenyl
Propane sulfonic acid sodium, sodium polydithio-dipropyl sulfonate, their Main Function is to improve electric current density and make coating crystal grain refinement.The
Two classes are the heterocyclic compound containing sulfenyl, such as 2- tetrahydro-thiazoles thioketone, 2- imidazole thiones, 2-mercaptobenzimidazole, and they can be
Wider temperature range is used, particularly evident to the brightness effect in low current density area.3rd class is polyether surfactant,
Such as Polyethylene Glycol, the cathodic polarization effect of plating solution can be improved.4th class is the derivant of aromatic sulphonate, such as dodecyl
Sodium sulfonate, the bright range that low current density area can be expanded and the frosted state for eliminating coating surface.
Effect according to additive in liquid is crossed can be divided into brightener, leveling agent, surfactant etc..Brightener also known as
Accelerator or grain refiner, can produce high overpotential and ensure high adatome degree of supersaturation or logical by increasing polarization
Cross this to cause the randomness that adatome enters lattice to increase or hinder adatome to spread to growth center in surface adsorption,
Coating to obtaining bright and smooth has certain effect.
Leveling agent is difficult to distinguish clear with brightener, and their common ground is the presence of-C=C- ,-C ≡ in molecular structure
The unsaturated bonds such as C- ,-N=N- and π keys.Research thinks have because there is conjugated structure in the dye molecule with azo group
Leveling effect, and conjugation is bigger, and Surface flat is better.Such as crystal violet, Janus green B, phenazine dyes.Leveling agent and copper from
Son equally carries very strong electropositive, it is easy to by sorption in plating piece surface current density eminence, make copper atom in high current
Place is difficult to stop over, and the copper facing in low current area is not so affected again so that originally up-and-down surface becomes flat.
Surfactant reduces to a certain extent the surface tension of parent metal, makes additive be easy to absorption, can be with
Increase the dispersibility of solution.There is the class of derivant two of polyethers and aromatic sulphonate in the surfactant applied at present,
It is conventional have Polyethylene Glycol, dodecyl sodium sulfate, octyl phenol polyglycol ether (OP is serial), the quaternary ammonium salt of polyethyleneimine,
Polyethylene Glycol formal etc..
The coating for obtaining, it is necessary to the plating solution having had, and play a major role is brightener.Brightener includes that key light is bright
Agent, surfactant and leveling agent.Main brightener is mostly organic sulfur compound, and it can improve the covering power and hole wall of plating solution
Structure, affects the crystalline structure of layers of copper.But these organic sulfur compounds are also mixed in coating or are mixed on lattice, under making ductility
Drop, fragility is raised, and the catabolite of especially these brighteners is changed into different objectionable impurities and remains in plating solution, also more or less
In being clipped in coating.The carrier of brightener is mostly the larger surfactant of molecular weight, such as Polyethylene Glycol, OP emulsifying agents, they
The nonionic surfactant being made up of hydrophilic group and hydrophobic group.It can improve the cathodic polarization effect of plating solution, reduce
Plating solution and base metal surface tension force, make to be easy to plated with copper.But they have very strong characterization of adsorption in copper facing layer surface again, so as to
There is hydrophobic film in the copper coating surface for making light, affects the adhesion of other coating.Leveling agent in brightener mostly is jeterocyclic chemistry
Compound and dyestuff, such as crystal violet, phenolphthalein etc..The leveling performance of their brightness and solution to low current density area has notable shadow
Ring, these leveling agents dissolubility in water is little, to be first dissolved in after ethanol mixing with other components again, plays a secondary role.
For the low copper system of peracid, in the case of low current area and plating piece surface texture complexity, the items of its coating
Can not as good as low sour high-copper system, most prominent performance is the low copper system of peracid in low current area coating and parent metal adhesion
Difference, causes that ductility of electrodeposited film is poor, low intensity, and low sour high-copper system can well overcome these deficiencies.But peracid copper facing system
Deep plating it is more preferable with covering power.
The use temperature range of existing electro-coppering brightener is narrow, and coating easily plays pit, the pliability of copper coating and
Bright property is general.
The content of the invention
In order to solve prior art problem, it is bright that a kind of electro-coppering height of a first aspect of the present invention offer fills and leads up sour bronzing
Agent, in parts by weight, it at least contains dye composition 7-8 parts, sodium polydithio-dipropyl sulfonate 3.4-3.6 parts, tetrathio pair
Phthalate 4.2-4.4 parts, 1,4- butynediols 1.8-2 parts, thiomorpholine 5.6-5.8 parts, tetrahydrofuran 12-15 parts, water
85-88 parts.
In some embodiments, in parts by weight, it at least contains 7.4 parts of dye composition, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 4.2 parts of tetrathio terephthalate, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, 15 parts of tetrahydrofuran,
85 parts of water.
In some embodiments, the dye composition is thiazine dye.
In some embodiments, the tetrathio terephthalate is tetrathio terephthaldehyde's acid ammonium salt.
In some embodiments, the tetrathio terephthalate is tetrathio p-phthalic acid 4-butyl ammonium.
A second aspect of the present invention provides a kind of electro-coppering electroplate liquid, and comprising electro-coppering height as above acid is filled and led up
Copper brightener.
In some embodiments, its composition includes copper sulfate 180-220g/L, sulphuric acid 30-45mL/L, chloride ion 80-
150mg/L, electro-coppering height fill and lead up brightening agent for acid copper electroplating 4-6mL/L.
In some embodiments, its composition includes copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, plating
Copper height fills and leads up brightening agent for acid copper electroplating 4.8mL/L.
In some embodiments, temperature when it is used is 15-40 DEG C.
In some embodiments, electric current density when it is used is 1-6A/dm3。
The electro-coppering height that the present invention is provided fills and leads up brightening agent for acid copper electroplating, quickly goes out light, fills and leads up ability extra-heavy, electronegative potential area
Can quickly fill and lead up.The effect that walks is good, and electronegative potential area is not easy the mist that blacks or send out.Bath stability, easy operational control.Coating is flexible
Property is good, pin hole or pit is not likely to produce, with good corrosion resisting property.Suitable for electroplate lamp decoration, iron pipe, furniture, sanitary ware,
Handware etc. requires to fill and lead up stronger workpiece.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
Quality, concentration, temperature, time or other values or parameter are preferred with scope, preferred scope or a series of upper limits
During the Range Representation that value and lower preferable values are limited, this is appreciated that and specifically discloses by any range limit or preferred value
The all scopes formed with arbitrary pairing of any range lower limit or preferred value, regardless of whether whether the scope separately discloses.
For example, the scope of 1-50 be understood to include selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,
19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、
44th, 45,46,47,48,49 or 50 any numeral, number combinatorics on words or subrange and all between above-mentioned integer
Fractional value, for example, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.With regard to subrange, specifically consider from scope
Interior any end points starts " the nested subrange " for extending.For example, the nested subrange of exemplary range 1-50 can include
1-10,1-20,1-30 and 1-40 on one direction, or 50-40,50-30,50-20 and the 50-10 on other direction.
A first aspect of the present invention provides a kind of electro-coppering height and fills and leads up brightening agent for acid copper electroplating, and in parts by weight, it at least contains
Have dye composition 7-8 parts, sodium polydithio-dipropyl sulfonate 3.4-3.6 parts, tetrathio terephthalate 4.2-4.4 parts, 1,
4- butynediols 1.8-2 parts, thiomorpholine 5.6-5.8 parts, tetrahydrofuran 12-15 parts, water 85-88 parts.
In some embodiments, in parts by weight, it at least contains 7.4 parts of dye composition, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 4.2 parts of tetrathio terephthalate, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, 15 parts of tetrahydrofuran,
85 parts of water.
In some embodiments, the dye composition is thiazine dye.
The thiazine dye is that methylene blue or methylene are green.
Sodium polydithio-dipropyl sulfonate is obtained by the Material synthesis comprising 1,3- propane sultones.1,3- propane sultones
Synthetic method it is as follows：120g sodium sulfite is dissolved in 200mL pure water, in pouring 500mL three-necked bottles after heating for dissolving into, is opened
Dynamic agitator, with sulfur acid for adjusting pH to subacidity, is passed through air, makes reactant liquor be changed into milky.By 20mL propenyls and cold
The dilute sulfuric acid mixing of 20mL 10wt%, pours Dropping funnel into, and after sodium sulfite liquid is cooled to room temperature Deca inward, time are started
In 1.5-2h, reaction maintains pH value 6.5 or so automatically for control.PH value is adjusted to 2 or so, heating is concentrated after dripping off with dilute sulfuric acid
To the 1/3 of original volume, cooling removes sodium sulfate crystal, obtains hydroxypropanesulfonic acid sodium, adds 60mL concentrated hydrochloric acid and 80mL ethanol, stirs
Uniform rear standing is mixed, crystallization Sodium Chloride is filtered off, filtrate carries out vacuum distillation and removes solvent and hydrochloric acid, obtains rufous oily hydroxyl third
Sulfonic acid.In being then placed in 50mL three-necked bottles, under reduced pressure more than 100 DEG C are heated to hot oil bath, make hydroxy-propanesulfonic acid be dehydrated shape
Into 1,3- propane sultones.
The synthetic method of sodium polydithio-dipropyl sulfonate is, 15g sodium sulfide is added in 50mL three-necked bottles, in boiling water bath plus
Heat dissolves it, and Cosan 1.2g is dividedly in some parts under agitation, continues to stir to being changed into dark red liquid after adding.In 250mL
100mL ethanol is added in three-necked bottle, above-mentioned solution is slowly poured into wherein under agitation, obtain yellow green suspension, Ran Hou
The lower Deca 10.5g PS of stirring, temperature control obtains white slurry body, filters below 50 DEG C, and drying is obtained
To white powder sodium polydithio-dipropyl sulfonate.
The early stage of acid bright copper plating exploitation uses the brightener of the single addition of multicomponent, i.e. MSHOD systems and SBP
System.In MSHOD systems, M is methyl blue, and S is polydithio-dipropyl sulfonate, and H is 2-mercaptothiazoline, and O is polyoxy second
Allylic alkylation 2, 2-Oxydiphenol, D is sodium metnylene bis-naphthalene sulfonate.In SBP systems, S is poly- dithiopropane sulfonate, and B is ethyl thiourea, P
It is Polyethylene Glycol.These components are all added separately in plating solution, and consumption is mostly per liter several milligrams, is reached by synergism
To leveling and the purpose of light.
Existing Technology Bright Acidic agent at present is compound additive by single component package development.The one-component of early stage adds
Plus agent all develops into the intermediate of acid copper plating brightening agent.The mechanism of action of brightener is probably fine grain theory, crystal plane orientation
Theoretical, colloid film theory and electronics flow freely theoretical.Brightener has certain increase polarization, and light is due to crystal grain
Visible wavelength is smaller in size than, and is caused with the structure for necessarily aligning, this structural plane should be parallel to surface.Plated film
Gloss depend not only on coated surface or whether body surface smooths, and depending on the miniaturization of plated film crystal grain, reaching can
See the degree of light not irregular reference.
There is substantial connection between polarization behavior and bright property.Overpotential is bigger, and the easier formation of nucleus, the size of nucleus is got over
It is little, crystallize finer and close.Brightener fundamental characteristics is that in wider potential range, have great absorption in coating surface, is risen
To the effect for affecting coating crystallization process, that is, increase polarization, bright property is better.The strong and weak direct acting factor of bright property is crystal grain
Size, crystal grain orientation, the structural constituent at interface；Indirect acting factor is the suction type of additive, adsorbs on strong and weak, electrode
Size of cooperative effect etc. between electrochemical behavior and each component.
The factor for producing dislocation and nucleation increase can be caused all to play a part of crystal grain thinning.Additive is by increase
Polarization, produces high overpotential and ensures high adatome saturation, or causes atom to enter lattice in surface adsorption by this
Randomness increase or hinder adatome to growth center spread.Crystal grain refinement can significantly improve coating performance.
It is thicker that the leveling effect of electroplating additive refers to that electroplate liquid is deposited at the local dent of metal surface, at convex protrusion
The ability for depositing relatively thin.It is divided into macroscopic view leveling and microcosmic leveling, and the former is made by uniform CURRENT DISTRIBUTION on metal surface
Into now geometric profile of the thickness of diffusion layer along surface is uniformly distributed, i.e. the thickness of diffusion layer is equal everywhere.And the latter be by
The electric current density of the recess on electrode surface more than caused by the electric current density at convex protrusion, now the border of diffusion layer from
It is smooth to open at a certain distance from electrode surface, and in the thickness of coating of recess the thickness of coating at convex protrusion is more than.The work of leveling
It is theoretical mainly according to diffusion control resistanceization with mechanism.Absorption leveling agent molecule at the electrode surface in electrodeposition process not
Disconnected to consume, diffusion of its depletion rate than leveling agent from solution bulk to electrode surface is very fast, i.e., its leveling effect is to be spread
Control.
Chloride ion can form precipitation and coordination compound with cuprous ion.Chloride ion energy and Cu+Form water-fast Cu2Cl2It is heavy
Form sediment, reduce Cu2O is adhered on negative electrode.Chloride ion can also increase polarization, reach refinement coating crystallization, improve crystal habit,
The purpose of orientation.But the content of chloride ion can not be too high, can not be too low.In general, when the content of chloride ion is less than
During 30mg/L, it is impossible to form complete film layer, do not reach effect.When the content of chloride ion is more than 120mg/L, can be formed again molten
In the CuCl of water2 -、CuCl3 2-、CuCl4 3-Deng, on the contrary increase cathode current, cause the coarse tarnish of coating.
The content of chloride ion can be by adding hydrochloric acid to adjust.
Chloride ion is additive indispensable in acid bright copper plating, and general consumption is 20-80mL/L.The salt acidic plating of sulphuric acid
The chloride ion of addition appropriate amount changes the discharge type of adsorbable complex in copper, shows that chloride ion passes through ionic bridge mechanism shape
Into tridimensional network and participate in electric discharge, so as to block the discharge process of copper ion, control copper crystallization and grow up speed, from
And make coating show good performance.If without this effect of chloride ion, under the leveling performance of plating solution and brightness all meetings
Drop, easily produces dendroid coating.But if chloride ion excess, the brightness of coating also can decline, and can increase light
The consumption of agent.Presence of the chloride ion in acid copper-plating can make the OCP of acid copper-plating shuffle 10mV or so, be conducive to electricity
Son is oriented to copper ion from electrode, improves the concentration of electrode surface copper ion, reduces cathode chamber electric double layer electric smelting and reduces activation pole
Change, be conducive to the growth of nucleus, thicker crystal grain is obtained, be conducive to eliminating the stress of coating.Chloride ion is helped as catalyst
Brightener is helped to plate out smooth, bright, fine and close copper coating.Without chloride ion or during too low chloride ion content, the brightness of coating and
The leveling ability of plating solution declines, and coating easily ups and downs striped occurs in high, middle voltage belt, and has mist in electronegative potential area
Shape is deposited.When chloride ion content is too high, the brightness of coating and degree of filling and leading up can be weakened, and low current density area does not work, and anode
Surface will generate copper chloride, form one layer of canescence thin film, cause anodic passivity.Appropriate chloride ion can be used to precipitate C u+,
To avoid Cu+Uneven and the expansion of semi-gloss clear zone the negative interaction of brightness for causing, while promoting anodic solution normally to feed plating
Cu in liquid2+, make Cu in plating solution2+Tend to normal.
There is cooperative effect in chloride ion and electroplating additive, chloride ion and many additives are used in combination all in copper deposition
Decline can coating stress.During chloride ion individualism, not only do not play and act on, or even also opposite effect；If but only
In the presence of additive, similarly cannot get the copper coating of light；If it is used in combination with additive, polarizability can be increased,
The negative shifting of polarization potential is made, coating bright property and Surface flat is improved.
In some embodiments, the tetrathio terephthalate is tetrathio terephthaldehyde's acid ammonium salt.
In some embodiments, the tetrathio terephthalate is tetrathio p-phthalic acid 4-butyl ammonium.
The synthetic method of tetrathio p-phthalic acid 4-butyl ammonium is, by 10mmol Isosorbide-5-Nitraes-be dispersed in benzyl dichloride
In 30mL methanol, 42mmol sulfur and 22mmol Feldalat NMs are added, be heated to reflux 15h.Filtration after having reacted, adds in filtrate
30mL chloroforms, add hydrochloric acid, until solution layering occurs and upper strata becomes colourless.Lower floor's solution is separated with separatory funnel, is used
Solution is concentrated into 2mL by Rotary Evaporators, is subsequently adding the TBAH aqueous solution of 10mL mass fractions 25%, then will
Solvent is evaporated, and obtains final product.Yield 82%.
A second aspect of the present invention provides a kind of electro-coppering electroplate liquid, and comprising electro-coppering height as above acid is filled and led up
Copper brightener.
In some embodiments, its composition includes copper sulfate 180-220g/L, sulphuric acid 30-45mL/L, chloride ion 80-
150mg/L, electro-coppering height fill and lead up brightening agent for acid copper electroplating 4-6mL/L.
In some embodiments, its composition includes copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, plating
Copper height fills and leads up brightening agent for acid copper electroplating 4.8mL/L.
In plating solution, sour copper ratio is most important.Copper sulfate is the main salt in electroplate liquid, there is provided copper ion, so that in workpiece
Copper coating is reduced on surface.Copper content is too low in plating solution, and response speed slows down, and the amount for depositing copper is few, it is impossible to which matrix is complete
Cover, reduce the brightness of coating, and displacement reaction can occur, cause binding force of cladding material to decline, be also easy in high potential area
Cause to burn phenomenon.When copper content is too high, response speed is accelerated, and layers of copper is loose, and adhesion is bad, but also can reduce plating solution
Dispersibility, meanwhile, copper sulfate is possible to crystallization and separates out, and is led to anode polarization.
Sulphuric acid can improve the electric conductivity and current efficiency of plating solution, because sulphuric acid is a kind of strong electrolyte, in certain model
Interior its content of raising is enclosed, it is possible to decrease the ratio resistance of solution, while also ensuring that the normal dissolving of anode.Due to common-ion effect,
It can reduce the valid density of copper ion, improve cathodic polarization effect, improve the dispersibility of plating solution.Sulfuric acid concentration is too low,
Solution conductivity performance is poor, and solution dispersibility declines, and anode is it is possible that the incomplete oxidation of copper, generates Cu2O, makes coating
There is burr；It is too high, the mobility of copper ion can be reduced, efficiency is reduced, unfavorable to the percentage elongation of copper coating, and coating
Glossiness and Surface flat decline.
The addition of brightener can not it is too high can not be too low, a certain amount of bright agent content can improve the crystal grain of copper coating
Tissue, plays the special role of brightener, and makes coating obtain desired Surface flat.If addition is too low, do not have
Light is stated, is flattened and is uniformly acted on.If adding too much, the product for coming is decomposited from it can be caused copper coating embrittlement, take off
The phenomenons such as layer.
In some embodiments, temperature when it is used is 15-40 DEG C.
The operation temperature of sulfate bright copper plating has much relations with the species of the brightener for being adopted.Due to electroplating process
Middle generation heat, summer operation needs to lower the temperature slightly, and winter then somewhat heats.Operation temperature is too low, and copper sulfate will be tied
Partial crystallization goes out, and electric current density declines, and electroplating velocity slows down.Operation temperature is too high, reduces can bright range, or even cannot light
Coating, copper coating sends out mist or coarse, and brightener decomposes to be accelerated.
In some embodiments, electric current density when it is used is 1-6A/dm3。
It should be noted that the superposition of single additive component effect and it is not equal to the effect of additive package, sometimes very
Effect to one-component is contrary with multicomponent synergism.Therefore the selection of each component is not in the additive of electro-coppering
It is conventional to select, inventor substantial amounts of it was found that, the change of some parameters and component can cause larger change, even
Contrary result, will obtain suitable formula and have to pay creative work.
During the present invention is completed, inventor is found surprisingly that tetrathio p-phthalic acid 4-butyl ammonium can increase
Temperature range is used during big plating, not only with splendid bright performance and performance is filled and led up, pit will not be also produced on coating,
The brightness effect of low current density areas is clearly.Realize light, flatten, the effect that walks it is three-in-one, make the present invention offer
Electro-coppering electroplate liquid is broadened using the scope of temperature, reaches 15-40 DEG C.This may be with tetrathio p-phthalic acid TBuA
Delocalized electron in salt is relevant, reduces the energy required for electron transition.Simultaneously the radius of sulphur atom is larger, can with copper from
The radius size matching of son, enhances three-in-one effect.Isosorbide-5-Nitrae-butynediols and thiomorpholine can aid in dye composition, gather
The propane sulfonic acid sodium of two sulfur two obtains bright speed faster.It is high electro-coppering to be adjusted after tetrahydrofuran and the mixing of water certain proportion
Fill and lead up the polarity of bright agent solution.
The electro-coppering that the present invention is provided is easily controlled with electroplate liquid, goes out light soon, and coating degree of filling and leading up is splendid.Coating is not likely to produce
Pin hole, internal stress is low, rich ductility.Current density range is broad, and coating degree of filling and leading up may be up to 80%, up to cause brightness effect.It is heavy
Product speed is express, under the electric current density of 4.5 amperes/square decimeter, the layers of copper for plating 1 micron per minute, electroplating time thus
Shorten.Plating layer resistivity is low, therefore is very suitable for the electronics industry high to coating physical property requirements.Can be applicable to various differences
The parent metal of type, ironware, zinc alloy piece, plastic parts etc. are equally applicable.Impurity Tolerance is high, typically using a period of time
(about 800-1000 ampere-hours/liter) after, just need to be processed with activated carbon powder.
The present invention is expanded on further with reference to specific embodiment.
The synthetic method of tetrathio p-phthalic acid 4-butyl ammonium is in embodiment, by 10mmol Isosorbide-5-Nitraes-to benzyl dichloride
In being dispersed in 30mL methanol, 42mmol sulfur and 22mmol Feldalat NMs are added, be heated to reflux 15h.Filtration after having reacted, in filtrate
30mL chloroforms are added, hydrochloric acid is added, until solution layering occurs and upper strata becomes colourless.It is molten lower floor to be separated with separatory funnel
Liquid, 2mL is concentrated into Rotary Evaporators by solution, and the TBAH for being subsequently adding 10mL mass fractions 25% is water-soluble
Liquid, then solvent is evaporated, obtain final product.Yield 82%.
Embodiment 1
Electro-coppering height fills and leads up brightening agent for acid copper electroplating, in parts by weight, containing 7.4 parts of methylene blue, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 4.2 parts of tetrathio p-phthalic acid 4-butyl ammonium, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, tetrahydrochysene
15 parts of furan, 85 parts of water.
Embodiment 2
Electro-coppering height fills and leads up brightening agent for acid copper electroplating, in parts by weight, containing methylene is green 7.4 parts, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 4.2 parts of tetrathio p-phthalic acid 4-butyl ammonium, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, tetrahydrochysene
15 parts of furan, 85 parts of water.
Embodiment 3
Electro-coppering height fills and leads up brightening agent for acid copper electroplating, in parts by weight, containing 7 parts of methylene blue, polydithio-dipropyl sulfonic acid
3.4 parts of sodium, 4.4 parts of tetrathio p-phthalic acid 4-butyl ammonium, 1.8 parts of 1,4- butynediols, 5.6 parts of thiomorpholine, tetrahydrochysene
12 parts of furan, 88 parts of water.
Embodiment 4
Electro-coppering height fills and leads up brightening agent for acid copper electroplating, in parts by weight, containing 7.4 parts of methylene blue, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 3.2 parts of tetrathio p-phthalic acid 4-butyl ammonium, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, tetrahydrochysene
15 parts of furan, 85 parts of water.
Embodiment 5
Electro-coppering height fills and leads up brightening agent for acid copper electroplating, in parts by weight, containing 7.4 parts of methylene blue, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 5.8 parts of tetrathio p-phthalic acid 4-butyl ammonium, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, tetrahydrochysene
15 parts of furan, 85 parts of water.
Embodiment 6
Electro-coppering height fills and leads up brightening agent for acid copper electroplating, in parts by weight, containing 7.4 parts of methylene blue, polydithio-dipropyl sulphur
3.6 parts of sour sodium, 2 parts of 1,4- butynediols, 5.8 parts of thiomorpholine, 15 parts of tetrahydrofuran, 85 parts of water.
Embodiment 7
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, embodiment 1
4.8mL/L。
Embodiment 8
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, embodiment 2
4.8mL/L。
Embodiment 9
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, embodiment 3
4.8mL/L。
Embodiment 10
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, embodiment 4
4.8mL/L。
Embodiment 11
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, embodiment 5
4.8mL/L。
Embodiment 12
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 115mg/L, embodiment 6
4.8mL/L。
Embodiment 13
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 150mg/L, embodiment 1
4.8mL/L。
Embodiment 14
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 150mg/L, embodiment 4
4.8mL/L。
Embodiment 15
Electro-coppering electroplate liquid, including copper sulfate 190g/L, sulphuric acid 32mL/L, chloride ion 150mg/L, embodiment 5
4.8mL/L。
Tested with HL-10AT Hulls groove experiment instrument, electric current density is 1-6A/dm3.Electroplating time is 1-10min, temperature
Spend for 15-40 DEG C.Observation coating surface, is recorded as bright, half light, dark, ribbon, coarse, powder, foaming, pit, dew
Bottom.Test result is listed in the table below.
| Electro-coppering electroplate liquid | Temperature DEG C | Electric current density A/dm3 | Time min | Effect |
| Example 7 | 40 | 1 | 2 | Light |
| Example 7 | 40 | 4.5 | 2 | Light |
| Example 8 | 35 | 2 | 2 | Light |
| Example 9 | 30 | 3 | 2 | Light |
| Example 10 | 25 | 4 | 5 | Half light |
| Example 11 | 20 | 5 | 8 | Half light |
| Example 12 | 15 | 6 | 2 | Secretly |
| Example 12 | 15 | 1 | 2 | Powder |
| Example 13 | 30 | 4.5 | 2 | It is coarse |
| Example 13 | 30 | 1 | 2 | Pit |
| Example 14 | 30 | 4.5 | 2 | Foaming |
| Example 14 | 30 | 1 | 2 | It is show-through |
| Example 15 | 30 | 4.5 | 2 | Pit |
| Example 15 | 30 | 1 | 2 | It is show-through |
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology will be formed due to language performance inaccurate reason and not
The possible equivalent or son being presently considered is replaced, and these changes also should be interpreted in the conceived case by appended
Claim is covered.
Claims (10)
1. electro-coppering height fills and leads up brightening agent for acid copper electroplating, it is characterised in that in parts by weight, and it at least contains dye composition 7-8
Part, sodium polydithio-dipropyl sulfonate 3.4-3.6 parts, tetrathio terephthalate 4.2-4.4 parts, 1,4- butynediols 1.8-2
Part, thiomorpholine 5.6-5.8 parts, tetrahydrofuran 12-15 parts, water 85-88 parts.
2. electro-coppering height as claimed in claim 1 fills and leads up brightening agent for acid copper electroplating, it is characterised in that in parts by weight, and it is at least
Containing 7.4 parts of dye composition, 3.6 parts of sodium polydithio-dipropyl sulfonate, 4.2 parts of tetrathio terephthalate, 1,4- butine
2 parts of glycol, 5.8 parts of thiomorpholine, 15 parts of tetrahydrofuran, 85 parts of water.
3. electro-coppering height as claimed in claim 1 fills and leads up brightening agent for acid copper electroplating, it is characterised in that the dye composition is thiophene
Piperazine dyestuff.
4. electro-coppering height as claimed in claim 1 fills and leads up brightening agent for acid copper electroplating, it is characterised in that the tetrathio terephthaldehyde
Hydrochlorate is tetrathio terephthaldehyde's acid ammonium salt.
5. electro-coppering height as claimed in claim 3 fills and leads up brightening agent for acid copper electroplating, it is characterised in that the tetrathio terephthaldehyde
Hydrochlorate is tetrathio p-phthalic acid 4-butyl ammonium.
6. a kind of electro-coppering electroplate liquid, it is characterised in that comprising the electricity as described in any one of claim 1-5 claim
Copper facing height fills and leads up brightening agent for acid copper electroplating.
7. electro-coppering electroplate liquid as claimed in claim 6, it is characterised in that its composition include copper sulfate 180-220g/L,
Sulphuric acid 30-45mL/L, chloride ion 80-150mg/L, electro-coppering height fill and lead up brightening agent for acid copper electroplating 4-6mL/L.
8. electro-coppering electroplate liquid as claimed in claim 6, it is characterised in that its composition includes copper sulfate 190g/L, sulphuric acid
32mL/L, chloride ion 115mg/L, electro-coppering height fill and lead up brightening agent for acid copper electroplating 4.8mL/L.
9. electro-coppering electroplate liquid as claimed in claim 6, it is characterised in that temperature when it is used is 15-40 DEG C.
10. electro-coppering electroplate liquid as claimed in claim 6, it is characterised in that electric current density when it is used is 1-6A/
dm3。
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| CN108642534A (en) * | 2018-05-29 | 2018-10-12 | 韶关硕成化工有限公司 | VCP vertical continuous copper plating additives |
| CN109666954A (en) * | 2019-03-05 | 2019-04-23 | 惠州市鸿泰达电子材料有限公司 | A kind of tin plating additive and preparation method thereof |
| CN111058065A (en) * | 2020-01-17 | 2020-04-24 | 浙江金欣新材料科技股份有限公司 | Composite electroplating brightener and preparation method thereof |
| CN111793810A (en) * | 2020-07-22 | 2020-10-20 | 六安市金安区宝德龙科技创新有限公司 | Slightly-acidic brightening agent for bright copper plating of plating solution and preparation method thereof |
| CN112301386A (en) * | 2019-08-02 | 2021-02-02 | 丹阳市华美可化工有限公司 | Non-dye type environment-friendly bright acidic copper plating additive and application thereof in preparation of plating solution |
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| CN108642534A (en) * | 2018-05-29 | 2018-10-12 | 韶关硕成化工有限公司 | VCP vertical continuous copper plating additives |
| CN109666954A (en) * | 2019-03-05 | 2019-04-23 | 惠州市鸿泰达电子材料有限公司 | A kind of tin plating additive and preparation method thereof |
| CN112301386A (en) * | 2019-08-02 | 2021-02-02 | 丹阳市华美可化工有限公司 | Non-dye type environment-friendly bright acidic copper plating additive and application thereof in preparation of plating solution |
| CN111058065A (en) * | 2020-01-17 | 2020-04-24 | 浙江金欣新材料科技股份有限公司 | Composite electroplating brightener and preparation method thereof |
| CN111793810A (en) * | 2020-07-22 | 2020-10-20 | 六安市金安区宝德龙科技创新有限公司 | Slightly-acidic brightening agent for bright copper plating of plating solution and preparation method thereof |
| CN113026065A (en) * | 2021-02-20 | 2021-06-25 | 鞍山市同益光电科技有限公司 | Production process of copper plating additive |
| CN115094490A (en) * | 2022-07-21 | 2022-09-23 | 惠州市泛亚精饰新材料有限公司 | Method for manufacturing sulfuric acid copper plating brightener with high leveling and quick brightening |
| WO2024016330A1 (en) * | 2022-07-22 | 2024-01-25 | 扬州纳力新材料科技有限公司 | Cyanide-free copper plating grain refiner, cyanide-free copper plating solution, preparation method therefor, and application thereof |
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