CN114959665B - Preparation method of colloid palladium activating solution for electroless copper plating of printed circuit board - Google Patents
Preparation method of colloid palladium activating solution for electroless copper plating of printed circuit board Download PDFInfo
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- CN114959665B CN114959665B CN202210437637.1A CN202210437637A CN114959665B CN 114959665 B CN114959665 B CN 114959665B CN 202210437637 A CN202210437637 A CN 202210437637A CN 114959665 B CN114959665 B CN 114959665B
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- electroless copper
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 89
- 239000000084 colloidal system Substances 0.000 title claims abstract description 38
- 238000007747 plating Methods 0.000 title claims abstract description 32
- 230000003213 activating effect Effects 0.000 title claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 41
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000001119 stannous chloride Substances 0.000 claims abstract description 20
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 20
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 19
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 18
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 18
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims description 27
- ROADCYAOHVSOLQ-UHFFFAOYSA-N 3-oxetanone Chemical group O=C1COC1 ROADCYAOHVSOLQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 7
- 230000006698 induction Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 229910003445 palladium oxide Inorganic materials 0.000 description 3
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- 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
Abstract
The invention relates to a preparation method of colloid palladium activating solution for electroless copper plating of a printed circuit board, which comprises the steps of adding deionized water into tetra-ammine palladium dichloride and ammonium chloride to be stirred and dissolved to obtain mixed solution with palladium content of 2-3%; then stannous chloride is added into the mixed solution, and the mixed solution is stirred uniformly and heated to 40 ℃ for reaction; when the system turns into brown from yellow, adding hydrazine hydrate with the volume concentration of 80%, uniformly stirring, heating to 60 ℃ and curing for 2 hours; and cooling to room temperature after the reaction is finished, finally adding an adsorption accelerator and dilute hydrochloric acid, uniformly stirring, and filtering to obtain the colloid palladium activated liquid. The invention improves the product yield and can obtain the colloid palladium activating solution with high activity. The colloid palladium activating liquid prepared by the method can shorten the induction time of electroless copper plating and obtain high backlight level of copper plating.
Description
Technical Field
The invention relates to the field of noble metal activating solution synthesis, in particular to a preparation method of colloid palladium activating solution for electroless copper plating of a printed circuit board.
Background
The printed circuit boards for computers and communication are all nonmetallic materials, most of them are non-conductors, and the conductive film must be prepared first for electroplating, and the common method is electroless plating. Prior to electroless plating, the surface must be pre-treated for activation. The purpose of activation is to adsorb a certain amount of activation centers on the nonmetallic substrate in order to induce subsequent electroless plating. The activation of the substrate is by means of a catalytically active metal compound solution, uniformly and firmly adsorbing a certain amount of catalytically active particles, i.e. catalysts, on the non-metallic substrate to induce the subsequent electroless plating. Activation not only determines the quality of the electroless plating layer, but also the quality of the whole plating layer, and is a hot spot and an important point of research in recent years in the field of PCB electroless plating.
The colloid palladium activating solution is prepared by taking palladium chloride as a raw material. According to the preparation method of the colloid palladium activation liquid disclosed in CN101928937A, the colloid palladium activation liquid contains palladium activation liquid, sodium chloride, glyoxylic acid, hydrochloric acid and a stabilizer for stabilizing stannous chloride. The colloid palladium activating solution provided by the method is used for activating the surface of the nonmetal substrate, and the glyoxylic acid in the activating solution can be preferentially adsorbed on the surface of the nonmetal substrate, so that the binding force of colloid palladium particles and the nonmetal substrate is enhanced; the plating layer has uniform thickness and smooth surface after chemical plating, but the adhesion force between the plating layer and the substrate is not high. According to the method disclosed in patent CN109837575A, N-methylolacrylamide is adopted as an organic ligand for synthesizing palladium salt activating solution, and the preparation method of the novel salt-based palladium activating solution has the advantages of simple process, low preparation cost and low activity.
In the method, palladium chloride is used as a starting material, and in a reaction system, a trace amount of palladium ions in the starting material are hydrolyzed into palladium oxide particles which are wrapped in palladium atoms, so that the catalytic activity is low when chemical plating is performed, and the problem of plating omission occurs when serious. Therefore, a large amount of reducing agent is required to be used in the subsequent reduction process to meet the product standards. Although the inclusion of palladium oxide is reduced to a certain extent by technical improvement and condition control, the method is easy to have high cost due to long reaction period and harsh reaction conditions.
Palladium is extremely rare in distribution in the crust, difficult to mine and enrich, high in cost, expensive in platinum group metal, and high in recovery and refining cost due to special chemical properties of palladium. Therefore, the preparation of the colloid palladium activation liquid with high stability and high catalytic activity has great significance.
Disclosure of Invention
The invention aims to provide a preparation method of colloid palladium activating solution for electroless copper plating of a printed wiring board with high yield and high activity.
In order to solve the problems, the preparation method of the colloid palladium activating solution for electroless copper plating of the printed circuit board is characterized by comprising the following steps: firstly, adding deionized water into tetra-ammine palladium dichloride and ammonium chloride, stirring and dissolving to obtain a mixed solution with the palladium content of 2-3%; then stannous chloride is added into the mixed solution, and the mixed solution is stirred uniformly and heated to 40 ℃ for reaction; when the system turns into brown from yellow, adding hydrazine hydrate with the volume concentration of 80%, uniformly stirring, heating to 60 ℃ and curing for 2 hours; and cooling to room temperature after the reaction is finished, finally adding an adsorption accelerator and dilute hydrochloric acid, uniformly stirring, and filtering to obtain the colloid palladium activated liquid.
The palladium tetra-ammine dichloride is pale yellow powder with the palladium content of 42.3 percent.
The ammonium chloride is added according to the molar ratio of 2.1-2.8 of the ammonium chloride to the tetraammine palladium dichloride.
The dosage of stannous chloride is added according to the molar ratio of stannous chloride to palladium tetra-ammine dichloride of 12-18.
The dosage of the hydrazine hydrate is 1 according to the molar ratio of the hydrazine hydrate to the tetraammine palladium dichloride: 1.
The adsorption promoter is 3-oxetanone.
The content of the adsorption promoter in the colloid palladium activation solution is 0.1-1 g/L.
The mass concentration of the dilute hydrochloric acid is 10%.
The mass concentration of palladium in the colloid palladium activating solution is 0.968-1.042%.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, palladium ion stability is improved through palladium tetra-chloride, and product purity is improved while product yield is improved.
2. According to the invention, palladium chloride is used as a raw material, side reactions such as hydrolysis of palladium chloride under a medium alkaline condition are avoided, palladium ion hydrolysis is inhibited, no palladium oxide is introduced in the whole reaction process, and meanwhile, an adsorption promoter is added to obtain a high-activity colloid palladium activating solution, and the consumption of a reducing agent and the adsorption promoter is reduced.
3. The colloid palladium activating liquid prepared by the method can shorten the induction time of electroless copper plating and obtain high backlight level of copper plating.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is an SEM photograph of an electroless copper plating layer of example 5 of the invention. Wherein: the left plot is at 15000 magnification; the right image is magnified 3000 times.
Detailed Description
A preparation method of colloid palladium activating solution for electroless copper plating of a printed wiring board comprises the following steps:
firstly, adding deionized water into tetra-ammine palladium dichloride and ammonium chloride, stirring and dissolving until a system is clear and no insoluble matters are visible to the naked eye, and obtaining a mixed solution with the palladium content of 2-3%; then stannous chloride is added into the mixed solution, and the mixed solution is stirred uniformly and heated to 40 ℃ for reaction; when the system turns into brown from yellow, the palladium ions of the system are converted into fine palladium simple substances, hydrazine hydrate with the volume concentration of 80% is added, the mixture is stirred uniformly and heated to 60 ℃ for curing for 2 hours, and the system turns into dark brown; and cooling to room temperature after the reaction is finished, finally adding 3-oxetanone serving as an adsorption promoter and 10% of dilute hydrochloric acid, uniformly stirring, and filtering to obtain the colloidal palladium activation solution with the adsorption promoter content of 0.1-1 g/L and the palladium mass concentration of 0.968-1.042%.
Wherein: tetraamminepalladium dichloride is a pale yellow powder with a palladium content of 42.3%, which is close to the theoretical palladium content.
The ammonium chloride is added according to the molar ratio of 2.1-2.8 of the ammonium chloride to the tetraammine palladium dichloride.
The stannous chloride is white powder, and the dosage of the stannous chloride is added according to the molar ratio of 12-18 of the stannous chloride to the palladium tetra-ammine dichloride.
The dosage of the hydrazine hydrate is 1 according to the molar ratio of the hydrazine hydrate to the tetraamminepalladium dichloride: 1.
The addition amount of the dilute hydrochloric acid is added according to the mass concentration of palladium in the colloid palladium activation solution which is kept to be 0.968-1.042%.
Example 1
In a three-neck flask with a reflux condenser, adding 500 g of deionized water into 0.1 mol of tetra-ammine palladium dichloride and 0.21 mol of ammonium chloride, stirring until the system is clear, adding 1.2 mol of stannous chloride, heating to 40 ℃, after the system turns brown from yellow, adding 0.1 mol of hydrazine hydrate, stirring uniformly, heating to 60 ℃ for curing for 2 hours, turning the system into dark brown, cooling down to room temperature, adding 0.1 g of 3-oxetanone serving as an adsorption promoter and 500 g of 10% diluted hydrochloric acid, stirring uniformly, and filtering to obtain 1021.0 g of colloid palladium activating solution, wherein the palladium content is 1.0414%.
Example 2
In a three-neck flask with a reflux condenser, adding 450 g of deionized water into 0.1 mol of tetra-chloroammonium palladium and 0.25 mol of ammonium chloride, stirring until the system is clear, adding 1.4 mol of stannous chloride, heating to 40 ℃, after the system turns brown from yellow, adding 0.1 mol of hydrazine hydrate, stirring uniformly, heating to 60 ℃ for curing for 2 hours, turning the system into dark brown, cooling down to room temperature, adding 0.2 g of 3-oxetanone serving as an adsorption promoter and 550 g of 10% diluted hydrochloric acid, stirring uniformly, and filtering to obtain 1022.5 g of colloid palladium activating solution with the palladium content of 1.0399%.
Example 3
In a three-neck flask with a reflux condenser, 0.1 mol of tetra-ammine palladium dichloride and 0.26 mol of ammonium chloride are added with 400g of deionized water, stirred until the system is clear, 1.7 mol of stannous chloride is added, then the temperature is raised to 40 ℃, after the system turns into brown from yellow, 0.1 mol of hydrazine hydrate is added, the mixture is uniformly stirred, the temperature is raised to 60 ℃ for curing for 2 hours, the system turns into dark brown, the mixture is cooled down to room temperature, 0.3 g of 3-oxetanone as an adsorption promoter and 600 g of 10% diluted hydrochloric acid are added, the mixture is uniformly stirred and filtered to obtain 1023.7 g of colloid palladium activating solution, and the palladium content is 1.0388%.
Example 4
In a three-neck flask with a reflux condenser, adding 380 g of deionized water into 0.1 mol of tetra-ammine palladium dichloride and 0.28 mol of ammonium chloride, stirring until the system is clear, adding 1.8 mol of stannous chloride, heating to 40 ℃, after the system turns brown from yellow, adding 0.1 mol of hydrazine hydrate, stirring uniformly, heating to 60 ℃ for curing for 2 hours, turning the system into dark brown, cooling down to room temperature, adding 0.6 g of 3-oxetanone as an adsorption promoter and 620 g of 10% diluted hydrochloric acid, stirring uniformly, and filtering to obtain 1021.8 g of colloid palladium activation liquid with the palladium content of 1.0406%.
Example 5
In a three-neck flask with a reflux condenser, 0.1 mol of tetra-ammine palladium dichloride and 0.28 mol of ammonium chloride are added with 350 g of deionized water, stirred until the system is clear, 1.8 mol of stannous chloride is added, then the temperature is raised to 40 ℃, after the system turns into brown from yellow, 0.1 mol of hydrazine hydrate is added, the mixture is uniformly stirred, the temperature is raised to 60 ℃ for curing for 2 hours, the system turns into dark brown, the mixture is cooled down to room temperature, 0.8 g of 3-oxetanone as an adsorption promoter and 650 g of 10% diluted hydrochloric acid are added, the mixture is uniformly stirred and filtered to obtain 1022.1 g of colloid palladium activating solution, and the palladium content is 1.0404%.
Example 6
In a three-neck flask with a reflux condenser, adding 450 g of deionized water into 0.1 mol of tetra-ammine palladium dichloride and 0.26 mol of ammonium chloride, stirring until the system is clear, adding 1.7 mol of stannous chloride, heating to 40 ℃, after the system turns brown from yellow, adding 0.1 mol of hydrazine hydrate, stirring uniformly, heating to 60 ℃ for curing for 2 hours, turning the system into dark brown, cooling down to room temperature, adding 0.9g of 3-oxetanone serving as an adsorption promoter and 550 g of 10% diluted hydrochloric acid, stirring uniformly, and filtering to obtain 1021.9 g of colloid palladium activating solution, wherein the palladium content is 1.0405%.
Example 7
In a three-neck flask with a reflux condenser, adding 500 g of deionized water into 0.1 mol of tetra-chloroammonium palladium and 0.24 mol of ammonium chloride, stirring until the system is clear, adding 1.5 mol of stannous chloride, heating to 40 ℃, after the system turns brown from yellow, adding 0.1 mol of hydrazine hydrate, stirring uniformly, heating to 60 ℃ for curing for 2 hours, turning the system into dark brown, cooling down to room temperature, adding 1.0 g of 3-oxetanone serving as an adsorption promoter and 500 g of 10% diluted hydrochloric acid, stirring uniformly, and filtering 1022.3 g of colloid palladium activating solution, wherein the palladium content is 1.0402%.
Comparative example
In a three-neck flask with a reflux condenser, adding 450 g of deionized water into 0.1 mol of tetra-ammine palladium dichloride and 0.22 mol of ammonium chloride, stirring until the system is clear, adding 1.8 mol of stannous chloride, heating to 40 ℃, adding 0.1 mol of hydrazine hydrate after the system turns brown, stirring uniformly, heating to 60 ℃ and curing for 2 hours, cooling down to room temperature, adding 550 g of 10% diluted hydrochloric acid by mass fraction, stirring uniformly, and filtering to obtain 1021.3 g of colloid palladium activation liquid, wherein the palladium content is 0.9681%.
The yields and analysis results of the products obtained in examples 1 to 7 and comparative examples are shown in Table 1.
Colloidal palladium yield = (mass of colloidal palladium activation solution×mass fraction of palladium)/(weight of tetraamminepalladium dichloride×42.3%) ×100%.
TABLE 1 product yields and analytical results
As can be seen from Table 1, the addition of the adsorption promoter in examples 1 to 7 can stabilize the colloidal palladium activation solution, prevent the active component palladium in the colloidal palladium activation solution from aggregating into large-particle-size palladium and precipitating in a precipitate form to reduce the yield of the product. Thus, the products obtained in examples 1 to 7 can obtain the object of high yield.
The copper plating layer on the ABS substrate using the colloidal palladium activation solutions prepared in examples 1 to 7 and comparative examples described above was obtained by the following method.
Destressing the ABS base material (immersing the part to be plated in glacial acetic acid for 25-30 s, immediately washing the part with water), removing oil (sodium hydroxide 30 g.L) -1 5min, washing) to coarsening (chromium trioxide 400 g.L -1 200 ml.L of 98% concentrated sulfuric acid -1 65 ℃ for 10 min) to surface modification (hexadecyl trimethyl ammonium bromide 0.5 g.L) -1 Silane coupling agent 20 ml.L -1 The method comprises the steps of carrying out a first treatment on the surface of the 55 ℃ for 4 min) to presoaking (37% hydrochloric acid 200 ml.L) -1 The method comprises the steps of carrying out a first treatment on the surface of the 25 ℃,30-60 s) to activation (Pd 0.4 g.L) -1 ，SnCl 2 1g·L -1 ，HCl 50-300ml·L -1 ) De-gelling (sodium hydroxide 30 g.L) -1 Copper sulfate 3 g.L -1 Ethylene diamine tetraacetic acid disodium 15 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the 55 ℃,7 min), electroless copper plating (300R 16mL/L,365C 45mL/L, 365S 4.5mL/L, 365B 8.5mL/L,45 ℃,4 min), water washing, and drying (45 ℃).
Backlight stage number test equipment: an Oss micro microscope SZM-41.
SEM test equipment: zeiss LSM 900.
And (3) testing the binding force: the plating layer is subjected to cold and hot circulation experiments for 3 periods, does not bubble, peel and fall off, and meets the requirement of the binding force of the plastic chemical plating piece.
The ABS resin plate was subjected to electroless copper plating using the colloidal palladium activation solution, and the induction time and the complete coverage time of the catalytic activity of the reaction activation solution were recorded, respectively, and the number of backlight stages of the electroless copper plating substrate was recorded, respectively, as shown in table 2.
TABLE 2 electroless copper plating test results
As can be seen from table 2, the activity and the adhesion rate of the colloidal palladium activation solution using the adsorption promoter are significantly improved under the same palladium concentration. Under the condition of the same palladium concentration, the addition amount of the adsorption promoter directly influences the activity and the adhesion rate of the colloidal palladium activating solution. As can be seen from examples 4, 5 and 6, the concentration of the colloidal palladium activated liquid adsorption accelerator is controlled to be about 0.6-0.9 g/L, and the effect is optimal.
SEM inspection was also performed on the electroless copper plating layer of example 5, as shown in fig. 1. As can be seen from the figure 1, the copper plating layer is compact and uniform, and the colloidal palladium activation solution obtained by the invention has the advantages of low impurity content, good stability and high catalytic activity.
Claims (5)
1. A preparation method of colloid palladium activating solution for electroless copper plating of a printed circuit board is characterized by comprising the following steps: firstly, adding deionized water into tetra-ammine palladium dichloride and ammonium chloride, stirring and dissolving to obtain a mixed solution with the palladium content of 2-3%; then stannous chloride is added into the mixed solution, and the mixed solution is stirred uniformly and heated to 40 ℃ for reaction; when the system turns into brown from yellow, adding hydrazine hydrate with the volume concentration of 80%, uniformly stirring, heating to 60 ℃ and curing for 2 hours; cooling to room temperature after the reaction is finished, adding an adsorption accelerator and dilute hydrochloric acid, uniformly stirring, and filtering to obtain a colloid palladium activated liquid; the palladium tetra-ammine dichloride is pale yellow powder with the palladium content of 42.3 percent; the adsorption promoter is 3-oxetanone; the content of the adsorption promoter in the colloid palladium activating solution is 0.1-1 g/L; the mass concentration of palladium in the colloid palladium activating solution is 0.968-1.042%.
2. The method for preparing the colloid palladium activation solution for electroless copper plating of a printed wiring board according to claim 1, wherein the method comprises the following steps: the ammonium chloride is added according to the molar ratio of 2.1-2.8 of the ammonium chloride to the tetraammine palladium dichloride.
3. The method for preparing the colloid palladium activation solution for electroless copper plating of a printed wiring board according to claim 1, wherein the method comprises the following steps: the dosage of stannous chloride is added according to the molar ratio of stannous chloride to palladium tetra-ammine dichloride of 12-18.
4. The method for preparing the colloid palladium activation solution for electroless copper plating of a printed wiring board according to claim 1, wherein the method comprises the following steps: the dosage of the hydrazine hydrate is 1 according to the molar ratio of the hydrazine hydrate to the tetraammine palladium dichloride: 1.
5. The method for preparing the colloid palladium activation solution for electroless copper plating of a printed wiring board according to claim 1, wherein the method comprises the following steps: the mass concentration of the dilute hydrochloric acid is 10%.
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