CN116648003A - Hole metallization solution and preparation method and application thereof - Google Patents
Hole metallization solution and preparation method and application thereof Download PDFInfo
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- CN116648003A CN116648003A CN202210136820.8A CN202210136820A CN116648003A CN 116648003 A CN116648003 A CN 116648003A CN 202210136820 A CN202210136820 A CN 202210136820A CN 116648003 A CN116648003 A CN 116648003A
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- 238000001465 metallisation Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
-
- 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
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
Abstract
The invention provides a pore metallization solution, a preparation method and application thereof, wherein the pore metallization solution comprises, by mass, 2-10% of graphite, 0.1-10% of a water-soluble dispersing agent and 0.01-10% of a water-soluble binder; the well metallization solution further includes a buffer solution and water. The hole metallization solution provided by the invention has good dispersibility, good stability and strong impact resistance, and can be applied to a printed circuit board to effectively improve the electric conductivity of the product and improve the quality of the product.
Description
Technical Field
The invention belongs to the field of surface metallization treatment of insulating materials, and particularly relates to a pore metallization solution, a preparation method and application thereof, in particular to a pore metallization solution with strong graphite adhesion, and a preparation method and application thereof.
Background
The printed circuit board is mainly composed of an insulating base material and a conductor, plays roles of supporting and interconnecting in electronic equipment, and is an essential basic component of electronic information products. The 5G communication with the characteristics of high bandwidth, low time delay and large connection is beyond the current two application markets of intelligent terminals and automobile electronics in the global scope, and becomes a first engine for driving the industry of printed circuit boards to grow. The printed circuit boards required for 5G antennas and other signal transmission require the use of high frequency, high speed materials, which present new challenges to the production of printed circuit boards.
Hole metallization and methods thereof are key steps and core techniques for printed circuit board production. For a long time, the hole metallization is realized mainly by adopting an electroless copper plating method in the industry, but the method has complex process, needs a large amount of noble metal palladium and has high cost; hydrogen is generated during electroless copper plating, so that holes in holes are easy to cause; the process uses formaldehyde reducer and organic complexing agent to produce great amount of waste water and carcinogen, which seriously threatens ecological environment and human health. With the continuous miniaturization and portability of communication electronic equipment, the integration level of a printed circuit board is higher and higher, and the aperture and the diameter-depth ratio related to the printed circuit board, which play a role in conducting between layers, are smaller and smaller. Conventional electroless copper plating hole metallization processes have not been adapted to the requirements of technological development and direct electroplating of holes is being adopted by more and more printed circuit board manufacturers.
Since the 80 s of the 20 th century, new hole direct plating methods, including metallic palladium conductive film, polymeric conductive film and blackening method, have been internationally sought, with blackening method being most widely used. The black hole direct electroplating technology has low production cost, less types of used chemical reagents, no toxicity or harm, easy sewage treatment cost, simple process flow and high production efficiency, and is an environment-friendly and advanced production and manufacturing technology. The core of the black hole electroplating process is hole metalizing liquid, which is theoretically conductive slurry mainly composed of conductive carbon materials such as carbon black, carbon nano tubes, graphite and the like. The carbon black has small and uniform particle size and good conductivity, and is a main current conductive carrier prepared by the pore metalizing liquid. However, since carbon black is a granular zero-dimensional material, a dense conductive network is difficult to form in pores, and the pore breakage rate is high, so that a plurality of blackening processes are generally required, and the operation time is long. Patent CN109825863a discloses a formulation of a black hole liquid, which uses carbon nanotubes as one-dimensional material to replace carbon black, so as to improve the conductivity of the black hole film, but the corresponding metallization process is still longer, and the total time is as long as 14-22 minutes after the water washing and drying time is deducted. With the continuous development and improvement of the technology, the carbon black conductive matrix has been gradually replaced by graphite to form a new generation of metallization reagent-shadow. Compared with carbon black, graphite has a thin lamellar crystal structure, electrons can transfer on a two-dimensional plane, and after film formation on the pore wall, pores and deep holes can be endowed with better conductivity, and a thinner conductive layer network can be obtained. However, due to the special structure of graphite, the dispersibility of graphite is worse, and the difficulty for preparing the pore metalizing liquid is higher. The patent CN104562115a improves the dispersibility of graphite by adding a large amount of surfactant (0.8-1.2 parts), water-soluble polymer (1-2 parts) and its corresponding poor solvent (15-25 parts), organic solvent (8-12 parts), defoamer (0.4-1 parts), inorganic binder (0.5-1.5 parts) and the like, but the use of a large amount of polymer solvent seriously reduces the conductivity of graphite and affects the usability. At present, the domestic black hole method is mainly in the carbon black conductive matrix stage, and the black shadow metallization method taking graphite as a main body still has the defects of difficult dispersion, easy agglomeration, insufficient adhesion with an insulating surface, poor solution stability, easy failure after a period of time, and the like, and needs to be continuously improved.
Therefore, the development of the direct electroplating hole metallization solution which has good dispersibility, strong graphite adhesion, good conductivity after hole metallization, long-term stable use and convenient large-scale preparation and the preparation method thereof are very important and urgent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a pore metallization solution and a preparation method and application thereof, in particular to a pore metallization solution with strong graphite adhesion and a preparation method and application thereof. The hole metallization solution provided by the invention has good dispersibility, good stability and strong impact resistance, and can be applied to a printed circuit board to effectively improve the electric conductivity of the product and improve the quality of the product.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a pore metalizing solution comprising, by mass, 2-10% of graphite, 0.1-10% of a water-soluble dispersing agent, and 0.01-10% of a water-soluble binder.
The well metallization solution further includes a buffer solution and water.
The mass percentage of the graphite may be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, the mass percentage of the water-soluble dispersant may be 0.1%, 0.2%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., the mass percentage of the water-soluble binder may be 0.01%, 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., but the present invention is not limited to the above-listed values, and other values not listed in the above-listed value range are equally applicable.
The pore metallization solution can effectively improve the dispersibility, stability and impact resistance of the product by adopting specific components and proportions, and can effectively improve the conductivity and quality of the printed circuit board.
Preferably, the pore metallization solution comprises, by mass, 4-8% of graphite, 2-10% of a water-soluble dispersing agent and 0.01-2% of a water-soluble binder.
The well metallization solution further includes a buffer solution and water.
The specific proportion can further improve the dispersibility, stability and impact resistance of the product, and can further improve the conductivity and quality of the printed circuit board.
Preferably, the particle size of the graphite is not more than 10 μm, for example, 10 μm, 9 μm, 8 μm, 7 μm, 6 μm or 5 μm, etc., but not limited to the values recited above, and other values not recited in the above-mentioned value ranges are equally applicable, preferably not more than 1 μm.
Preferably, the graphite is subjected to a pretreatment including a plasma pretreatment or a liquid phase oxidation pretreatment.
The pretreatment process can lead the surface of the graphite to form rich oxygen-containing functional groups, endow the graphite with excellent electronegativity, and lead the graphite to be mutually exclusive in water static electricity, thereby achieving the effects of stable dispersion and inhibiting particle agglomeration.
Preferably, the plasma pretreatment comprises the steps of:
and (3) forming oxygen plasma by using a plasma generating device, sending the graphite into a plasma cracking chamber through nitrogen, and carrying out oxidation treatment on the surface of the graphite to obtain the graphite pretreated by the plasma.
Preferably, the oxygen plasma is a low temperature plasma having a temperature of not more than 500 ℃, for example 500 ℃, 450 ℃, 400 ℃, 350 ℃, or the like, but is not limited to the values listed above, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the liquid-phase oxidation pretreatment comprises the steps of:
mixing graphite with an oxidizing solution, stirring for 1-4h, filtering, and washing with water to obtain graphite subjected to liquid-phase oxidation treatment.
The stirring time may be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, or 4h, etc., but is not limited to the above-listed values, and other non-listed values within the above-listed ranges are equally applicable.
Preferably, the oxidizing solution is selected from any one or a combination of at least two of sulfuric acid, nitric acid and hydrogen peroxide, for example, a combination of sulfuric acid and nitric acid, a combination of sulfuric acid and hydrogen peroxide, or a combination of nitric acid and hydrogen peroxide, etc., but is not limited to the above-listed combinations, and other non-listed combinations within the above-listed combinations are equally applicable, and the combination of sulfuric acid and nitric acid is preferred.
Preferably, the water-soluble dispersant includes any one or a combination of at least two of polyacrylate, ethylene glycol, polyethylene glycol, glycerin, and n-butanol, for example, a combination of ethylene glycol and polyacrylate, a combination of ethylene glycol and polyethylene glycol, or a combination of glycerin and n-butanol, etc., but is not limited to the above-listed combinations, and other non-listed combinations within the above-listed combinations are equally applicable, preferably a combination of polyethylene glycol, glycerin, and n-butanol.
The specific dispersing agent can effectively improve the dispersibility of the product, further improve the stability of the product, improve the conductivity of the hole wall after hole metallization, and finally improve the conductivity and quality of the printed circuit board; meanwhile, the dispersibility of the product can be further improved by adopting a specific combination, so that the stability of the product is further improved, the conductivity of the hole wall after hole metallization is improved, and the conductivity and quality of the printed circuit board are improved.
Preferably, the water-soluble binder includes any one or a combination of at least two of glucose, fructose, sucrose, gelatin, dextran, agarose, chitosan, acrylic acid, methyl acrylate, methylcellulose, carboxymethyl cellulose salt, polyvinyl alcohol, alginate, anionic polyacrylamide, dextran, or agarose, for example, a combination of glucose and fructose, a combination of methyl acrylate and methyl cellulose, or a combination of polyvinyl alcohol and carboxymethyl cellulose salt, etc., but not limited to the above-listed combinations, other non-listed combinations within the above-listed combinations are equally applicable, preferably a combination of methyl cellulose, carboxymethyl cellulose, and carboxymethyl cellulose salt.
The specific water-soluble adhesive can improve the adhesive force of graphite and the insulating surface of the hole wall, enhance the interconnection between graphite particles, improve the conductivity of the hole wall after hole metallization, and further improve the conductivity and quality of the printed circuit board; meanwhile, the specific combination is adopted, so that the adhesion force between the graphite particles and the insulating surface of the hole wall can be further improved, the interconnection between the graphite particles is enhanced, the conductivity of the hole wall after hole metallization is improved, and the conductivity and the quality of the printed circuit board are further improved.
Preferably, the buffer solution comprises any one of borate system buffer solution, carbonate system buffer solution or barbital system buffer solution.
The buffer solution can effectively adjust and stabilize the pH value of the product, so that the product has good stability in the use process.
Preferably, the pore metalizing solution has a pH of 8 to 12, such as 8, 9, 10, 11 or 12, etc., but is not limited to the values recited above, and other non-recited values within the above range are equally applicable.
In a second aspect, the present invention provides a method of preparing a pore metalizing solution as described above, the method comprising the steps of:
and mixing graphite, a water-soluble dispersing agent, a water-soluble binder, a buffer solution and water to obtain the hole metallization solution.
In a third aspect, the invention also provides the use of a hole metallization solution as described above for the preparation of a printed circuit board.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a hole metallization solution, which can effectively improve the dispersibility, stability and impact resistance of a product and can effectively improve the conductivity and quality of a printed circuit board by adopting specific components and proportions; the dispersibility and stability of the product and the adhesive force of the insulating surface of the hole wall can be effectively improved by adopting the specific water-soluble dispersing agent and the water-soluble adhesive, the conductivity of the hole wall after hole metallization is improved, and the conductivity and quality of the printed circuit board are further improved.
Detailed Description
In order to further describe the technical means adopted by the present invention and the effects thereof, the following describes the technical scheme of the present invention in combination with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
In the examples below, the required raw medicines and reagents were purchased from national drug group chemical reagent company, inc.
Example 1
The embodiment provides a hole metallization solution, which comprises the following components in percentage by mass:
6% of graphite, 0.2% of polyethylene glycol, 0.2% of glycerol, 0.1% of n-butanol, 0.2% of methyl cellulose, 0.2% of carboxymethyl cellulose, 0.1% of sodium carboxymethyl cellulose, a carbonate system buffer solution (adjusting the pH of a pore metallization solution to 10) and the balance of water.
The preparation method comprises the following steps:
(1) Forming low-temperature oxygen plasma by using a plasma generating device, sending graphite into a plasma cracking chamber through nitrogen, controlling the temperature to be 500 ℃, and carrying out oxidation treatment (10 s) on the surface of the graphite to obtain high-dispersity graphite;
(2) Adding the high-dispersivity graphite obtained in the step (1) into water, adding polyethylene glycol, glycerol, n-butanol, methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose and carbonate system buffer solution under stirring, and carrying out ultrasonic stirring to obtain the pore metallization solution.
Example 2
The embodiment provides a hole metallization solution, which comprises the following components in percentage by mass:
4% of graphite, 10% of polyacrylate, 0.01% of glucose, a borate system buffer solution (adjusting the pH of a pore metallization solution to 8) and the balance of water.
The preparation method comprises the following steps:
(1) Dispersing graphite in an acidic solution of concentrated sulfuric acid (98.3%) and concentrated nitric acid (68%), stirring for 2 hours at 20 ℃, filtering and washing to obtain high-dispersivity graphite;
(2) And (3) adding the high-dispersity graphite obtained in the step (1) into water, adding the polyacrylate, glucose and borate system buffer solution under stirring, and carrying out ultrasonic stirring to obtain the pore metallization solution.
Example 3
The embodiment provides a hole metallization solution, which comprises the following components in percentage by mass:
graphite 8%, glycerol 2%, methyl cellulose 2%, carbonate system buffer solution (adjusting pH of the hole metallization solution to 12), and the balance of water.
The preparation method comprises the following steps:
(1) Dispersing graphite in an acidic solution of concentrated sulfuric acid (98.3%) and concentrated nitric acid (68%), stirring for 2 hours at 20 ℃, filtering and washing to obtain high-dispersivity graphite;
(2) Adding the high-dispersivity graphite obtained in the step (1) into water, adding the buffer solution of the glycerol, the methylcellulose and the carbonate system under stirring, and carrying out ultrasonic stirring to obtain the pore metallization solution.
Example 4
The embodiment provides a hole metallization solution, which comprises the following components in percentage by mass:
10% of graphite, 0.1% of polyethylene glycol, 10% of agarose, a carbonate system buffer solution (adjusting the pH of a hole metallization solution to 12) and the balance of water.
The preparation method is described in example 1.
Example 5
The embodiment provides a hole metallization solution, which comprises the following components in percentage by mass:
2% of graphite, 10% of ethylene glycol, 0.01% of gelatin, a barbital system buffer solution (adjusting the pH of a pore metallization solution to 8) and the balance of water.
Example 6
This example provides a pore metalizing solution in accordance with example 1 except that the composition does not contain polyethylene glycol, and the reduced portion is proportionally distributed to glycerol and n-butanol.
Example 7
This example provides a pore metalizing solution in accordance with example 1 except that the composition does not contain glycerol and the reduced portion is proportionally distributed to polyethylene glycol and n-butanol.
Example 8
This example provides a pore metalizing solution in accordance with example 1 except that the composition does not contain n-butanol and the reduced portion is proportionally distributed to glycerol and polyethylene glycol.
Example 9
This example provides a pore metalizing solution in the same manner as example 1 except that the composition does not contain polyethylene glycol and glycerin, and a reduced fraction is assigned to n-butanol.
Example 10
This example provides a pore metalizing solution in accordance with example 1 except that the composition does not contain glycerol and n-butanol and the reduced portion is proportionally distributed to polyethylene glycol.
Example 11
This example provides a pore metalizing solution in accordance with example 1 except that the composition does not contain n-butanol and polyethylene glycol, and the reduced portion is proportionally distributed to glycerol.
Example 12
This example provides a pore metallizing solution in the same manner as in example 1 except that the composition does not contain sodium carboxymethyl cellulose, and the reduced portion is proportionally distributed to methyl cellulose and carboxymethyl cellulose.
Example 13
This example provides a pore metalizing solution in the same manner as in example 1 except that the composition does not contain methylcellulose, and the reduced portion is proportionally distributed to sodium carboxymethyl cellulose and carboxymethyl cellulose.
Example 14
This example provides a pore metalizing solution in the same manner as in example 1 except that the composition does not contain carboxymethyl cellulose, and the reduced portion is proportionally distributed to methyl cellulose and sodium carboxymethyl cellulose.
Example 15
This example provides a pore metalizing solution in the same manner as in example 1 except that the composition does not contain methylcellulose, carboxymethylcellulose, and a reduced fraction of the sodium carboxymethylcellulose is assigned.
Example 16
This example provides a pore metalizing solution in the same manner as in example 1 except that the composition does not contain sodium carboxymethyl cellulose, and a reduced fraction is assigned to methyl cellulose.
Example 17
This example provides a pore metalizing solution in the same manner as in example 1 except that the composition does not contain methylcellulose, sodium carboxymethylcellulose, and a reduced fraction of the composition is distributed to carboxymethylcellulose.
Example 18
This example provides a pore metalizing solution in the same composition as example 1 except that 0.2% methylcellulose, 0.2% carboxymethylcellulose, and 0.1% carboxymethylcellulose sodium were replaced with 0.5% sucrose.
Example 19
This example provides a pore metalizing solution having a composition consistent with example 1.
The preparation method was the same as in example 1 except that the step (1) was replaced with the step (1) in example 2.
Example 20
This example provides a pore metalizing solution having a composition consistent with example 1.
The preparation process was identical to example 1, except that step (1) was not included.
And (3) effect test:
the washed backlight test piece (pore diameter 1mm, thickness 1 mm) was placed in a pore-forming agent (MacDermid company, shawdow Cleaner Conditioner V pore-forming agent), ultrasonically washed at 30 ℃ for 70s, then water-washed for 20s, placed in a pore-metallizing solution (provided in examples 1-20, respectively), ultrasonically washed at 30 ℃ for 60s, then placed in a fixer (2% sulfuric acid solution) for 20s at 30 ℃, then water-washed for 20s, dried, then placed in a microetching agent (containing 10% sodium persulfate, 1% sulfuric acid) for 30s at 30 ℃, then water-washed for 20s, dried, and finally plated. And after the operation is finished, testing the double-sided conductivity, the copper plating backlight grade and the hole copper thickness of the circuit board before electroplating after the metallization of the backlight test piece holes. The same operation as above was performed using a plate with a hole diameter of 100 μm, a thickness of 50 μm and a copper layer thickness of 12 μm, and the holes were connected in series with each other by etching to test the resistance value of the hole chain and the hole copper thickness.
The conductivity test of the backlight test piece adopts an ohm meter to measure and determine the resistance between copper layers on two sides of the backlight test piece, so as to reflect the conductivity of the graphite deposition layer in the hole after hole metallization; the backlight grade test is used for examining the deposition effect of the metal plated with holes, polishing and polishing the holes after the holes are cut, observing the holes under a microscope, wherein the best effect is that almost no light passes through, the 10 grades are the best, the more the light passing points are, the lower the grade is, and the 1 grade is the worst. The thickness of the copper in the hole was measured after slicing through the hole. The Mo Kongkong chain resistance test of the plate is reflected by measuring the resistance between the first and last holes of the chain of holes.
The results were as follows:
the data show that the hole metallization solution provided by the invention can effectively conduct electricity and quality of a printed circuit board; comparing examples 1, 19, 20, it was found that the present invention can further improve the conductivity and quality of the printed circuit board by performing a specific pretreatment step on the graphite; comparing examples 1, 6-18, it can be found that the invention is further improved in the range of the preferable water-soluble dispersant and water-soluble binder, and the invention further provides the conductivity and quality of the printed circuit board by adopting the combination of polyethylene glycol, glycerin and n-butanol and the combination of methylcellulose, carboxymethyl cellulose and carboxymethyl cellulose salt, which has remarkable advantages.
The applicant states that the present invention is illustrated by the above examples of pore metallizing solutions, methods of making and using the same, but the invention is not limited to, i.e., does not mean that the invention must be practiced in dependence upon, the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (10)
1. The pore metallization solution is characterized by comprising, by mass, 2-10% of graphite, 0.1-10% of a water-soluble dispersing agent and 0.01-10% of a water-soluble binder;
the well metallization solution further includes a buffer solution and water.
2. The pore metallization solution of claim 1, wherein the pore metallization solution comprises, in mass percent, 4-8% graphite, 2-10% water-soluble dispersant, 0.01-2% water-soluble binder;
the well metallization solution further includes a buffer solution and water.
3. Pore metallizing solution according to claim 1 or 2, wherein the graphite has a particle size of not more than 10 μm, preferably not more than 1 μm;
preferably, the graphite is subjected to a pretreatment including a plasma pretreatment or a liquid phase oxidation pretreatment.
4. A pore metallizing solution according to claim 3, wherein said plasma pretreatment comprises the steps of:
forming oxygen plasma by using a plasma generating device, sending graphite into a plasma cracking chamber through nitrogen, and carrying out oxidation treatment on the surface of the graphite to obtain plasma pretreated graphite;
preferably, the oxygen plasma is a low temperature plasma having a temperature of not more than 500 ℃.
5. The pore metallizing solution according to claim 3 or 4, wherein said liquid phase oxidation pretreatment comprises the steps of:
mixing graphite with an oxidizing solution, stirring for 1-4h, filtering, and washing with water to obtain graphite subjected to liquid-phase oxidation treatment;
preferably, the oxidizing solution is selected from any one or a combination of at least two of sulfuric acid, nitric acid and hydrogen peroxide, preferably a combination of sulfuric acid and nitric acid.
6. The pore metalizing solution of any of claims 1-5, wherein the water soluble dispersant comprises any one or a combination of at least two of polyacrylate, ethylene glycol, polyethylene glycol, glycerol, n-butanol, preferably a combination of polyethylene glycol, glycerol, and n-butanol.
7. The pore metalizing solution of any of claims 1-6, wherein the water soluble binder comprises any one or a combination of at least two of glucose, fructose, sucrose, gelatin, dextran, agarose, chitosan, acrylic acid, methyl acrylate, methylcellulose, carboxymethylcellulose salts, polyvinyl alcohol, alginate, anionic polyacrylamide, dextran, or agarose, preferably a combination of methylcellulose, carboxymethylcellulose, and carboxymethylcellulose salts.
8. The pore metallization solution of any one of claims 1-7, wherein the buffer solution comprises any one of a borate system buffer solution, a carbonate system buffer solution, or a barbital system buffer solution;
preferably, the pore metalizing solution has a pH of 8-12.
9. A method of preparing a pore metallizing solution according to any one of claims 1-8, said method comprising the steps of:
and mixing graphite, a water-soluble dispersing agent, a water-soluble binder, a buffer solution and water to obtain the hole metallization solution.
10. Use of a hole metallization solution according to any one of claims 1-8 for the preparation of a printed circuit board.
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