CN111705312A - Chemical tin plating solution and preparation method and application thereof - Google Patents
Chemical tin plating solution and preparation method and application thereof Download PDFInfo
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- CN111705312A CN111705312A CN202010735714.2A CN202010735714A CN111705312A CN 111705312 A CN111705312 A CN 111705312A CN 202010735714 A CN202010735714 A CN 202010735714A CN 111705312 A CN111705312 A CN 111705312A
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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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
Abstract
The invention belongs to the technical field of surface treatment, and particularly relates to a chemical tin plating solution, and a preparation method and application thereof. The invention provides an electroless tin plating solution, which comprises the following components in concentration: 5-25g/L of tin salt, 70-80g/L of complexing agent, 100-120g/L of thiourea substance, 1-10g/L of surfactant, 40-70g/L of reducing agent and 1-10g/L of MZxOy, wherein M is at least one of V, Nb, Zr and Na; z is a hetero element; x is 0 to 2; y is 3 to 5. The applicant researches the chemical tin plating solution in a meticulous way, and all the components are mutually cooperated to play a role together, so that the deposition rate is high, the thickness of a plating layer is large, and the plating layer is uniform and compact.
Description
Technical Field
The invention belongs to the technical field of surface treatment, and particularly relates to a chemical tin plating solution, and a preparation method and application thereof.
Background
Tin is a silvery white metal, has the advantages of corrosion resistance, no toxicity, easy brazing and the like, and is widely applied to various fields in industrial production. Such as tin food packaging boxes and electronic component soldering layers. Based on the good solderability and corrosion resistance of tin, tin plating also has great application value in printing electroplating plates and ultra-large scale integrated circuit chips. In the early electronic packaging and electronic circuit board, tin-lead alloy is used as a solderable plating layer, and the electronic packaging and electronic circuit board has the advantages of low-temperature soldering, high bonding force, no tin whisker generation and the like.
In recent years, people pay more and more attention to health and environmental problems, and a tin-plated layer is widely applied to the industries of electronic components and semiconductor packaging which take copper and copper alloy as a base body as a solderable plating layer. Tin plating can be classified into hot dip tin plating, electrolytic tin plating and chemical tin plating according to the development process. Electroless plating is a process in which metal ions are deposited on the active surface of a substrate in a plating solution under the action of a reducing agent. Generally, the method is classified into a displacement method and a reduction method, and the displacement method deposits a thin metal coating on the surface of a substrate according to the displacement principle, so that the application is limited. The reduction method is a process of continuously depositing metal on the surface of a substrate by using a reducing agent in the plating solution, and plating layers with different thicknesses can be obtained according to requirements. The chemical plating has the advantages of good dispersion capability and covering capability of plating solution, uniform thickness of plating layer and no need of external power supply.
However, the development of the chemical tin plating solution is limited by the influence of the properties of tin and the plating conditions, such as thin plating thickness and slow deposition speed.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides an electroless tin plating solution comprising, in terms of concentration: 5-25g/L of tin salt, 70-80g/L of complexing agent, 100-120g/L of thiourea substance, 1-10g/L of surfactant, 40-70g/L of reducing agent and 1-6g/L of MZxOy, wherein M is at least one of V, Nb, Zr and Na; z is a hetero element; x is 0 to 2; y is 3 to 5.
As a preferred technical scheme, the tin salt is at least one selected from tin methane sulfonate, tin hydrochloride, tin sulfate and stannous fluoroborate.
As a preferable technical scheme, the complexing agent comprises at least one of citric acid, malic acid, citric acid and tartaric acid.
As a preferred technical solution, the reducing agent is at least one selected from sodium hypophosphite, titanium chloride, ammonium hypophosphite, potassium hypophosphite, borohydride and hydrazine hydrate.
As a preferred technical solution, said MZxOy, wherein M is at least one of V, Na; z is a hetero element; x is 0 to 2; y is 3 to 5.
As a preferred technical scheme, the surfactant is selected from at least one of cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, polyethylene glycol and polyoxyethylene polyoxypropylene block copolymer.
As a preferable embodiment, the average molecular weight of the polyoxyethylene polyoxypropylene block copolymer is 2000-2800.
As a preferable technical scheme, the chemical tin plating solution also comprises 16-20g/L of unsaturated compound containing polar groups.
The second aspect of the present invention provides a method for preparing the electroless tin plating solution, comprising the steps of: the components are mixed evenly.
The third aspect of the invention provides a using method of the chemical tin plating solution, wherein the plating condition of the chemical tin plating solution is 40-45 ℃, and the time is 10-15 min.
Has the advantages that: the applicant researches the chemical tin plating solution in a meticulous way, and all the components are mutually cooperated to play a role together, so that the deposition rate is high, the thickness of a plating layer is large, and the plating layer is uniform and compact.
Detailed Description
In order to solve the above problems, the present invention provides an electroless tin plating solution comprising, in terms of concentration: 5-25g/L of tin salt, 70-80g/L of complexing agent, 100-120g/L of thiourea substance, 1-10g/L of surfactant, 40-70g/L of reducing agent and 1-6g/L of MZxOy, wherein M is at least one of V, Nb, Zr and Na; z is a hetero element; x is 0 to 2; y is 3 to 5.
Preferably, the method comprises the following steps according to the concentration: 10-20g/L of tin salt, 70-80g/L of complexing agent, 100-120g/L of thiourea substance, 2-10g/L of surfactant, 40-60g/L of reducing agent and 1-3g/L of MZxOy, wherein M is at least one of V, Nb, Zr and Na; z is a hetero element; x is 0 to 2; y is 3 to 5.
Preferably, the tin salt is at least one selected from tin methane sulfonate, tin hydrochloride, tin sulfate and stannous fluoroborate. Tin salt can be selected according to the requirement, for example, tin methane sulfonate is selected, the toxicity is relatively low, the wastewater treatment is simple, and the plating layer is fine and smooth and is nano-scale crystal grains.
Preferably, the complexing agent comprises at least one of citric acid, malic acid, citric acid and tartaric acid. The complexing agent can generate a stable complex with tin ions, and tin liquid loss caused by direct reaction of tin and a reducing agent is prevented.
Preferably, the thiourea substances are selected from at least one of thiourea, thiosemicarbazide, vinylthiourea, divinylthiourea, 2, 3-indole dione 3-thiosemicarbazone, pyruvic acid thiosemicarbazone, acetone 4-phenyl-3-thiosemicarbazone and 2-butanone thiosemicarbazone. Preferably, the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone; the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 2-4: 1.
the reducing agent is selected from at least one of sodium hypophosphite, titanium chloride, ammonium hypophosphite, potassium hypophosphite, borohydride and hydrazine hydrate; the reducing agent is capable of promoting the reduction of tin ions.
The MZxOy, wherein M is at least one of V, Nb, Zr and Na; z is a hetero element; x is 0 to 2; y is 3 to 5. For example, M is a combination of V and Na elements, and M is a combination of Nb and Na elements; preferably, M is Na 2W; x is 0 and y is 4.
Because the hydrogen evolution potential of tin metal is too high in the chemical tinning process and the self-catalytic reduction capability is not available, the reducing agent is added to catalyze the tin to deposit through the hydrogen evolution reduction reaction; however, the existing reducing agents such as sodium hypochlorite, hydrazine hydrate and formaldehyde cannot effectively reduce tin, and the plating temperature cannot be higher than 45 ℃ in consideration of the influence of a PCB soft board circuit, so that the tin plating speed is slow, and the thickness of a plating layer is difficult to reach 1 mu m; applicants have found that when a certain amount of sodium hypophosphite is added, along with a thiourea-like material, MZxOy, Cu is promoted+Electrode potential of/Cu and Sn2+The potential difference between the/Sn electrode potentials is increased continuously, the deposition speed and the coating thickness are improved, and particularly M is Na 3V; when x is 0 and y is 4, the deposition speed exceeds 8 μm/h, and the thickness of the coating reaches nearly 1 μm.
The surfactant is selected from at least one of cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, polyethylene glycol and polyoxyethylene polyoxypropylene block copolymer; preferably, the polyoxyethylene polyoxypropylene block copolymer has an average molecular weight of 2000-2800; more preferably, the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the average molecular weight of the first polyoxyethylene polyoxypropylene block copolymer is 2000-2400, and the average molecular weight of the second polyoxyethylene polyoxypropylene block copolymer is 2400-2800; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 1-3: 1.
the addition of MZxOy, a reducing agent and the like increases the deposition speed and the thickness of a plating layer, but the plating layer is coarse in crystallization, and the tin plating solution can attack the ink on the PCB to loosen the ink, so that the use of the tin plating solution is severely limited due to a series of influences; the applicant has found that the thiourea-like material comprises 2, 3-indoledione 3-thiosemicarbazone, and a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer are added; the problem that the tin plating solution attacks the printing ink on the PCB can be well solved; it is presumed that the first polyoxyethylene polyoxypropylene block copolymer and the second polyoxyethylene polyoxypropylene block copolymer adsorb on the surface of the substrate, and the migration of 2, 3-indoledione 3-thiosemicarbazone or the like is hindered by a structure formed by the interaction of the hydrophobic segment and the hydrophilic segment.
As a preferred embodiment, the chemical tin plating solution also comprises 16-20g/L of unsaturated compound containing polar groups; the unsaturated compound containing polar groups comprises at least one of propargyl sodium sulfonate, 5-decyne-4, 7-diol, dimethyl octynediol, butynediol propoxylate and 4-methylpent-2-yne-1, 4-diol; the polar group-containing unsaturated compound comprises sodium propargyl sulfonate and 4-methylpent-2-alkyne-1, 4-diol, wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-alkyne-1, 4-diol is 1: 3-5.
The applicant has also found that the polar group-containing unsaturated compound comprises sodium propargyl sulfonate and 4-methylpent-2-yne-1, 4-diol in a concentration ratio of 1: 3-5, the polyoxyethylene polyoxypropylene block copolymer promotes the tendency adsorption of sodium propargyl sulfonate and 4-methylpent-2-yne-1, 4-diol at the concave and convex parts of the unevenness, so that tin is arranged in the same crystal phase, the glossiness of the tin coating is very good, and the thickness of the coating exceeds 1.0 μm.
The preparation of the chemical tin plating solution is a preparation method commonly used in the field, is not particularly limited, and can be realized by uniformly mixing all the components.
The plating condition of the chemical tin plating solution is 40-45 ℃ and the time is 10-15 min.
The applicant researches the chemical tin plating solution in a meticulous way, and all the components are mutually cooperated to play a role together, so that the deposition rate is high, the thickness of a plating layer is large, and the plating layer is uniform and compact.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, MZxOy2g/L and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 in model number, has an average molecular weight of 2200, and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer has a model number of L63 and an average molecular weight of 2650, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 2
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 0g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer is L63, and is purchased from Haian petrochemical plants of Jiangsu province.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 3
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 8g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer is L63, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 4
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 2g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 0.5: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer is L63, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 5
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 2g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 6: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer is L63, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 6
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 2g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L42 in model number, has an average molecular weight of 1630, and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer has a model number of L63 and an average molecular weight of 2650, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 7
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 2g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 3: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 in model number, has an average molecular weight of 2200, and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer has the model number of L65, the average molecular weight of 3500, and is purchased from Haian petrochemical plants in Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 8
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 2g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 1: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 in model number, has an average molecular weight of 2200, and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer has a model number of L63 and an average molecular weight of 2650, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 9
An electroless tin plating solution comprising, in concentrations: 15g/L of tin methane sulfonate, 78g/L of complexing agent citric acid, 110g/L of thiourea substances, 4g/L of surfactant, 50g/L of reducing agent, 2g/L of MZxOy and 18g/L of unsaturated compound containing polar groups;
the thiourea substances comprise thiourea and 2, 3-indole dione 3-thiosemicarbazone (CAS number: 487-16-1); the concentration ratio of the thiourea to the 2, 3-indole dione 3-thiosemicarbazone is 6: 1;
the surfactant is polyoxyethylene polyoxypropylene block copolymer; the polyoxyethylene polyoxypropylene block copolymer comprises a first polyoxyethylene polyoxypropylene block copolymer and a second polyoxyethylene polyoxypropylene block copolymer; the weight ratio of the first polyoxyethylene polyoxypropylene block copolymer to the second polyoxyethylene polyoxypropylene block copolymer is 2: 1; the first polyoxyethylene polyoxypropylene block copolymer is L44 in model number, has an average molecular weight of 2200, and is purchased from Haian petrochemical plants of Jiangsu province; the second polyoxyethylene polyoxypropylene block copolymer has a model number of L63 and an average molecular weight of 2650, and is purchased from Haian petrochemical plants of Jiangsu province.
In MZxOy, M is Na2W; x is 0, y is 4, and the CAS number of MZxOy is 10213-10-2.
The polar group-containing unsaturated compound comprises sodium propargyl sulfonate (CAS number: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS number: 10605-66-0), wherein the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 4.
the preparation method of the chemical tin plating solution comprises the step of uniformly mixing the components.
Example 10
An electroless tin plating solution, according to the same embodiment as that of example 1, is different in that 2, 3-indoledione 3-thiosemicarbazone is replaced with thiosemicarbazone.
Example 11
An electroless tin plating solution, according to the embodiment, is the same as that of example 1, except that the polar group-containing unsaturated compound includes sodium propargyl sulfonate (CAS No: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS No: 10605-66-0), and the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 7.
example 12
An electroless tin plating solution, according to the embodiment, is the same as that of example 1, except that the polar group-containing unsaturated compound includes sodium propargyl sulfonate (CAS No: 55947-46-1) and 4-methylpent-2-yne-1, 4-diol (CAS No: 10605-66-0), and the concentration ratio of the sodium propargyl sulfonate to the 4-methylpent-2-yne-1, 4-diol is 1: 1.
example 13
An electroless tin plating solution, according to the embodiment, is the same as that of example 1, except that the polar group-containing unsaturated compound includes sodium propargyl sulfonate (CAS number: 55947-46-1) and butynediol ethoxylate, and the concentration ratio of the sodium propargyl sulfonate to the butynediol ethoxylate is 1: 4.
the plating conditions of the tin plating solutions described in examples 1 to 13 were 45 ℃ for 15min, and the plating object was a flexible PCB.
Performance testing
Coating thickness: measuring the thickness of the coating by using an intelligent electrolytic thickness gauge; the thickness is evaluated as excellent at more than 1.0 μm (including 1), the thickness is evaluated as poor at less than 0.6 μm in the range of 0.6 to 1.0 μm (including 0.6).
Deposition rate: and (3) measuring the thickness of the plating layer at each of 3 positions on the front and back surfaces of the PCB soft board, and dividing the average value by the plating time. The deposition rate was evaluated as excellent at more than 8 μm/h (including 8), the deposition rate was evaluated as medium at 5 to 8 μm/h (including 5), and the deposition rate was evaluated as poor at less than 5 μm/h.
Testing the ink aggressiveness; observing whether the printing ink of the PCB flexible board is loose by using a microscope, and if the printing ink is loose, determining that the printing ink is unqualified; no loose, qualified.
The appearance of the plating layer: the morphology of the plating was visualized.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. An electroless tin plating solution, comprising, in terms of concentration: 5-25g/L of tin salt, 70-80g/L of complexing agent, 100-120g/L of thiourea substance, 1-10g/L of surfactant, 40-70g/L of reducing agent and MZxOy1-6g/L, wherein M is at least one of V, Nb, Zr and Na; z is a hetero element; x is 0 to 2; y is 3 to 5.
2. The electroless tin plating solution according to claim 1, wherein the tin salt is at least one selected from the group consisting of tin methane sulfonate, tin hydrochloride, tin sulfate, and stannous fluoroborate.
3. The electroless tin plating solution of claim 1, wherein the complexing agent comprises at least one of citric acid, malic acid, citric acid, tartaric acid.
4. The electroless tin plating solution of claim 1, wherein the reducing agent is selected from at least one of sodium hypophosphite, titanium chloride, ammonium hypophosphite, potassium hypophosphite, borohydride, and hydrazine hydrate.
5. The electroless tin plating solution of claim 1, wherein MZxOy, wherein M is at least one of V, Na; z is a hetero element; x is 0 to 2; y is 3 to 5.
6. The electroless tin plating solution of claim 1, wherein the surfactant is selected from at least one of cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride, polyethylene glycol, polyoxyethylene polyoxypropylene block copolymer.
7. The electroless tin plating solution as claimed in claim 6, wherein the average molecular weight of the polyoxyethylene polyoxypropylene block copolymer is 2000-2800.
8. The electroless tin plating solution according to claim 1, further comprising 16 to 20g/L of an unsaturated compound containing a polar group.
9. A method for preparing an electroless tin plating solution according to any one of claims 1 to 8, comprising the steps of: the components are mixed evenly.
10. A method of using the electroless tin plating solution according to any one of claims 1 to 8, wherein the electroless tin plating solution is applied under the condition of 40 to 45 ℃ for 10 to 15 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113737164A (en) * | 2021-08-31 | 2021-12-03 | 深圳市正天伟科技有限公司 | Stable tin chemical plating solution and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113737164A (en) * | 2021-08-31 | 2021-12-03 | 深圳市正天伟科技有限公司 | Stable tin chemical plating solution and application thereof |
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