CN112159997B - Metal-containing/carbon nanoparticle composition for rigid plate hole metallization - Google Patents
Metal-containing/carbon nanoparticle composition for rigid plate hole metallization Download PDFInfo
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- CN112159997B CN112159997B CN202010992980.3A CN202010992980A CN112159997B CN 112159997 B CN112159997 B CN 112159997B CN 202010992980 A CN202010992980 A CN 202010992980A CN 112159997 B CN112159997 B CN 112159997B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
Abstract
The invention relates to the field of printed circuit board hole metallization, and particularly provides a metal nanoparticle and carbon nanoparticle composition for rigid board hole metallization and a preparation method thereof. The invention provides a metal-containing/carbon nanoparticle composition for rigid plate hole metallization, which comprises nano carbon powder, metal salt, a reducing agent, an electrolyte, a dispersion medium, a dispersing agent and water; wherein the dispersant comprises a nonionic dispersant and an ionic dispersant; the nonionic dispersant comprises aromatic heterocyclic compounds and/or epoxy compounds and/or organic polymers and/or reactant products thereof; the ionic dispersant comprises a compound containing a hydrophilic group and/or an epoxy compound and/or an anionic dispersant and/or a reactant product thereof.
Description
Technical Field
The invention relates to the field of printed circuit board hole metallization, and particularly provides a metal nanoparticle and carbon nanoparticle composition for rigid board hole metallization and a preparation method thereof.
Background
The traditional rigid multilayer printed circuit board hole metallization is mainly completed by chemical copper plating, the process flow is complicated, a palladium-containing catalyst is used in the process, the copper plating process is expensive, and the process can cause environmental pollution, so the carbon nano composition electroplating technology is produced at the discretion.
The direct electroplating technology of carbon nanometer composition is one new process to replace chemical copper plating. Carbon powder or graphite with strong conductive capability is used as a conductive material, and a layer of conductive carbon black film is coated in a hole to realize metallization in the hole of the circuit board, so that subsequent electrolytic copper plating can be smoothly carried out. The method has the characteristics of simplifying the hole metallization process, saving working hours, reducing material consumption, effectively controlling the discharge amount of waste water and reducing the production cost of the PCB.
However, with the gradual application and upgrade of the carbon hole direct electroplating technology from a flexible single-layer circuit board to a flexible multilayer circuit board, a rigid flexible circuit board, a rigid single-layer board and a rigid multilayer board, the requirement for the carbon hole solution is increased due to the small hole and the increase of the board thickness. Particularly, carbon materials have certain short boards in material resistance, adsorbability, stability and reliability, and the application of the carbon materials in multi-layer boards and the like is limited. Therefore, improving the conductivity and the adsorption performance of the carbon pore liquid is a key technology for solving the problem of short carbon pore liquid plates.
Disclosure of Invention
The invention mainly solves the problem of insufficient conductivity and adsorption performance of the existing carbon pore liquid, and provides a high-conductivity and high-adsorption metal nanoparticle and carbon nanoparticle composition for a PCB.
The invention provides a metal-containing/carbon nanoparticle composition for rigid plate hole metallization, which comprises nano carbon powder, metal salt, a reducing agent, an electrolyte, a dispersion medium, a dispersing agent and water; wherein the dispersant comprises a nonionic dispersant and an ionic dispersant; the nonionic dispersant comprises aromatic heterocyclic compounds and/or epoxy compounds and/or organic polymers and/or reactant products thereof; the ionic dispersant comprises a compound containing a hydrophilic group and/or an epoxy compound and/or an anionic dispersant and/or a reactant product thereof.
As a preferred technical scheme, the composition comprises 2-15 wt% of nano carbon powder, metal salt, a reducing agent, 0.05-5 wt% of electrolyte, 0.3-20 wt% of a dispersion medium, 1.2-20 wt% of a dispersing agent and the balance of water; the concentration of the metal salt is 0.0001-0.04mol/L, and the concentration of the reducing agent is 0.0001-0.01 mol/L; preferably, the composition comprises 3-8% of nano carbon powder, metal salt, a reducing agent, 0.05-1% of electrolyte, 5-12% of dispersion medium, 1.8-2.5% of dispersing agent and the balance of water by weight percentage; the concentration of the metal salt is 0.003-0.005mol/L, and the concentration of the reducing agent is 0.03-0.05 mol/L.
The carbon nano powder is a carbon microcrystal aggregate of spherical or approximately spherical primary sound particles with a laminated structure, and preferably, the carbon nano powder comprises the following elements in percentage by weight: 0.1-8% of oxygen, 0.01-0.7% of sulfur, 0.01-0.6% of ash and the balance of carbon.
The particle size of the carbon nano powder is not particularly limited, and is preferably 10 nm-500 mu m; more preferably 10nm to 300 nm.
The invention adopts carbon black as the solid matter of the carbon nano powder, and the invention carries out pretreatment on the carbon black, and the pretreatment method comprises the following steps:
(1) soaking 4wt% of carbon black in an oxidant solution at 45-55 ℃ for 1.5-2.5 h; dispersing carbon black into nano particles by an ultrasonic cell crusher; the oxidant solution is selected from one or more of perchloric acid solution, hydrogen peroxide solution, sodium persulfate solution and ammonium persulfate solution;
(2) dissolving 2.5 wt% of silane coupling agent A151 in 50% ethanol solution, adding 25g of deionized water, adjusting the pH value of the system to 8.5 by using ammonia water, and adding the nanoparticles obtained in the step (1); transferring the system into a reaction kettle, reacting at 40 ℃ for 24h, centrifuging at high speed, washing, drying, grinding and crushing by a crusher, and filtering by a 200-mesh filter screen to obtain the product.
The dispersion medium of the present invention is a compound or polymer well known to those skilled in the art, and is not particularly limited, such as but not limited to: 1, 4-dioxane, carbon tetrachloride, xylene, benzene, toluene, aniline, thiophene, pyrrole, trichloromethane, tetrahydrofuran, 1, 2-dichloropropane, 1, 2-dichloroethane, pyridine, 2-butanone, cyclohexanone, isopropanol, acetone, ethanol, N-methylpyrrolidone, methanol, dimethylformamide, gamma-hydroxybutyric lactone, glycerol, ethylene-propylene copolymer, triacontahexaene, polydimethylsiloxane and butanol.
In one embodiment, the dispersion medium comprises N-methylpyrrolidone and gamma-hydroxybutyric lactone; preferably, the weight ratio of the N-methylpyrrolidone to the gamma-hydroxybutyric lactone is 1 (0.8-1.2); more preferably, the weight ratio of N-methylpyrrolidone to gamma-hydroxybutyrate lactone is 1: 1.
In another embodiment, the dispersion medium comprises N, N-dimethylamide and dimethylsulfoxide; preferably, the weight ratio of N, N-dimethylamide to dimethylsulfoxide is 1: (0.8 to 1.2); more preferably, the weight ratio of N, N-dimethylamide to dimethylsulfoxide is 1: 1.
The metal salt is not particularly limited in the present invention, and may be metal salt substances used for metallization of printed circuit board holes, which are well known to those skilled in the art, and is preferably sulfate, nitrate, hydrochloride, acetate, citrate of copper, nickel, silver, cobalt, such as, but not limited to, silver nitrate, copper nitrate, nickel citrate, etc.
The reducing agent is not particularly difficult to be limited in the present invention, and may be reducing substances for metallization of holes of printed circuit boards, which are well known to those skilled in the art, such as but not limited to: hydrazine hydrate, ethylenediamine, ethanolamine, phenylhydrazine, 2-aminopyridine, methylhydrazine, ethylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol and the like.
As a preferable technical scheme of the invention, the weight ratio of the nonionic dispersant to the ionic dispersant is 1: (1-10); preferably, the weight ratio of the nonionic dispersant to the ionic dispersant is 1: (1-5); more preferably, the weight ratio of the nonionic dispersant to the ionic dispersant is 1: 3.
the reactant product of the nonionic dispersant comprises the reaction product of the aromatic heterocyclic compound, the epoxy compound and/or the organic polymer and/or the reactant product thereof.
The reactant product of the ionic dispersant comprises a hydrophilic group-containing compound and/or an epoxy compound and/or an anionic dispersant and/or a reactant product of the anionic dispersant and/or the reactant product of the anionic dispersant, and the reaction product of the hydrophilic group-containing compound, the epoxy compound and the anionic dispersant is the reaction product of the hydrophilic group-containing compound, the epoxy compound and the anionic dispersant.
As a preferable technical scheme of the invention, the aromatic heterocyclic compound comprises a compound represented by a general formula (1) and/or a general formula (2) and/or a general formula (3),
（1）
（2）（3）
in the general formula (1), Xe is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl and substituted or unsubstituted aryl;
in the general formulae (1) to (3), R1、R2、R3、R4、R5、R6、R7、R8Each independently represents any one of H, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted aryl, cyano, isocyanate, alkenoyl, aldehyde, hydroxyl, amino, carboxyl, sulfydryl, sulfonic group, nitro, amido, alkenyl, alkynyl, aryl and azo, and R is1、R2Not H at the same time; r3、R4Not H at the same time; r6、R7Not H at the same time.
In a preferred embodiment of the present invention, the epoxy compound contains at least one of 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, di (ethylene glycol) diglycidyl ether, poly (ethylene glycol) diglycidyl ether compound, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, propylene glycol diglycidyl ether, di (propylene glycol) diglycidyl ether, and poly (propylene glycol) diglycidyl ether.
In a preferred embodiment of the present invention, the organic polymer includes at least one of polyethylene glycol, polyvinyl alcohol, polyetheramine, ethylene oxide-propylene oxide block polyether, alkylphenol ethoxylate, and polyvinylpyrrolidone.
The anionic dispersant comprises sulfonate and carboxylate, wherein the sulfonate and the carboxylate respectively and independently contain at least one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted C1-C500 epoxy and substituted or unsubstituted C1-C500 etheramine.
As a preferable embodiment of the present invention, the hydrophilic group-containing compound comprises a compound represented by the general formula (3),
—Rn—Y—V
（4）
in the general formula (3), Rn is selected from any one of arylene, heteroarylene and alkylene;
v is selected from any one of carboxyl, sulfonic acid group, phosphoric acid group, hydroxyl, amine group, ester group, amide group, carboxylate, sulfonate, phosphonate, amine salt and amide salt;
y is a spacer selected from the group consisting of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted C1-C500 epoxy, substituted or unsubstituted C1-C500 etheramine, -CO2-、-O2C-、-CO-、-OSO2-、-SO3-、-SO2-、-SO2C2H4O-、-SO2C2H4S-、-SO2C2H4NR"-、-O-、-S-、-NR"-、–-NR"CO-、-CONR"-、-NR"CO2-、-O2CNR"-、-NR"CONR"-、-N(COR")CO-、-CON(COR")-、-NR"COCH(CH2CO2R ') -and cyclic imides therefrom, -NR' COCH2CH(CO2R') -and cyclic imides therefrom, -CH (CH)2CO2R ') CONR' -and cyclic imides, -CH (CO) therefrom2R")CH2CONR '-and cyclic imides, sulfonamide groups, arylene groups, alkylene groups derived therefrom, and R' is selected from any one of hydrogen, substituted and unsubstituted C5-C20 aryl groups, and substituted and unsubstituted C1-C6 alkyl groups; r' are identical or different from one another.
As a preferable technical proposal of the invention, the dispersant also comprises a high molecular dispersant which is a compound represented by the general formula (5) and/or the general formula (6),
（5）（6）
wherein X1, X2 and X3 are respectively and independently selected from one of H, substituted or unsubstituted cyano, isocyanic acid, olefine acid, aldehyde group, hydroxyl, amino, carboxyl, sulfydryl, sulfonic acid group, nitro, amido, alkenyl, alkynyl, aryl and azo; rn is any one selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl and substituted or unsubstituted aryl; y1, Y2, Y3, K1, K2, K3 and P are central atoms and are respectively and independently selected from one of sulfur, nitrogen, phosphorus, oxygen and carbon; x1 are the same as or different from each other; x2 are the same as or different from each other; x3 are the same as or different from each other; y1 are the same as or different from each other; y2 are the same as or different from each other; y3 are the same as or different from each other; k1 are the same as or different from each other; k2 are the same as or different from each other; k3 are the same as or different from each other; rn are the same as or different from each other; p are the same as or different from each other.
The alkyl groups described in the present invention, for example but not limited to: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, tert-pentyl group, n-hexyl group, 1-dimethylbutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group and the like, and they may be the same or different from each other.
The alkenyl group in the present invention is exemplified by, but not limited to: vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 1-methyl-2-propenyl, 1-methyl-2-butenyl, 1-dimethyl-2-propenyl, and the like, which may be the same as or different from each other.
Alkylene groups described herein, such as but not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, isopentylene, sec-pentylene, tert-pentylene, neopentylene, n-hexylene, isohexylene, sec-hexylene, tert-hexylene, n-heptylene, isoheptylene, sec-heptylene, tert-heptylene, n-octylene, sec-octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, cyclododecylene, cyclotridecylene, cyclohexadecylene, cyclooctylene, cyclooctadecyl, cycloeicosylene, and the like, among them, methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, nonylene, decylene, undecylene, dodecylene and the like are preferable, and they may be the same as or different from each other.
As more specific aromatic ring compounds, for example, but not limited to; diphenylmethane diisocyanate, p-aminobenzaldehyde, and the like.
As more specific hydrophilic group-containing compounds or anionic dispersants, there are exemplified, but not limited to: sodium nonylphenol polyetheramine alkylsulfonate, sodium polyaniline sulfonate and the like.
As more specific examples of the polymeric dispersant, for example, but not limited to: polyvinylpyrrolidone, and the like.
The second aspect of the invention provides a preparation method of the composition, and the composition is put into a sand mill for grinding, wherein grinding balls used in the grinding process are zirconium balls, and the particle size of the zirconium balls is 0.3 mm. Preferably, the content of the zirconium beads is 73 to 77wt% based on the total weight percentage of the zirconium beads and the composition.
More preferably, the method of preparation of the composition comprises the steps of:
(1) firstly, mixing a macromolecular dispersant with metal salt, adding water, adding a reducing agent, stirring at a high temperature, and drying to obtain metal powder with the particle size of less than 200 nm;
(2) and (2) mixing the metal powder obtained in the step (1) with the rest components of the composition, and grinding the mixture in a sand mill.
The conditions in the grinding process are not particularly limited, and are within the range known by the skilled person, preferably, the current of the motor used in the grinding process is 40-50A, the frequency is 40-50 HZ, the rotating speed is 700-800 RMP, and the temperature of the cavity is 25-30 ℃.
In a third aspect, the present invention provides a process for preparing the composition, comprising the steps of: sequentially carrying out first micro-etching, water washing, cleaning, water washing, carbon hole soaking, drying, pore-finishing, water washing, carbon hole soaking, drying, second micro-etching, water washing and drying.
The preparation process of the composition is carried out in corresponding preparation tanks, for example, the preparation process comprises cleaning in a cleaning tank, washing in a washing tank, pore-forming in a pore-forming tank and carbon pore soaking in a carbon pore-forming tank; wherein the tank has corresponding water quality standard requirements, DI water is needed for water quality, the conductivity is less than 25us/cm, and the water hardness is less than 5 ppm; the DI water is deionized water.
The groove matching procedures of different grooves are as follows:
1. cleaning tank
DI water 95wt%
Cleaning solution SCC-665 wt%
Slot fitting program
1. DI water was first injected into the tank at about 1/2 volumes;
2. adding 5% of the tank volume of SCC-66 cleaning liquid produced by Guangdong Shuocho technology;
3. supplementing with DI water to standard liquid level;
4. starting a heater and circulating, and uniformly stirring for 40-60 s at 47-53 ℃.
2. Whole hole groove
DI water 95wt%
Whole pore solution SCC-675 wt%
Slot fitting program
Injecting DI water into the tank body by about 1/2 vol;
adding 5% of the volume of the tank of SCC-67 whole-pore liquid medicine produced by Guangdong Shuichi technology;
3. supplementing with DI water to standard liquid level;
4. starting a heater and circulating, and uniformly stirring for 40-60 s at 28-32 ℃.
3. Carbon hole groove
100wt% of carbon pore liquid
Slot fitting program
1. Adding the composition water solution to the standard liquid level in the tank;
2. starting a heater and circulating, and uniformly stirring for 50-70 s at 30-35 ℃.
4 micro-etching groove
The composition of the invention is subjected to first microetching and second microetching in the preparation process, the actual concentrations used in the two treatment processes are different, and the used solution components are as follows:
first microetching: comprises 2-4 wt% of concentrated sulfuric acid and the balance of water, and also comprises 70-90 g/L of sodium persulfate and 0.1-25 g/L of copper sulfate.
And (3) second microetching: comprises 2-4 wt% of concentrated sulfuric acid and the balance of water, and also comprises 90-130 g/L of sodium persulfate and 0.1-25 g/L of copper sulfate.
Slot fitting program
1. Injecting DI water into the tank body by about 3/4 volume;
2. starting circulation, adding a standard amount of sodium persulfate into the tank, and stirring until the sodium persulfate is dissolved;
3. adding standard amount of sulfuric acid and copper sulfate powder;
4. supplementing with DI water to standard liquid level;
5. starting a heater and circulating, and uniformly stirring, wherein the first micro-etching time is 15-30 s, and the temperature is 30-35 ℃; the time of the second micro-etching is 40-60 s, and the temperature is 30-35 ℃.
Compared with the prior art, the method has the following positive effects: the high-conductivity and high-adsorption metal nanoparticle and carbon nanoparticle composition for the PCB multilayer board is prepared, has extremely strong conductivity, the on-resistance of less than 60 ohms, good stability, the stable period of the particle size of 1 year and high effective concentration, the super-concentrated solid content of carbon black of 13 percent, avoids the problem of sedimentation in the use process, reduces the frequency of replacing bath solution, is non-toxic and pollution-free, and is environment-friendly.
The dispersion has good stability: the composition is used for preparing a dispersion liquid of a metal nanoparticle and carbon nanoparticle composition through the combined action of a dispersing agent and a reducing agent, and simultaneously, a high-speed grinding machine used in the preparation process enables conductive metal particles and carbon nanoparticles in the dispersion liquid to be stably controlled between 50 and 200 nanometers.
The conductivity is good: when the conductive carbon material is applied to the production of a printed circuit board, the conductive carbon material can be uniformly adsorbed on the hole wall through the electric charge adjustment of the pretreatment, and the resistance is tested to be between 1 and 30 ohms after the procedure is completed.
Drawings
FIG. 1: particle size distribution diagram of the carbon powder prepared in example 1;
FIG. 2: a schematic diagram of a DTV original film;
FIG. 3: schematic of DTV sheet treated with carbon nano-composition of example 1;
FIG. 4: schematic of the carbon nanocomposite treated DTV sheet of example 2;
FIG. 5: schematic of the carbon nanocomposite treated DTV sheet of example 3.
Detailed Description
In order to further understand the structure, characteristics and other objects of the present invention, the following detailed description is given with reference to the accompanying preferred embodiments, which are only used for illustrating the technical solutions of the present invention and are not limited to the present invention. The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein.
Example 1
the electrolyte is sodium silicate; the dispersion medium comprises N-methyl pyrrolidone and gamma-hydroxybutyric lactone, and the weight ratio of the N-methyl pyrrolidone to the gamma-hydroxybutyric lactone is 1: 1; the reducing agent is ethylene glycol; the metal salt is silver nitrate;
the dispersant comprises nonionic dispersant, ionic dispersant and high molecular dispersant; the weight ratio of the nonionic dispersant to the ionic dispersant to the polymeric dispersant is 1: 3: 0.4;
the nonionic dispersant is a copolymer of diphenylmethane diisocyanate/p-aminobenzaldehyde/ethylene glycol diglycidyl ether; the ionic dispersing agent is sodium nonyl phenol polyether amine alkyl sulfonate; the macromolecular dispersant is urea/chitosan oligosaccharide/ethylenediamine copolymer;
the carbon powder is pretreated carbon black, and the treatment process comprises the following steps:
(1) soaking 4wt% of carbon black in 40wt% perchloric acid solution at 45-55 ℃ for 1.5-2.5 h; dispersing carbon black into nano particles by an ultrasonic cell crusher;
(2) dissolving 2.5 wt% of silane coupling agent A151 in 50% ethanol solution, adding 25g of deionized water, adjusting the pH value of the system to 8.5 by using ammonia water, and adding the nanoparticles obtained in the step (1); transferring the system into a reaction kettle, reacting at 40 ℃ for 24 hours, centrifuging at a high speed, washing, drying, grinding and crushing by using a crusher, and filtering by using a 200-mesh filter screen to obtain the product;
the preparation method of the composition comprises the following steps:
(1) firstly, urea/chitosan oligosaccharide/ethylenediamine polymer solution and AgNO3Mixing the solutions, and reacting at 50-60 deg.C for 60-80 min;
(2) mixing the substance obtained in the step (1) with the rest components of the composition, and grinding the mixture in a sand mill until the particle size is less than 180 nm; wherein, the grinding balls used in the grinding process are zirconium balls, and the particle size of the zirconium balls is 0.3 mm; the zirconium bead content was 75wt% based on the total weight percent of the zirconium beads and the carbon nanocomposite; in the grinding process, the current of the motor is 45A, the frequency is 45HZ, the rotating speed is 750RMP, and the temperature of the cavity is 27 ℃.
Example 2
Embodiment 2 of the present invention provides a metal-containing/carbon nanoparticle composition for rigid plate hole metallization, which comprises, by weight, 3.2% of nano carbon powder, a metal salt, a reducing agent, 0.05% of an electrolyte, 10% of a dispersion medium, 2.2% of a dispersant, and the balance of water; the concentration of the metal salt is 0.002mol/L, and the concentration of the reducing agent is 0.035 mol/L;
the electrolyte is sodium silicate; the dispersion medium comprises N, N-dimethyl amide and dimethyl sulfoxide, and the weight ratio of the N, N-dimethyl amide to the dimethyl sulfoxide is 1: 1; the reducing agent is ethylene glycol; the metal salt is nickel citrate;
the dispersant comprises nonionic dispersant, ionic dispersant and high molecular dispersant; the weight ratio of the nonionic dispersant to the ionic dispersant to the polymeric dispersant is 1: 3: 0.4;
the nonionic dispersant is a diphenylmethane diisocyanate/polyetheramine/ethylene glycol diglycidyl ether copolymer; the ionic dispersant is sodium polyaniline sulfonate; the macromolecular dispersant is polyvinylpyrrolidone;
the carbon powder is pretreated carbon black, and the treatment process is the same as that of the embodiment 1;
the preparation method of the composition comprises the following steps:
(1) dissolving nickel citrate and polyvinylpyrrolidone into 2 liters of water, mixing, adding ethylene glycol, heating within the range of 150 ℃, reacting for 4 hours under the condition of high-speed stirring, and drying at 50 ℃ to obtain nano nickel powder with the diameter of less than 200 nm;
(2) mixing the substance obtained in the step (1) with the rest components of the composition, and grinding the mixture in a sand mill until the particle size is less than 180 nm; wherein, the grinding balls used in the grinding process are zirconium balls, and the particle size of the zirconium balls is 0.3 mm; the zirconium bead content was 75wt% based on the total weight percent of the zirconium beads and the carbon nanocomposite; in the grinding process, the current of the motor is 45A, the frequency is 45HZ, the rotating speed is 750RMP, and the temperature of the cavity is 27 ℃.
Example 3
Embodiment 2 of the present invention provides a metal-containing/carbon nanoparticle composition for rigid plate hole metallization, which comprises, by weight, 3.2% of nano carbon powder, a metal salt, a reducing agent, 0.05% of an electrolyte, 10% of a dispersion medium, 2.2% of a dispersant, and the balance of water; the concentration of the metal salt is 0.002mol/L, and the concentration of the reducing agent is 0.035 mol/L;
the electrolyte is sodium silicate; the dispersion medium comprises N, N-dimethyl amide and dimethyl sulfoxide, and the weight ratio of the N, N-dimethyl amide to the dimethyl sulfoxide is 1: 1; the reducing agent is ethylene glycol; the metal salt is silver nitrate;
the dispersant comprises nonionic dispersant, ionic dispersant and high molecular dispersant; the weight ratio of the nonionic dispersant to the ionic dispersant to the polymeric dispersant is 1: 3: 0.4;
the nonionic dispersant is a diphenylmethane diisocyanate/polyetheramine/ethylene glycol diglycidyl ether copolymer; the ionic dispersant is sodium polyaniline sulfonate; the macromolecular dispersant is polyvinylpyrrolidone-K30;
the carbon powder is pretreated carbon black, and the treatment process is the same as that of the embodiment 1;
the preparation method of the composition comprises the following steps:
(1) dissolving silver nitrate and polyvinylpyrrolidone into 1 liter of water, mixing, adding ethylene glycol, heating at 130 ℃, reacting for 4 hours under high-speed stirring, and drying at 50 ℃ to obtain nano nickel powder with the diameter of less than 200 nm;
(2) mixing the substance obtained in the step (1) with the rest components of the composition, and grinding the mixture in a sand mill until the particle size is less than 180 nm; wherein, the grinding balls used in the grinding process are zirconium balls, and the particle size of the zirconium balls is 0.3 mm; the zirconium bead content was 75wt% based on the total weight percent of the zirconium beads and the carbon nanocomposite; in the grinding process, the current of the motor is 45A, the frequency is 45HZ, the rotating speed is 750RMP, and the temperature of the cavity is 27 ℃.
Performance evaluation
1. Measurement of particle diameter and potential of carbon Black
Taking 0.05mL of carbon black dispersion, diluting the carbon black dispersion by 2000 times by deionized water, and then respectively testing the particle size by using a Malvern potential and particle size analyzer of British corporation, wherein the test result is shown in figure 1, namely the particle size distribution diagram of the carbon powder prepared in the example 1;
2. DTV testing
Based on the conductivity measurement of DTV-Chain/Hull panel: 25ASF area is not less than 6 holes, and 10ASF area is not less than 5 holes, wherein the hole diameter is 0.3mm, the plate thickness is 1.2 mm; the inspection method is electroplating under the following conditions: the current is 1A, and the time is 10 min; the test standard is as follows: high >5 wells, low >3 wells; the inspection tool is a Ha's groove; wherein, fig. 2 is a schematic diagram of a DTV original film; FIG. 3 is a schematic diagram of a DTV sheet treated with the carbon nano-composition of example 1; FIG. 4 is a schematic diagram of a DTV sheet treated with the carbon nano-composition of example 2; fig. 5 is a schematic view of the DTV chip treated by the carbon nano-composition of example 3.
The nanocarbon dispersion agents prepared in the embodiments 1,2 and 3 of the present invention and the carbon nanocomposite liquids prepared from nanocarbon have the characteristics of high particle size concentration, strong stability and good electrical conductivity.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. Finally, it is intended that all such modifications, equivalents and improvements as fall within the spirit and principles of the invention are included within the scope of the invention.
Claims (3)
1. A metal-containing/carbon nanoparticle composition for rigid plate hole metallization, which is characterized by comprising 3.2% of nano carbon powder, metal salt, a reducing agent, 0.05% of electrolyte, 10% of dispersion medium, 2.2% of dispersing agent and the balance of water in percentage by weight of the composition; the concentration of the metal salt is 0.002mol/L, and the concentration of the reducing agent is 0.035 mol/L;
the electrolyte is sodium silicate; the dispersion medium comprises N-methyl pyrrolidone and gamma-hydroxybutyric lactone, and the weight ratio of the N-methyl pyrrolidone to the gamma-hydroxybutyric lactone is 1: 1; the reducing agent is ethylene glycol; the metal salt is silver nitrate;
the dispersant comprises nonionic dispersant, ionic dispersant and high molecular dispersant; the weight ratio of the nonionic dispersant to the ionic dispersant to the polymeric dispersant is 1: 3: 0.4;
the nonionic dispersant is a copolymer of diphenylmethane diisocyanate/p-aminobenzaldehyde/ethylene glycol diglycidyl ether; the ionic dispersing agent is sodium nonyl phenol polyether amine alkyl sulfonate; the macromolecular dispersant is urea/chitosan oligosaccharide/ethylenediamine copolymer;
the carbon powder is pretreated carbon black, and the treatment process comprises the following steps:
(1) soaking 4wt% of carbon black in 40wt% perchloric acid solution at 45-55 ℃ for 1.5-2.5 h; dispersing carbon black into nano particles by an ultrasonic cell crusher;
(2) dissolving 2.5 wt% of silane coupling agent A151 in 50% ethanol solution, adding 25g of deionized water, adjusting the pH value of the system to 8.5 by using ammonia water, and adding the nanoparticles obtained in the step (1); transferring the system into a reaction kettle, reacting at 40 ℃ for 24h, centrifuging at high speed, washing, drying, grinding and crushing by a crusher, and filtering by a 200-mesh filter screen to obtain the product.
2. A method of preparing the metal-containing nanoparticle/carbon nanoparticle composition for rigid board via metallization of claim 1 comprising:
(1) firstly, urea/chitosan oligosaccharide/ethylenediamine polymer solution and AgNO3Mixing the solutions, and reacting at 50-60 deg.C for 60-80 min;
(2) mixing the substance obtained in the step (1) with the rest components of the composition, and grinding the mixture in a sand mill until the particle size is less than 180 nm; wherein, the grinding balls used in the grinding process are zirconium balls, and the particle size of the zirconium balls is 0.3 mm; the zirconium bead content was 75wt% based on the total weight percent of the zirconium beads and the carbon nanocomposite; in the grinding process, the current of the motor is 45A, the frequency is 45HZ, the rotating speed is 750RMP, and the temperature of the cavity is 27 ℃.
3. The process of claim 1 for preparing the metal-containing nanoparticle/carbon nanoparticle composition for rigid board via metallization, comprising the steps of: sequentially carrying out first micro-etching, water washing, cleaning, water washing, carbon hole soaking, drying, pore-finishing, water washing, carbon hole soaking, drying, second micro-etching, water washing and drying.
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| US4964948A (en) * | 1985-04-16 | 1990-10-23 | Protocad, Inc. | Printed circuit board through hole technique |
| JP2005118684A (en) * | 2003-10-17 | 2005-05-12 | Nippon Shokubai Co Ltd | Dispersant |
| CN101394712B (en) * | 2007-09-21 | 2010-08-25 | 清华大学 | Hole blackening solution and preparation thereof |
| JP2009106903A (en) * | 2007-10-31 | 2009-05-21 | Toyo Ink Mfg Co Ltd | Manufacturing method of metallic luster coat |
| WO2013059985A1 (en) * | 2011-10-25 | 2013-05-02 | 建业（惠州）电路版有限公司 | Process for metallisation of holes in printed circuit board |
| CN106653141B (en) * | 2016-11-18 | 2018-06-29 | 珠海特普力高精细化工有限公司 | A kind of manufacture of water-soluble conducting nanometer silver carbon slurry and its application process |
| CN107645829B (en) * | 2017-10-16 | 2020-07-10 | 广东天承科技有限公司 | Circuit board conductive liquid and preparation method and application thereof |
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| CN104818506A (en) * | 2015-05-28 | 2015-08-05 | 哈尔滨工业大学 | Solution for metalizing printed circuit board hole |
| CN106559961A (en) * | 2016-08-31 | 2017-04-05 | 广州市天承化工有限公司 | A kind of conduction liquid and preparation method thereof and conductive processing method |
| CN106634059A (en) * | 2016-12-16 | 2017-05-10 | 江南大学 | Preparation method of aqueous self-dispersing nanometer carbon black |
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