CN107460459A - A kind of Nanometer Copper activating solution and preparation method thereof - Google Patents
A kind of Nanometer Copper activating solution and preparation method thereof Download PDFInfo
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- CN107460459A CN107460459A CN201710513891.4A CN201710513891A CN107460459A CN 107460459 A CN107460459 A CN 107460459A CN 201710513891 A CN201710513891 A CN 201710513891A CN 107460459 A CN107460459 A CN 107460459A
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- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
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- 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of Nanometer Copper activating solution, technique is simple, is sufficiently mixed the reducing agent and stabilizer, prepares the Nanometer Copper activating solution that stability is good, activation capacity is strong.The Nanometer Copper activating solution of the present invention, using nano copper particle as activated centre, used reducing agent can avoid nanometer copper particle from being oxidized, and Nanometer Copper activating solution is had strong inoxidizability.It is charge that used stabilizer can improve nanometer copper particle, prevent from reuniting between particle, be that Nanometer Copper activating solution has long-time stability, storage time was up to more than 2 years.Compared with existing colloid palladium, the Nanometer Copper activating solution of the inventive method, using cheap metallic copper as activated centre, dispergation processing need not be carried out in use, simplifies the use step of activating solution, technique is simple, green.
Description
Technical field
Present invention relates particularly to a kind of non-metal base plate chemical plating Nanometer Copper activating solution and preparation method thereof, belongs to metal electricity
Coating technology field.
Background technology
Most important application is the conductive interconnection metal in circuit board (PCB) manufacturing process to electroless copper in the electronics industry
Change.But PCB substrate is insulating materials, to make the conductive interconnection that circuit is realized between bilayer or multilayer circuit board, just must be right
Metallization process is carried out in insulating substrate hole wall；And electroless plating technology can then carry out the heavy of conductive metal layer on insulated substrate
Product, form conducting wire.During whole Electroless Plating Procedure, activation is a step of most critical.Activation step is that can decision
Carry out electroless copper plating, and the prerequisite of coat of metal electric conductivity quality.Because intrinsic urge is not present in insulated substrate surface
Change avtive spot, before electroless copper, it is necessary to which activation process is carried out to insulated substrate.In activation step, activated species are first
First adsorb on the insulated substrate after roughening and pre-preg.Then, the Cu ions in chemical plating fluid are being insulated with adsorbing
Centered on activated species on substrate, catalytic oxidation-reduction is into metallic copper in the presence of formaldehyde or other material reducing agents
Grain, then metal copper layer is reduced into the further autocatalysis of the copper particle of reduction, it is uniformly deposited on insulated substrate surface.Chemistry
Plating directly influences quality, integrality, adhesion and the outward appearance of insulated substrate surface chemical plating layers of copper with the quality of activating solution.
In theory, the metal such as Cu, Ni, Au, Ag, Rh, Pt and Pd all has certain catalytic activity, but due to adsorption capacity,
The reason for activation capacity, mithridatism and long-time stability etc., such as noble metal of only a small amount of good in oxidation resistance, Ag, Pd
It is used for chemical plating activated catalyst.Chemical plating catalyst mainly has divalence precious metal salt activating solution, the step of sensitization-activation two at present
Method activating solution, colloidal pd activation solution, ionic palladium activating solution etc., wherein, it is extensive to be applied with Pd/Sn colloidal activation solutions.Pd/Sn glue
Body activating solution is with Sn2+Ion coated is adsorbed in Sn in metal Pd core, then with counter ion Cl-2+Top layer, prevented based on electrostatic effect
Reunite between colloidal particle, have the function that to stablize whole colloidal particle.Just because of Sn2+It is coated on metal Pd particle table
Face, contact of the Pd active materials with chemical plating fluid is shielded, is needed before electroless copper to having adsorbed on insulated substrate
Pd/Sn colloids carry out appropriate dispergation processing, remove the Sn on surface2+, Pd active materials are exposed, can be effectively catalyzed
Copper ion is reduced into metal copper atom.
But in the plating solution after long-term use, it is coated on the Sn of Pd particle surfaces2+Stabilized zone, easily it is dissolved
O in the solution2Be oxidized to Sn4+, make to precipitate between Pd/Sn colloids, reduce the long-time stability of activating solution.Tradition
Pd/Sn colloidal pd activation solution costs it is high, expensive, stability is poor, environmental pollution is big.
The content of the invention
Based on problem above, it is an object of the invention to provide a kind of technique is simple, production efficiency is high, properties of product are stable and
The preparation method of the low chemical plating Nanometer Copper activating solution of production cost.
A further object is to provide a kind of high-performance, green chemical plating nanometer copper activity liquid and preparation method thereof.
According to the preparation method of the Nanometer Copper activating solution of the present invention, comprise the following steps：
(1) reducing agent and stabilizer are dissolved in solvent, keep heating, and constantly stirred, obtain mixed liquor；
(2) in a heated condition, copper salt solution is added in the mixed liquor that step (1) obtains, keeps heating, it is fully anti-
Should, complete the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the reducing agent is 1-20g/L, and the concentration of the stabilizer is 2-50g/L, institute
The concentration for stating mantoquita is 5-50g/L.
When also including the metal salt according to the preparing raw material of the Nanometer Copper activating solution of the present invention, the preparation method is also wrapped
Include, in addition to will be added after metal salt solution in the mixed liquor that is obtained to step (2), holding is heated to 100-150 DEG C, fully anti-
0.1-5 hours are answered, obtain Nanometer Copper activating solution；In the activating solution, the concentration of the metal salt is 0.1-10g/L.
According to the preparation method of the Nanometer Copper activating solution of the present invention, the reducing agent is glucose, ascorbic acid, hydration
One or more in hydrazine, sodium borohydride, glyoxalic acid, formaldehyde, ethylene glycol.Introduced reducing agent has long-term reproducibility,
The nanometer copper particle in activating solution can be avoided to be oxidized, ensure that the long-time stability of activating solution without failing, extend activation
The service life of liquid.
According to the preparation method of the Nanometer Copper activating solution of the present invention, the stabilizer is polyvinylpyrrolidone, dodecane
Base sodium sulphate, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyacrylic acid, monoethanolamine, polyacrylamide
One or more in amine, citric acid, trisodium citrate.The stabilizer used can be effectively adsorbed in nano copper particle
Around, make nano copper particle that there is bigger charging property, disperse evenly, colloidal nanoparticles particle diameter is smaller, avoids nanometer
Reunite between grain, make activating solution increased activity.
According to the preparation method of the Nanometer Copper activating solution of the present invention, the solvent is water, methanol, ethanol, ethylene glycol, poly- second
One or more in glycol, dimethylformamide, oleic acid, 1-METHYLPYRROLIDONE.
According to the present invention Nanometer Copper activating solution preparation method, described mantoquita be copper sulphate, copper chloride, copper nitrate,
One or more in Kocide SD, copper acetate.
According to the present invention Nanometer Copper activating solution preparation method, described metal salt be metallic copper, nickel, palladium, iron, cobalt,
One or more in the corresponding metal salt of gold, silver, platinum.
According to the preparation method of the Nanometer Copper activating solution of the present invention, in order to ensure the reducing agent and stabilizer described molten
Quick fully dissolving in agent, and ensure not influenceing its action activity, in step (1), heating-up temperature is 100 DEG C -300 DEG C.
According to the preparation method of the Nanometer Copper activating solution of the present invention, in order to ensure the mantoquita highly effective reaction introduced, in step
(2) in, 0.5-5 hours are reacted at 100-240 DEG C.
Preparation in accordance with the present invention, obtained Nanometer Copper activating solution, Nanometer Copper is used as main avtive spot, it is described
The particle diameter of nano copper particle is 1-50nm.
Beneficial effects of the present invention are：
According to the preparation method of the Nanometer Copper activating solution of the present invention, technique is simple, is sufficiently mixed the reducing agent and stably
Agent, prepare the Nanometer Copper activating solution that stability is good, activation capacity is strong.
According to the Nanometer Copper activating solution of the present invention, using nano copper particle as activated centre, used reducing agent can be kept away
Exempt from nanometer copper particle to be oxidized, make Nanometer Copper activating solution that there is strong inoxidizability.Used stabilizer can improve nanometer
Copper particle is charge, prevents from reuniting between particle, is that Nanometer Copper activating solution has long-time stability, storage time was up to 2 years
More than.Compared with existing colloid palladium, the Nanometer Copper activating solution of the inventive method, using cheap metallic copper as activated centre,
Dispergation processing need not be carried out during use, simplifies the use step of activating solution, technique is simple, green.
Brief description of the drawings
Fig. 1 is that the rear backlight of wiring board hole metallization is real after the Nanometer Copper activating solution processing of various concentrations in embodiment 1
Test figure.
Fig. 2 be the wiring board after the activating solution processing obtained with embodiment 4 it is metallized after, its through hole hole wall SEM
Picture.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Detailed description.Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are resulting on the premise of creative work is not made to be owned
Other embodiment, belong to the scope that the present invention is protected.
Embodiment 1
The preparation method of Nanometer Copper activating solution, comprises the following steps：
(1) first 1g sodium borohydrides are dissolved in 800mL deionized waters, add 10g polyvinylpyrrolidones, be heated to
100 DEG C, and constantly stir, obtain mixed liquor；
(2) in a heated condition, 5g cupric sulfate pentahydrates are dissolved in after the aqueous solution is made in 200mL deionized waters, are added to step
Suddenly in the mixed liquor that (1) obtains, holding is heated to 100 DEG C, stirring, fully reaction 0.5 hour, is cooled to 22 DEG C, described in completion
The preparation of Nanometer Copper activating solution；
In the activating solution, the concentration of the sodium borohydride is 1g/L, and the concentration of the polyvinylpyrrolidone is
10g/L, the concentration of the cupric sulfate pentahydrate is 5g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 2
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) first 20g glucose is dissolved in 800mL deionized waters, adds 20g lauryl sodium sulfate, be heated to 100
DEG C, and constantly stir, obtain mixed liquor；
(2) in a heated condition, 50g copper chlorides are dissolved in after the aqueous solution is made in 150mL deionized waters, are added to step
(1) in the mixed liquor obtained, holding is heated to 150 DEG C, stirring, fully reaction 1.5 hours；
(3) 0.1 nickel chloride is dissolved in after the aqueous solution is made in 50mL deionized waters, adds the mixed liquor obtained to step (2)
In, and holding is heated to 150 DEG C and reacted 0.5 hour, is cooled to 28 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the glucose is 20g/L, and the concentration of the lauryl sodium sulfate is 20g/
L, the concentration of the copper chloride is 50g/L, and the concentration of the nickel chloride is 0.1g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 3
(1) first 10g ascorbic acid is dissolved in the solvent being mixed to get by 400mL deionized waters and 300mL ethanol, then added
Enter 10g cetyl trimethylammonium bromides and 10g hexadecyltrimethylammonium chlorides, be heated to 200 DEG C, and be stirred continuously
It is even, obtain mixed liquor；
(2) in a heated condition, 15g copper nitrates are dissolved in after the aqueous solution is made in 150mL deionized waters, are added to step
(1) in the mixed liquor obtained, holding is heated to 150 DEG C, stirring, fully reaction 1.5 hours；
(3) 0.5g palladium bichlorides are dissolved in after the aqueous solution is made in 50mL deionized waters, add the mixed liquor obtained to step (2)
In, and holding is heated to 100 DEG C and reacted 1 hour, is cooled to 25 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the ascorbic acid is 10g/L, the cetyl trimethylammonium bromide and ten
The concentration of six alkyl trimethyl ammonium chlorides is 20g/L, and the concentration of the copper nitrate is 15g/L, and the concentration of the palladium bichloride is
0.5g/L。
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 4
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) 8g glyoxalic acids are first dissolved in the solvent being mixed to get by 400mL dimethylformamides and 400mL polyethylene glycol
In, 20g polyacrylic acid and 20g monoethanolamines are added, is heated to 240 DEG C, and constantly stir, obtain mixed liquor；
(2) in a heated condition, 15g copper nitrates are dissolved in after solution is made in 150mL dimethylformamides, are added to step
(1) in the mixed liquor obtained, holding is heated to 240 DEG C, stirring, fully reaction 0.5 hour；
(3) 0.1g silver nitrates are dissolved in after the aqueous solution is made in 50mL deionized waters, add the mixed liquor obtained to step (2)
In, and holding is heated to 100 DEG C and reacted 1 hour, is cooled to 25 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the glyoxalic acid is 10g/L, and the concentration of the polyacrylic acid and monoethanolamine is
40g/L, the concentration of the copper nitrate is 15g/L, and the concentration of the palladium bichloride is 0.1g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 5
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) first 2g glucose, 10g ascorbic acid and 3g ethylene glycol are dissolved in 800mL oleic acid, add 20g polyethylene
Pyrrolidones and 8g citric acids, are heated to 300 DEG C, and constantly stir, and obtain mixed liquor；
(2) in a heated condition, 40g copper nitrates are dissolved in after solution is made in 150mL dimethylformamides, are added to step
(1) in the mixed liquor obtained, holding is heated to 140 DEG C, stirring, fully reaction 3 hours；
(3) 0.2g chloroplatinic acids are dissolved in after the aqueous solution is made in 50mL deionized waters, add the mixed liquor obtained to step (2)
In, and holding is heated to 100 DEG C and reacted 0.5 hour, is cooled to 25 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the reducing agent of the glucose, ascorbic acid and ethylene glycol composition is 15g/L,
The concentration of the stabilizer of polyvinylpyrrolidone and the citric acid composition is 28g/L, and the concentration of the copper nitrate is 40g/L,
The concentration of the chloroplatinic acid is 0.2g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 6
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) first 20g formaldehyde is dissolved in 800mL polyethylene glycol, adds 2g polyacrylamides, be heated to 240 DEG C, not
It is disconnected to stir, obtain mixed liquor；
(2) in a heated condition, 15g copper chlorides are dissolved in after solution is made in 150mL deionized waters, are added to step (1)
In obtained mixed liquor, holding is heated to 150 DEG C, stirring, fully reaction 5 hours；
(3) 1g cobalt chlorides are dissolved in after the aqueous solution is made in 50mL deionized waters, add the mixed liquor obtained to step (2)
In, and holding is heated to 100 DEG C and reacted 0.5 hour, is cooled to 25 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the formaldehyde is 20g/L, and the concentration of the polyacrylamide is 2g/L, described
The concentration of copper chloride is 15g/L, and the concentration of the cobalt chloride is 1g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 7
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) first 20g hydrazine hydrates are dissolved in 800mL ethylene glycol, add 20g polyvinylpyrrolidones and 10g citric acids
Sodium, 130 DEG C are heated to, and constantly stirred, obtain mixed liquor；
(2) in a heated condition, 5g Kocide SDs are dissolved in after solution is made in 150mL deionized waters, are added to step (1)
In obtained mixed liquor, holding is heated to 150 DEG C, stirring, fully reaction 5 hours；
(3) 0.1g gold chlorides and 1g palladium bichlorides are dissolved in after the aqueous solution is made in 50mL deionized waters, added to step (2)
To mixed liquor in, and keep be heated to 100 DEG C react 0.5 hour, be cooled to 25 DEG C, complete the system of the Nanometer Copper activating solution
It is standby；
In the activating solution, the concentration of the hydrazine hydrate is 20g/L, polyvinylpyrrolidone and the sodium citrate group
Concentration into mL stabilizers is 30g/L, and the concentration of the Kocide SD is 5g/L, the metal of gold chloride and the palladium bichloride composition
The concentration of salt is 1.1g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 8
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) first 20g sodium borohydrides are dissolved in 800mL deionized waters, add 50g trisodium citrates, be heated to 130
DEG C, and constantly stir, obtain mixed liquor；
(2) in a heated condition, 30g copper acetates are dissolved in after solution is made in 150mL deionized waters, are added to step (1)
In obtained mixed liquor, holding is heated to 130 DEG C, stirring, fully reaction 4 hours；
(3) 10g copper chlorides are dissolved in after the aqueous solution is made in 50mL deionized waters, add the mixed liquor obtained to step (2)
In, and holding is heated to 150 DEG C and reacted 5 hours, is cooled to 25 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the sodium borohydride is 20g/L, and the concentration of the trisodium citrate is 50g/L,
The concentration of the copper acetate is 30g/L, and the concentration of the copper chloride is 10g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Embodiment 9
The preparation method of described Nanometer Copper activating solution, comprises the following steps：
(1) first 20g glucose is dissolved in 800mLN- methyl pyrrolidones, adds 10g trisodium citrates and 10g lemons
Lemon acid, is heated to 120 DEG C, and constantly stirs, and obtains mixed liquor；
(2) in a heated condition, 5g copper acetates and 5g copper nitrates are dissolved in after solution is made in 150mL methanol, are added to step
Suddenly in the mixed liquor that (1) obtains, holding is heated to 120 DEG C, stirring, fully reaction 5 hours；
(3) 0.2g iron chloride is dissolved in after the aqueous solution is made in 50mL deionized waters, adds the mixed liquor obtained to step (2)
In, and holding is heated to 150 DEG C and reacted 0.1 hour, is cooled to 22 DEG C, completes the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the glucose is 20g/L, and the trisodium citrate and citric acid form steady
The concentration for determining agent is 20g/L, and the concentration of the copper acetate is 10g/L, and the concentration of the iron chloride is 0.2g/L.
Nanometer Copper activating solution made from described preparation method, the nano copper particle particle diameter in the activating solution is 1-
50nm。
Performance test：
1st, Nanometer Copper activating solution life test：By the Nanometer Copper activating solution sample that embodiment 1-5 is obtained respectively take 20mL in
In unlimited cuvette, stood under normal temperature, the life-span of record Nanometer Copper activating solution discoloration resolving time, as activating solution.Test
As a result it is as shown in table 1.
2nd, activating solution performance test：Activating solution in 1-5 of the embodiment of the present invention is used for non-metallic substrate chemical plating
Reason, method are as follows：
(1) base material treatment：By wiring boards of the 5cm × 5cm × 0.2cm with through hole after oil removing, from distilled water cleaning,
Immerse in conditioner and carry out whole hole processing, cleaned after taking-up with distilled water.
(2) activate：Through hole wiring board is carried with hair-dryer cold wind drying step (1), is then immersed in the embodiment of the present invention
In the activating solution made from 1-5,3-5 minutes are soaked at 35 DEG C, taking-up is cleaned with distilled water.
(3) chemical plating：The wiring board of above-mentioned 2) activated processing is immersed in 500mL chemical plating baths, carries out chemical plating
Copper 20 minutes, in chemical plating fluid, concentration of copper sulfate 10g/L, EDTA 30g/L, potassium ferrocyanide 0.01g/L, dodecane
Base benzene sulfonic acid sodium salt is 0.8g/L, and 2,2- bipyridyls are 0.03g/L, glyoxalic acid 2.25g/L.After the completion of electroless copper, spend from
Sub- water cleans wiring board, obtains plating piece.
In step (3), record triggers the cycle, i.e., wiring board immerses in chemical plating bath and starts to produce bubble institute to surface
Take time；And complete Plating times, i.e., wiring board since immersing in chemical plating bath to the time required to the complete plating in surface.
Test result is as shown in table 1.The test result surface activating solution of the present invention of table 1 has long-time stability, storage time
Up to even more than 3 years 2 years, after being handled with activating solution, the initiation cycle of chemical plating was short, completely the cycle the time required to coating
It is short, substantially increase the production efficiency of chemical plating.
Table 1
| Sample | Life-span/day | Trigger cycles/sec | Complete Plating times/second |
| S1 | ＞ 360 | 10 | 125 |
| S2 | ＞ 360 | 8 | 110 |
| S3 | ＞ 720 | 15 | 132 |
| S4 | ＞ 720 | 18 | 138 |
| S5 | ＞ 180 | 16 | 133 |
3rd, empty negative phototropism test：Wiring board after metallization is cut in the axial direction, sample with holes is horizontal along axis
To placement, make in hole layers of copper upward, from privately throw light, with layers of copper coverage condition in light microscope peep hole.Fig. 1 institutes
Show, for by activating solution made from embodiment 1 and distilled water with 20mL：1L、40mL：1L and 80mL：1L proportional arrangement into it is dilute
Release the backlight lab diagram after the wiring board hole metallization after activating solution processing.
Fig. 2 be the wiring board after the activating solution processing obtained with embodiment 4 it is metallized after, its through hole hole wall SEM
Picture.It is can be seen that by Fig. 1 and Fig. 2 after activating solution of the present invention processing, the coating excellent effect of PCB surface metal.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of preparation method of Nanometer Copper activating solution, it is characterised in that comprise the following steps：
(1) reducing agent and stabilizer are dissolved in solvent, keep heating, and constantly stirred, obtain mixed liquor；
(2) in a heated condition, copper salt solution is added in the mixed liquor that step (1) obtains, keeps heating, fully reaction,
Complete the preparation of the Nanometer Copper activating solution；
In the activating solution, the concentration of the reducing agent is 1-20g/L, and the concentration of the stabilizer is 2-50g/L, the copper
The concentration of salt is 5-50g/L.
2. preparation method according to claim 1, it is characterised in that also include to add to step after metal salt solution
(2) in the mixed liquor obtained, keep heating and abundant, obtain Nanometer Copper activating solution；
In the activating solution, the concentration of the metal salt is 0.1-10g/L.
3. preparation method according to claim 1, it is characterised in that the reducing agent is glucose, ascorbic acid, hydration
One or more in hydrazine, sodium borohydride, glyoxalic acid, formaldehyde, ethylene glycol.
4. preparation method according to claim 1, it is characterised in that the stabilizer is polyvinylpyrrolidone, 12
Sodium alkyl sulfate, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, polyacrylic acid, monoethanolamine, polyacrylamide
One or more in amine, citric acid, trisodium citrate.
5. preparation method according to claim 1, it is characterised in that the solvent is water, methanol, ethanol, ethylene glycol, poly-
One or more in ethylene glycol, dimethylformamide, oleic acid, 1-METHYLPYRROLIDONE.
6. preparation method according to claim 1, it is characterised in that described mantoquita is copper sulphate, copper chloride, nitric acid
One or more in copper, Kocide SD, copper acetate.
7. preparation method according to claim 2, it is characterised in that described metal salt be metallic copper, nickel, palladium, iron,
One or more in the corresponding metal salt of cobalt, gold, silver, platinum.
8. preparation method according to claim 1, it is characterised in that in step (1), heating-up temperature is 100 DEG C -300
℃。
9. preparation method according to claim 1, it is characterised in that in step (2), react 0.5-5 at 100-240 DEG C
Hour.
10. Nanometer Copper activating solution made from any described preparation methods of claim 1-9, the Nanometer Copper in the activating solution
Grain particle diameter is 1-50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710513891.4A CN107460459A (en) | 2017-06-29 | 2017-06-29 | A kind of Nanometer Copper activating solution and preparation method thereof |
Applications Claiming Priority (1)
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| CN110385443A (en) * | 2019-07-28 | 2019-10-29 | 长春黄金研究院烟台贵金属材料研究所有限公司 | A kind of preparation method of acid system Nanometer Copper colloidal sol |
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| CN110385443A (en) * | 2019-07-28 | 2019-10-29 | 长春黄金研究院烟台贵金属材料研究所有限公司 | A kind of preparation method of acid system Nanometer Copper colloidal sol |
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| CN111421143A (en) * | 2020-04-01 | 2020-07-17 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of nano-copper particles for treating inflammatory diseases |
| WO2022043417A1 (en) | 2020-08-27 | 2022-03-03 | Atotech Deutschland GmbH & Co. KG | A method for activating a surface of a non-conductive or carbon-fibres containing substrate for metallization |
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