CN115820039A - Porous conductive ink, preparation method and application thereof - Google Patents
Porous conductive ink, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a porous conductive ink, comprising: 5-15 parts of graphene; 0.5 to 5 parts by weight of conductive particles; 12-45 parts of a binder; 0.5 to 2 parts by weight of hydrophilic oxide; 25-48 parts of high-boiling-point solvent; 7-30 parts of low-boiling-point solvent. Compared with the prior art, the conductive ink layer formed by using solvents with different high and low boiling points forms a porous structure after being dried, and metal is deposited in micropores after electroplating, so that reliable adhesive force is provided by means of physical inlaying; and the conductive ink can complete the conductivity after being cured, so that the conductive ink can be electroplated, the pollution problem of hexavalent chromium in industry is solved, the process is simple, chemical plating is not needed, noble metal activation can be avoided, the cost is further reduced, the conductive ink is suitable for various functional plastic products needing electroplating, and the adhesive force can meet the requirement.
Description
Technical Field
The invention belongs to the technical field of electroplating processes, and particularly relates to porous conductive ink, and a preparation method and application thereof.
Background
The surface metal plating technology is a surface engineering technology for decorating and protecting the surface of a substrate and obtaining certain special performance, and is also a metal deposition technology.
Surface metal coating techniques can be divided into wet coating and dry coating. The wet plating can be divided into chemical plating, electroplating and hot dipping. Chemical plating is a method for forming a compact plating layer on the surface of various materials by reducing metal ions into metal in a solution containing the metal ions by using a strengthening reducing agent according to the principle of redox reaction without electrifying. The electroplating process is an electrochemical reduction process that occurs at the interface of the metal and the electrolyte, with the prerequisite that adequate contact between the electrolyte and the metal is ensured. The purpose of chemical plating is to form a conductive metal film (generally copper plating or nickel plating) on the surface of the plastic product, so as to create conditions for electroplating the metal layer on the plastic product.
In order to obtain a good plating layer with good bonding force and different surface textures in the existing industry, the traditional roughening-activating-chemical plating conductive pretreatment and electroplating process are still adopted. However, hexavalent chromium used in the roughening process has serious environmental pollution, and has more obvious irreversible damage to direct-contact workers at the first line, and related countries and regions have increasingly strict restrictions on the use of hexavalent chromium, and in addition, the use of noble metal palladium in the activation process and the need to meet related environmental regulations lead to the continuous increase of electroplating cost and wastewater treatment cost of electroplating plants, and the plastic electroplating industry needs an environmentally-friendly production process urgently.
At present, the main research directions for developing a novel environment-friendly plastic electroplating process are as follows: (1) The components of the etching agent are adjusted, the use of hexavalent chromium is avoided, for example, manganese dioxide is used to replace chromic acid, the use amount of sulfuric acid is increased to avoid the use of chromic acid, and hydrogen peroxide/nitric acid is used to replace chromic acid, although the schemes avoid the use of hexavalent chromium, the coarsening effect is poor, the yield is low, and the final adhesive force can not meet the requirements of practical application; (2) Modifying the surface of a matrix, such as grafting P-TES (6-azide-2, 4-bis (3-triethoxysilyl) propylamino-1, 3,5 triazine) on a plastic substrate by UV (ultraviolet irradiation), grafting N-TES (6-azide-2, 4-dithiol monosodium (3-triethoxysilyl) propylamino-1, 3,5 triazine) molecules on the surface of the plastic by self-assembly to form molecular bonding, chemically spraying Ag, adsorbing an Ag film on an organic functional group after the molecular bonding, and then electroplating, or hydrolyzing and modifying a cyano group on the surface of ABS (acrylonitrile-butadiene-styrene copolymer) into a carboxyl group by using a sodium hydroxide solution, adsorbing silver ions by the carboxyl group to replace palladium for activation, completing the conductive pretreatment by chemical copper plating, or grafting PAA (polyacrylic acid) on the surface of the plastic, adsorbing copper ions by the PAA, and completing the conductive pretreatment after reduction, wherein the use of hexavalent chromium and noble metal palladium can be avoided, but the steps are complicated, the steps of chemical plating are still needed, the cost is high, and the surface of the matrix can provide limited adhesion; (3) The scheme can avoid the use of hexavalent chromium and noble metal palladium, but the addition of the conductive material can influence the mechanical property of the plastic, the conductivity is to be improved, and good adhesive force cannot be ensured; (4) The scheme avoids the use of hexavalent chromium and noble metal palladium, has the advantages of simple process, suitability for industrial large-scale production and the like, but the difficulty reported at present is that the adhesive force cannot meet the requirement of practical application.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a porous conductive ink with strong adhesion, and a preparation method and an application thereof.
The invention provides a porous conductive ink, comprising:
preferably, the conductive particles are selected from one or more of carbon black, silver nanoparticles and nickel nanoparticles;
the binder is selected from one or more of epoxy resin, polyurethane, alkyd resin, phenolic resin, organic silicon resin and thermosetting acrylic resin;
the boiling point of the high boiling point solvent is more than 150 ℃;
the low boiling point solvent has a boiling point of less than 85 ℃.
Preferably, the hydrophilic oxide is selected from hydrophilic silica.
Preferably, the high boiling point solvent is selected from one or more of dimethylformamide, N-methylpyrrolidone, ethylene glycol butyl ether and dibasic acid ester.
Preferably, the low-boiling point solvent is selected from one or more of ethyl acetate, acetonitrile, acetone, diethyl ether, ethyl formate and dimethyltetrahydrofuran.
The invention also provides a preparation method of the porous conductive ink, which comprises the following steps:
and mixing the graphene, the conductive particles, the binder, the hydrophilic oxide, the high-boiling-point solvent and the low-boiling-point solvent to obtain the porous conductive ink.
The invention also provides application of the porous conductive ink in an electroplating pretreatment technology.
The invention also provides an electroplating method, which comprises the following steps:
and coating the porous conductive ink on a substrate, and then electroplating.
Preferably, the porous conductive ink is coated to a thickness of 10 to 200 micrometers.
Preferably, the electroplating is specifically: and sequentially carrying out cyanide-free pyrophosphate copper plating, bright copper electroplating and semi-bright nickel electroplating. Other metals can be electroplated subsequently according to specific application requirements.
The invention provides a porous conductive ink, which comprises: 5-15 parts of graphene; 0.5 to 5 parts by weight of conductive particles; 12-45 parts of a binder; 0.5 to 2 parts by weight of hydrophilic oxide; 25-48 parts of high-boiling-point solvent; 7-30 parts of low-boiling-point solvent. Compared with the prior art, the conductive ink layer formed by using solvents with different high and low boiling points forms a porous structure after being dried, and metal is deposited in micropores after electroplating, so that reliable adhesive force is provided by means of physical inlaying; and the conductive ink can complete the conductivity after being cured, so that the conductive ink can be electroplated, the problem of pollution of hexavalent chromium in industry is solved, the cost is further reduced, the conductive ink is suitable for various functional plastic products needing to be electroplated, and the adhesive force can meet the requirement.
Further preferably, the method adopts a cyanide-free process in electroplating, and is green and environment-friendly.
Drawings
FIG. 1 is a laser microscope test chart for measuring the shape of a cured layer of a conductive ink prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2;
FIG. 2 is a scanning electron microscope test chart of the cured layers of the conductive inks prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2;
fig. 3 is a graph showing the results of a 90 ° tensile test of the conductive plastic substrates prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a porous conductive ink, comprising: 5-15 parts of graphene; 0.5 to 5 parts by weight of conductive particles; 12-45 parts of a binder; 0.5 to 2 parts by weight of hydrophilic oxide; 25-48 parts of high-boiling-point solvent; 7-30 parts of low-boiling-point solvent.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The content of the graphene in the porous conductive ink provided by the invention is preferably 8-15 parts by weight; in the embodiment provided by the invention, the content of the graphene in the porous conductive ink is specifically 10 parts by weight, 15 parts by weight or 8 parts by weight.
The porous conductive ink provided by the invention comprises conductive particles, wherein the conductive particles can be filled between graphene lamella layers to improve conductivity; the content of the conductive particles in the porous graphene is preferably 1 to 5 parts by weight, more preferably 2 to 5 parts by weight, and still more preferably 3 to 5 parts by weight; the kind of the conductive particles is not particularly limited as long as the conductive particles are well known to those skilled in the art, and one or more of carbon black, silver nanoparticles and nickel nanoparticles are preferable in the present invention.
The content of the binder in the porous conductive ink provided by the invention is preferably 15-45 parts by weight, more preferably 20-40 parts by weight, still more preferably 25-40 parts by weight, and most preferably 26-35 parts by weight; in the embodiment provided by the invention, the content of the binder in the porous conductive graphite is 33 parts by weight, 28 parts by weight, 26 parts by weight or 35 parts by weight; the kind of the binder is not particularly limited as long as the binder is a resin known to those skilled in the art and can be used as a binder, and in the present invention, one or more of epoxy resin (used with a curing agent), polyurethane, alkyd resin, phenolic resin, silicone resin, and thermosetting acrylic resin is preferred, and polyurethane is more preferred; in the present invention, the molecular weight of the polyurethane is preferably 2000 to 10000, more preferably 4000 to 8000, still more preferably 6000 to 7000, and most preferably 6500; the tensile strength of the polyurethane is preferably 50 to 100MPa, more preferably 60 to 90MPa, and still more preferably 70 to 80MPa.
The hydrophilic oxide is added into the printing ink, so that the hydrophilicity of the printing ink can be improved, the surface of the printing ink is in a porous structure after the printing ink is solidified into a film, the film layer is ensured to have good hydrophilicity, the electroplating solution can be infiltrated into the micropores, and metal particles are deposited in the holes of the film in the subsequent electroplating to form a physical riveting structure, so that good adhesive force is ensured. The content of the hydrophilic oxide in the porous conductive ink is preferably 0.8 to 2 parts by weight, and more preferably 1 to 2 parts by weight; the hydrophilic oxide is preferably hydrophilic silica, more preferably hydrophilic fumed silica; in the examples provided in the present invention, the example of the hydrophilic fumed silica a380 is specifically described.
According to the porous conductive ink provided by the invention, solvents with different high and low boiling points are used for enabling a cured film layer to form a porous structure; wherein, the high boiling point solvent refers to a solvent with the boiling point of 150-200 ℃, and the solvent has the characteristics of low evaporation speed and strong dissolving capacity; the low boiling point solvent refers to a solvent with a boiling point below 100 ℃, and the solvent has the characteristics of high evaporation speed, easy drying and low viscosity. The content of the high boiling point solvent in the porous conductive ink in the present invention is preferably 28 to 45 parts by weight, more preferably 30 to 45 parts by weight, and still more preferably 38 to 45 parts by weight; in the embodiment provided by the invention, the content of the high-boiling-point solvent in the porous conductive graphite is specifically 38 parts by weight, 40 parts by weight or 45 parts by weight; in the present invention, the boiling point of the high boiling point solvent is preferably more than 150 ℃; the high-boiling-point solvent is preferably one or more of Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dibasic acid ester (DBE); the content of the low-boiling point solvent in the porous conductive ink is preferably 10 to 30 parts by weight, more preferably 10 to 25 parts by weight, and still more preferably 10 to 20 parts by weight; in the embodiment provided by the invention, the content of the low-boiling-point solvent in the porous conductive graphite is specifically 15 parts by weight, 10 parts by weight or 20 parts by weight; the low boiling point solvent is not particularly limited, but is preferably an organic solvent having a boiling point of less than 85 ℃, and more preferably one or more of ethyl acetate, acetonitrile, acetone, diethyl ether, ethyl formate and dimethyltetrahydrofuran.
According to the invention, through using solvents with different high and low boiling points, the formed conductive ink layer forms a porous structure after being dried, and metal is deposited in micropores after electroplating, so that reliable adhesive force is provided by virtue of a physical embedding effect; and the conductive ink can complete the conductivity after being cured, so that the conductive ink can be electroplated, the problem of pollution of hexavalent chromium in industry is solved, the cost is further reduced, the conductive ink is suitable for various functional plastic products needing to be electroplated, and the adhesive force can meet the requirement.
The invention also provides a preparation method of the porous conductive ink, which comprises the following steps: and mixing the graphene, the conductive particles, the binder, the hydrophilic oxide, the high-boiling-point solvent and the low-boiling-point solvent to obtain the porous conductive ink.
The contents and types of the graphene, the conductive particles, the binder, the hydrophilic oxide, the high boiling point solvent and the low boiling point solvent are the same as those described above, and are not described herein again.
Mixing graphene, conductive particles, a binder, a hydrophilic oxide, a high boiling point solvent and a low boiling point solvent; the mixing method is not particularly limited as long as it is a method known to those skilled in the art, and in the present invention, ball milling or sand milling is preferable; the mixing time is preferably 1-4 h; the rotation speed of the mixing is preferably 200-500 rpm, more preferably 300-400 rpm, and still more preferably 350rpm; the ball-to-material ratio of the ball mill is preferably 1-1.5, and more preferably 1.1; the sanding is that 500g of zirconia ball grinding beads with the volume of 1 liter and the diameter of 0.65mm are added; the grinding balls used for ball milling or sanding preferably comprise grinding balls with different diameters, wherein the volume ratio of the large balls to the small balls is preferably (3-6): 1, more preferably (4 to 5): 1, more preferably 5:1; the diameter of the large ball is preferably 8-15 mm, and more preferably 10mm; the diameter of the pellet is preferably 3 to 6mm, more preferably 5mm.
Because the mixing is carried out by ball milling or sanding, the graphene in the porous conductive ink can be added in a precursor form; the graphene precursor is not particularly limited as long as it is a precursor well known to those skilled in the art, and expanded graphite is preferable in the present invention.
The invention also provides application of the porous conductive ink in an electroplating pretreatment technology. The porous conductive ink provided by the invention can be directly electroplated after being cured to form a film, so that the pollution problem of hexavalent chromium in industry is solved, the cost is further reduced, the porous conductive ink is suitable for various functional plastic products needing electroplating, and the adhesive force can meet the requirement.
The invention also provides an electroplating method, which comprises the following steps: and coating the porous conductive ink on a substrate, and then electroplating.
Coating porous conductive ink on a substrate; the coating method is a method well known to those skilled in the art, and blade coating, spraying, dipping and the like can be used without particular limitation; the thickness of the coating is preferably 10 to 200 micrometers (after drying), more preferably 20 to 150 micrometers, still more preferably 40 to 100 micrometers, and most preferably 60 to 70 micrometers; the substrate is not particularly limited as long as it is well known to those skilled in the art, and a non-conductive plastic substrate is preferable in the present invention.
After coating, curing to form a film; the method for curing and film forming is a method well known to those skilled in the art, and the methods of natural drying, blow drying, drying and the like are not particularly limited, and drying is preferred in the invention; the drying temperature is preferably 40-80 ℃, and more preferably 50-60 ℃; the drying time is preferably 1-3 h; the size of micropores on the surface of the film layer can be adjusted by adjusting different curing temperatures.
Then electroplating is carried out; the electroplating process is a plating process known to those skilled in the art, and is not particularly limited, and in the present invention, it is preferable to first perform cyanide-free pyrophosphate copper plating; the electroplating solution for cyanide-free pyrophosphate copper plating preferably comprises: 17 to 18 parts of pyrophosphate, 5.5 to 6 parts of copper salt, 5 to 6 parts of buffer salt, 0.6 to 1 part of ammonia water, 0.1 to 0.3 part of polyethylene glycol and 70 to 71 parts of water; the pyrophosphate is preferably potassium pyrophosphate; the copper salt is preferably copper sulfate; the buffer salt is preferably dipotassium hydrogen phosphate; the polyethylene glycol is preferably polyethylene glycol-600; the current density of the cyanide-free pyrophosphate copper plating is preferably 0.5-1 ASD; the time for plating the copper by the cyanide-free pyrophosphate is preferably 10-20 min; the pyrophosphate copper plating is used as the priming coating, so that the binding force between the coating and the substrate can be improved, and a cyanide-free process is further adopted, so that the method is green and environment-friendly.
After the cyanide-free pyrophosphate copper plating, bright copper is preferably electroplated, so that a plating layer with high corrosion resistance can be obtained; the plating solution for electroplating bright copper is a plating solution well known to those skilled in the art, and is not particularly limited, and the acid copper plating solution for electroplating bright copper in the invention preferably comprises 180-200 g/L of copper sulfate, 62-68 g/L of sulfuric acid, and 80-100 ppm of chloride ions; the current density of the electroplated bright copper is preferably 2-6 ASD; the time for electroplating bright copper is preferably 10-30 min.
After the bright copper is electroplated, electroplating semi-bright nickel is preferably also carried out; the plating solution used for electroplating the semi-gloss nickel preferably comprises 220-240 g/L of nickel sulfate, 60-70 g/L of nickel chloride and 40-50 g/L of boric acid; the current density of the electroplated semi-optical nickel is preferably 1-2 ASD; the time for electroplating the semi-gloss nickel is preferably 5-10 min.
In the invention, electroplating can be continuously carried out subsequently according to the requirements of products, such as all-gloss nickel, microporous nickel, bright chromium and the like.
After the plating, it is preferable to further dry; the drying method is a method well known to those skilled in the art, and is not particularly limited, and the drying time can be reduced by heating to dry, wherein the heating to dry can be performed under vacuum condition, or under normal pressure for a suitable time, or naturally left to dry; vacuum drying is preferred in the present invention; the drying temperature is preferably 40-100 ℃; the drying time is preferably 6 to 24 hours.
Compared with the traditional electroplating process flow, the method for coating the porous conductive ink on the non-conductive plastic substrate to realize the conductive treatment replaces the traditional conductive pretreatment method of degreasing, coarsening, activating and chemical plating, can avoid the use of hexavalent chromium in the coarsening process and the use of noble metal palladium in the activating process, simplifies the complex process flows of degreasing, neutralization, dispergation, chemical plating and the like, and not only is the process environment-friendly, but also the cost is greatly reduced.
In order to further illustrate the present invention, the following detailed description is made of a porous conductive ink, a preparation method and applications thereof.
The reagents used in the following examples are all commercially available; the hydrophilic silicas used in the examples and comparative examples were all a380 hydrophilic fumed silica purchased from degussa; molecular weight of polyurethane: 6500, tensile strength: 70MPa,100% modulus: 4.5; the graphene is 8-micron high-purity expanded graphite purchased by Qingdao rock-ocean carbon materials GmbH; the carbon BLACK is Cabot BLACK PEARLS 2000 superconducting carbon BLACK purchased from Calbot in USA; the nickel powder is 10 mu m flake conductive nickel powder purchased by Shanghai Naimeo nanometer technology limited; ABS is purchased by Xiamen Jianlin healthy household shares company Limited.
Example 1
Preparing porous conductive ink: 10 parts of graphene, 3 parts of carbon black, 1 part of hydrophilic silicon dioxide (brand: degussa, model A380 and hydrophilic fumed silica), 33 parts of polyurethane (molecular weight: 6500, tensile strength: 70MPa,100% modulus: 4.5), 38 parts of DMF (dimethyl formamide), and 15 parts of ethyl acetate; after mixing, ball milling was carried out at 350rpm for 3 hours using a planetary ball mill (mixed ball milling was carried out using large balls having a diameter of 10mm and small balls having a diameter of 5mm (large balls: small balls = 5), ball-to-material ratio (by volume) = 1.1).
Preparation of a conductive ink cured layer: transferring the porous conductive ink to an ABS plastic substrate by using a spraying method, wherein the coating thickness is as follows: 60 microns (after oven drying), curing conditions: drying at 60 ℃ under normal pressure for 2h.
Preparation of conductive plastic substrate: using cyanide-free alkaline pyrophosphate copper plating bath in sequence at 1A/dm 2 Electroplating for 10min, and bright acid copper plating solution at 4A/dm 2 Electroplating for 30min, and half-light nickel plating solution at 2A/dm 2 Electroplating for 5min. The components of the plating solution used are shown in tables 1 to 3.
TABLE 1 composition of copper pyrophosphate baths
TABLE 2 bright acid copper plating bath component table
TABLE 3 semi-gloss Nickel plating bath Components TABLE
And (3) post-processing parameters: drying for 24h at 60 ℃ under vacuum condition.
Example 2
Preparing porous conductive ink: 10 parts of graphene, 5 parts of nickel powder, 2 parts of hydrophilic silicon dioxide, 28 parts of polyurethane, 40 parts of DMF (dimethyl formamide), and 15 parts of ethyl acetate; the mixing was carried out in the same manner as in example 1.
Preparation of a conductive ink cured layer: transferring the porous conductive ink to an ABS plastic substrate by using a spraying method, wherein the coating thickness is as follows: 50 μm (after oven drying), curing conditions: drying at 60 ℃ under normal pressure for 3h.
Preparation of conductive plastic substrate: using cyanide-free alkaline pyrophosphate copper plating bath in sequence at 1A/dm 2 Electroplating for 10min, and polishing acid copper at 4A/dm 2 Electroplating for 30min, and half-light nickel plating solution at 2A/dm 2 Electroplating for 5min. The components of the plating solution used are shown in tables 1 to 3.
Example 3
Preparing porous conductive ink: 15 parts of graphene, 5 parts of carbon black, 1 part of hydrophilic silica, 26 parts of polyurethane, 45 parts of N-methylpyrrolidone and 10 parts of ethyl acetate; the mixing was carried out in the same manner as in example 1.
Preparation of a conductive ink cured layer: transferring the porous conductive ink to an ABS plastic substrate by using a spraying method, wherein the coating thickness is as follows: 65 μm (after oven drying), curing conditions: drying at 60 ℃ under normal pressure for 2.5h.
Preparation of conductive plastic substrate: using cyanide-free alkaline pyrophosphate copper plating bath in sequence at 1A/dm 2 Electroplating for 10min, and polishing acid copper at 4A/dm 2 Electroplating for 30min, and half-light nickel plating solution at 2A/dm 2 Electroplating for 5min. The components of the plating solution used are shown in tables 1 to 3.
Example 4
Preparing porous conductive ink: 8 parts of graphene, 3 parts of carbon black, 2 parts of hydrophilic silicon dioxide, 35 parts of polyurethane, 45 parts of DMF (dimethyl formamide), and 20 parts of 2-methyltetrahydrofuran; the mixing was carried out in the same manner as in example 1.
Preparation of a conductive ink cured layer: transferring the porous conductive ink to an ABS plastic substrate by using a spraying method, wherein the coating thickness is as follows: 50 microns (after oven drying), curing conditions: drying at 60 ℃ under normal pressure for 1.5h.
Preparation of conductive plastic substrate: using cyanide-free alkaline pyrophosphate copper plating bath in sequence at 1A/dm 2 Electroplating for 10min, and polishing acid copper at 4A/dm 2 Electroplating for 30min, and using semi-optical nickel plating solution at a concentration of 2A/dm 2 Electroplating for 5min. The plating bath compositions used are shown in tables 1-3.
Comparative example 1
Preparing conductive ink: 12 parts of graphene, 4 parts of carbon black, 2 parts of hydrophilic silicon dioxide, 40 parts of polyurethane and 42 parts of DMF (dimethyl formamide); the mixing was carried out in the same manner as in example 1.
Preparation of a conductive ink cured layer: transferring the porous conductive ink to an ABS plastic substrate by using a spraying method, wherein the coating thickness is as follows: 60 microns (after oven drying), curing conditions: drying at 60 ℃ under normal pressure for 3h.
Preparation of conductive plastic substrate: using cyanide-free alkaline pyrophosphate copper plating bath in sequence at a concentration of 1A/dm 2 Electroplating for 10min, and polishing acid copper at 4A/dm 2 Electroplating for 30min, and half-light nickel plating solution at 2A/dm 2 Electroplating for 5min. The components of the plating solution used are shown in tables 1 to 3.
Comparative example 2
Preparing conductive ink: 12 parts of graphene, 4 parts of carbon black, 2 parts of hydrophilic silica, 40 parts of polyurethane and 42 parts of ethyl acetate; the mixing was carried out in the same manner as in example 1.
Preparation of a conductive ink cured layer: transferring the porous conductive ink to an ABS plastic substrate by using a spraying method, wherein the coating thickness is as follows: 55 μm (after drying), curing conditions: drying at 60 ℃ under normal pressure for 2h.
Preparation of conductive plastic substrate: using cyanide-free alkaline pyrophosphate copper plating bath in sequence at 1A/dm 2 Electroplating for 10min, and polishing acid copper at 4A/dm 2 Electroplating for 30min, and using semi-optical nickel plating solution at a concentration of 2A/dm 2 Electroplating for 5min. The plating bath compositions used are shown in tables 1-3.
Performance detection
1. Conductive ink Performance testing
The conductive inks prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to a resistivity test and a sheet resistance test, respectively, and the results are shown in Table 4. As can be seen from table 4, compared to comparative examples 1 to 2, the sheet resistance and resistivity of the electroplated conductive ink layers prepared in examples 1 to 4 are lower, and the conductivity is better.
TABLE 4 results of resistivity/sheet resistance tests of conductive inks prepared in examples 1 to 4 and comparative examples 1 to 2
2. Testing of properties of cured layers of conductive ink
Shape measurement laser microscope test and scanning electron microscope test were performed on the cured layers of conductive inks prepared in examples 1 to 4 and comparative examples 1 to 2, respectively, and the results are shown in fig. 1 and 2. As can be seen from fig. 1 and 2, compared to the cured conductive ink layers prepared in comparative examples 1 to 2, which are flat film layers, the cured conductive ink layers prepared in examples 1 to 4 have porous structures on the surfaces and inside thereof, so that metal can be deposited in the micropores after electroplating, thereby improving the adhesion of the conductive ink layers.
The cured layers of the conductive inks prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to a sheet resistance test and a hundred grid test (ASTM D3359 standard test method), respectively, and the results are shown in table 5.
TABLE 5 cured layer Performance test results of conductive inks prepared in examples 1 to 4 and comparative examples 1 to 2
As can be seen from table 5, the cured layers of the conductive inks prepared in examples 1 to 4 were comparable to those prepared in comparative examples 1 to 2 at the level of the result of the hunger test, and the cured layers of the conductive inks prepared in examples 1 to 4 satisfied the requirements of commercial applications. The cured layers of the conductive inks prepared in examples 1 to 4 had lower sheet resistance and better conductivity than those of comparative examples 1 to 2.
3. Performance testing of conductive Plastic substrates
The conductive plastic substrates prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to a hundred grid test (ASTM D3359 standard test method and 90 ° tensile test (ASTM B533-85 (2013) standard test method), respectively), and the results are shown in table 6 and fig. 3.
As can be seen from table 6 and fig. 3, the level of the results of the baige test of the conductive plastic substrates prepared in examples 1 to 4 is equivalent to that of the conductive plastic substrates prepared in comparative examples 1 to 2, and the results of the 90 ° tensile test of the conductive plastic substrates prepared in examples 1 to 4 are significantly better than those of comparative examples 1 to 2, which indicates that the porous structure formed by the cured layer of the conductive ink significantly improves the adhesion of the plated film layer, and can be applied to a severer use environment.
TABLE 6 Baige and tensile test results for conductive plastic substrates prepared in examples 1-4 and comparative examples 1-2
| Total thickness of plating layer (mum) | Test results of the hundred squares | 90 degree pull (N/cm) | |
| Example 1 | 50 | 5B | 10.6 |
| Example 2 | 43 | 5B | 8.1 |
| Example 3 | 43 | 5B | 8.6 |
| Example 4 | 53 | 5B | 9.1 |
| Comparative example 1 | 40 | 5B | 4.5 |
| Comparative example 2 | 41 | 5B | 3.8 |
As can be seen from fig. 1 to 3 and tables 4 to 6, the conductive ink layer provided by the present invention has good adhesion and conductivity, and compared with the conventional electroplating process, the method of the present invention for coating the porous conductive ink on the non-conductive plastic substrate to achieve the conductive treatment replaces the conductive pretreatment method of the conventional process of degreasing, roughening, activating and chemical plating, thereby avoiding the use of hexavalent chromium in the roughening process and the use of noble metal palladium in the activating process, and in addition, simplifying the complex process flows of degreasing, neutralizing, dispergating, chemical plating and the like, not only the process is environment-friendly, but also the cost is greatly reduced.
Claims (10)
1. A porous conductive ink, comprising:
2. the porous conductive ink of claim 1, wherein the conductive particles are selected from one or more of carbon black, silver nanoparticles, and nickel nanoparticles;
the binder is selected from one or more of epoxy resin, polyurethane, alkyd resin, phenolic resin, organic silicon resin and thermosetting acrylic resin;
the boiling point of the high boiling point solvent is more than 150 ℃;
the low boiling point solvent has a boiling point of less than 85 ℃.
3. The porous conductive ink of claim 1, wherein the hydrophilic oxide is selected from hydrophilic silica.
4. The porous conductive ink according to claim 1, wherein the high boiling point solvent is selected from one or more of dimethylformamide, N-methylpyrrolidone, ethylene glycol butyl ether and dibasic acid ester.
5. The porous conductive ink according to claim 1, wherein the low boiling point solvent is selected from one or more of ethyl acetate, acetonitrile, acetone, diethyl ether, ethyl formate, and dimethyltetrahydrofuran.
6. A method of preparing the porous conductive ink of claim 1, comprising:
and mixing the graphene, the conductive particles, the binder, the hydrophilic oxide, the high-boiling-point solvent and the low-boiling-point solvent to obtain the porous conductive ink.
7. Use of the porous conductive ink of any one of claims 1 to 5 in a pre-plating treatment technique.
8. An electroplating method, comprising:
the porous conductive ink according to any one of claims 1 to 5 is coated on a substrate and then plated.
9. The electroplating method according to claim 8, wherein the porous conductive ink coating has a thickness of 10 to 200 μm.
10. The electroplating method according to claim 8, wherein the electroplating is specifically: and sequentially carrying out cyanide-free pyrophosphate copper plating, bright copper electroplating and semi-bright nickel electroplating.
Priority Applications (1)
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