CN108977862A - The method of insulating substrate electroplating surface metal - Google Patents
The method of insulating substrate electroplating surface metal Download PDFInfo
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- CN108977862A CN108977862A CN201811003652.5A CN201811003652A CN108977862A CN 108977862 A CN108977862 A CN 108977862A CN 201811003652 A CN201811003652 A CN 201811003652A CN 108977862 A CN108977862 A CN 108977862A
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- insulating substrate
- sodium
- electroplating surface
- surface metal
- manganese dioxide
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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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
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
Abstract
The present invention relates to a kind of method of insulating substrate electroplating surface metal, include the following steps: to contact the insulating substrate surface to generate modified surface with water soluble anion compound；The modified surface is contacted with the aqueous solution containing high manganese ion, to form manganese dioxide adsorption layer on the modified surface；Conductive polymer coating is formed in manganese dioxide absorption layer surface；Metal layer is formed in the conductive polymer coating electroplating surface.The above method is deposited using anionic compound on insulating substrate surface, the coat combined closely is formed between substrate surface, by this modification and absorption, it is formed uniformly and after there is certain thickness film on surface, under identical metal electroplating solution and plating conditions, the covering power and dispersibility of electroplate liquid can obtain larger raising, the gained coat of metal has flat, uniformly, the good feature of backlight effect, the generation for avoiding hole broken with the excessively thin phenomenon of individual site electroplated metal layers in hole.
Description
Technical field
The present invention relates to technical field of surface, more particularly to a kind of method of insulating substrate electroplating surface metal.
Background technique
With the fast development of electronics and information industry, interconnect the printed circuit board (Printed of carrier as electronics
Circuit Board, PCB) industry also high speed development.From pervious double-sided multi-layer to high density interconnection board HDI (High
Density Interconnector), then class support plate SLPCB (Substratelike-PCB) till now, technique requires more next
It is higher.In the past, for the electroless copper of the interlayer conduction of the technique using formaldehyde as reducing agent, formaldehyde is a kind of cause being more toxic
Cancer substance causes very big threat to the health of operator.In addition, having copper ion, nickel ion and palladium ion etc. in the technique
The use and discharge of metal ion, it is often more important that, the waste water containing a large amount of complexing agents generated in the technique is difficult to handle.Cause
This, present technique substitutes traditional chemical-copper-plating process using conducting polymer technique.Firstly, it is necessary in the hole of circuit board
One layer of Organic Conductive Films are deposited on wall insulating layer, and then carry out electroless plating using the electric conductivity of conductive film, finally in its table
Face forms one layer of permanent conductive layers of copper.The biggest advantage is to operating process environmental protection, process flows to shorten for the technique, not use
Formaldehyde, no heavy metal ion and its complexing agent using and discharging, and waste water treatment step is simple, and specific energy consumption reduces, running
Cost reduces.But there is also deadly defects for the technique, due to the charge characteristic of processed substrate surface (such as hole wall), if
Substrate directly is handled using solution containing MnO4, then in substrate surface, especially the manganese dioxide amount meeting of hole wall surface deposition
Seldom, thus can be than relatively thin in substrate surface formation Organic Conductive Films, the electric conductivity of organic conductive polymer is weaker, especially exists
Glass fibre site reaction in circuit board apertures is worse, often has the generation of empty (Void) in electroplating process, is commonly called as " disconnected copper ",
It will appear light transmission and cavity in backlight test.In addition, even if light transmission and cavity are not generated in backlight test, if some in hole
The copper thickness of position is extremely thin, still will affect the electric conductivity and stability of circuit board.
Therefore, the prior art still has much room for improvement.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of methods of insulating substrate electroplating surface metal.
Specific technical solution is as follows:
A kind of method of insulating substrate electroplating surface metal, includes the following steps:
Contact the insulating substrate surface with water soluble anion compound, to form modified surface；
The modified surface is contacted with the aqueous solution containing high manganese ion, to form two on the modified surface
Manganese oxide adsorption layer；
Conductive polymer coating is formed in manganese dioxide absorption layer surface；
Metal layer is formed in the conductive polymer coating electroplating surface.
The insulating substrate is impregnated it should be understood that the insulating substrate surface contacts can be with anionic compound
In the aqueous solution of anionic compound, wherein the concentration of anion is 0.1g/L-20g/L in anionic compound aqueous solution.
Using anionic compound processing substrate operation temperature can be carried out at 15 DEG C~80 DEG C, the operating time can be 50 seconds~
5 minutes.
In wherein some embodiments, the water soluble anion compound be selected from sulfonate, carboxylate, sulfuric acid and
One of phosphate ester salt is a variety of.
In wherein some embodiments, the sulfonate be selected from polybutadiene sulfonic acid sodium, neopelex, 16
Sodium alkyl sulfonate, Sodium Allyl Sulfonate and lignin sulfonic acid it is one or more；
The carboxylic acids is selected from enuatrol, sodium carboxymethylcellulose, sodium gluconate, AEO carboxylic acid sodium
It is one or more with odium stearate；
The sulfuric acid is selected from laureth sodium sulfovinate, lauryl sodium sulfate and lauramide sodium ethylsulfate
It is one or more；
The phosphate ester salt is selected from hexadecanyl phosphate sodium, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium and fatty alcohol polyoxyethylene ether phosphorus
Acid esters potassium it is one or more.
In wherein some embodiments, the concentration of the water soluble anion compound is 0.1g/L-20g/L.
In wherein some embodiments, the density of the manganese dioxide adsorption layer is 20 μ g/cm2-120μg/cm2。
In wherein some embodiments, the material of the metal layer is selected from copper, gold, silver or nickel.
In wherein some embodiments, the insulating substrate is selected from plastics, resin, glass fibre, ceramics or stone material.
It is a further object of the present invention to provide a kind of preparation methods of printed wiring board, including above-mentioned insulating substrate surface electricity
The method of plating metal.
It is a further object of the present invention to provide the printed wiring boards that above-mentioned preparation method obtains.
The principle of the present invention and advantage:
The method of above-mentioned insulating substrate electroplating surface metal makes the insulating substrate surface and water soluble anion first
Object contact is closed, modified surface is obtained；Water soluble anion compound has good binding force on insulating substrate surface, and works as and pass through
After the processing of anionic compound aqueous solution, deposition forms fine and close electrically charged multilayer reproducibility film on insulating substrate surface.This
Film layer can effectively improve the surface characteristic of insulating substrate, and by redox reaction, can adsorb former substrate surface cannot
Oxidant etc. in the substance effectively adsorbed, such as plating plating.
The modified surface is contacted with the aqueous solution containing high manganese ion again, to be formed on the modified surface
Manganese dioxide adsorption layer；The anionic compound deposited on modified surface described in the step plays the role of reducing agent, energy
Promote the absorption of oxidation product manganese dioxide.Also, the fine and close multi-layer thin that anionic compound deposits on insulating substrate surface
Film can make the more uniform deposition of manganese dioxide, avoid in subsequent copper facing, the relatively thin phenomenon of some site layers of copper occur.
Finally conductive polymer coating is formed in manganese dioxide absorption layer surface；In the conducting polymer layer surface electricity
Plating forms metal layer.
Compared with existing insulating substrate process for treating surface, the above method is using anionic compound in insulating substrate table
Face deposition, forms the coat combined closely between substrate surface, by this modification and absorption, surface formed uniformly and
After certain thickness film, under identical metal electroplating solution and plating conditions, the covering power and dispersion energy of electroplate liquid
Power can obtain larger raising, so that insulating substrate surface is very beneficial for being formed flat in subsequent plating and has and be suitable for
The coat of metal of thickness, the gained coat of metal have flat, and uniformly, backlight effect good feature is also easy to control during plating
The thickness of metal deposit processed, avoid hole broken or hole in some thin phenomenon of position copper generation.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
" water soluble anion compound " of the present invention, such as can be sulfonate, carboxylate, sulfuric acid and phosphorus
Acid esters salt, the compound of every kind of salt form can be polymer form or non-polymer form.The present invention mainly utilizes it exhausted
The coating with reproducibility that edge substrate surface is formed, generates manganese dioxide adsorption layer for sequential reduction permanganate.
" conducting polymer " is mainly that some polymer with conjugation Π key are formed after chemistry or electrochemical doping,
Conductivity can extend to a kind of high molecular material of conductor range from insulator.Such as can be common polythiophene, polyaniline,
Poly- furans, polypyrrole, poly styrene sulfonate and its derivative etc. can also mix various metals ion, such as lithium wherein
Ion, aluminium ion, sodium ion and potassium ion etc..
TP value used in embodiment (throwing power) is the synthesis of copper plating bath covering power and dispersibility
Evaluation index.According to different evaluation angles, TP value generally comprises TPstdAnd TPmin.Wherein TPstdIt is metal in evaluation substrate aperture
The overall situation of plating is equal to the ratio of hole copper center thickness of coating (average value) and aperture copper coating thickness (average value).
TPminThe case where being plate metal thickness thinnest point in evaluation substrate aperture, the copper coating thickness and aperture for being equal to the point lead to coating
The ratio of thickness (average value).Present invention uses identical copper plating baths and plating conditions to carry out metal lining.Therefore, last gold
The TP value for belonging to plating reflects the different water soluble anion compound of the present invention to the Modifying Capability on insulating substrate surface.Backlight
Test is to evaluate one of the method for metal deposition effect, and the result detected is indicated with backlight level, is divided into 0-10 grades, from every
The section for the 1mm thickness removed on block plate is placed under the transmission mode of conventional light microscope and is seen with 50 times of amplification factors
It examines.The quality of copper plating is to compare to obtain by backlight level picture general in the brightness and industry observed under the microscope
's.If not observing light, which is 10 grades of backlight level if being completely in black, indicates that copper is completely covered.If light is complete
Full impregnated is crossed without any dark area, is indicated few or is deposited on substrate surface without copper metal, which is 0 grade.If simultaneously
The region for having dark area and thering is light to penetrate, then according to from 1 to 9 classification compared with normal pictures.
Experimental method in following embodiments is unless otherwise specified conventional method.Original as used in the following examples
Material, reagent material etc. are commercially available products unless otherwise specified.
Embodiment 1
Substrate surface modification: taking the plastic base of two pieces of 1.6mm thickness, generates the logical of the aperture 0.2mm using laser on it
Hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then at 50 DEG C
Under, the allyl sulphonic acid sodium water solution for immersing 1g/L is handled 4.5 minutes, after washing, at 80 DEG C, immerses 60g/L, pH=
It is handled about 1.5 minutes in 6 (being adjusted with the boric acid of 10g/L) potassium permanganate solutions, it is spare through washing after processing completion.
The test of manganese dioxide adsorbance: taking one of processed substrate, contains 3% (volume fraction) sulphur with enough
Manganese dioxide on acid and 3% (volume fraction) mixed solution of hydrogen peroxide elution substrate, calculates manganese dioxide on substrate
Adsorbance (density) be 38.18 μ g/cm2。
Electro-coppering: by another piece of processed substrate, 3, the 4- ethylene dioxy thiophene of the 10ml/L containing following ingredient is immersed
Pheno, 6g/L p-methyl benzenesulfonic acid, 7ml/L OP emulsifier mixed solution in 3 minutes.After the completion, substrate immersion is contained 80g/L
Cupric sulfate pentahydrate, 1g/L sulfuric acid (adjusting pH=2), the chloride ion of 40mg/L, 8mg/L dithio-bis-propylene sulfonic acid sodium salt, the poly- second of 1g/L
In the copper electroplating liquid of glycol, apply 2A/dm2Electric current be electroplated 60 minutes, on the surface of the substrate, plating in through-hole and blind hole
Copper.Finally, testing detection display by backlight, backlight level is up to 9 grades, electroplating effect TPstdValue is 84%, TPminValue is 70%.
Embodiment 2
Substrate surface modification: taking the glass fabric of two pieces of 1.6mm thickness, generates the aperture 0.2mm using laser on it
Through-hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then 30
At DEG C, the sodium dodecyl benzene sulfonate aqueous solution for immersing 5g/L is handled about 2 minutes, after washing, at 80 DEG C, immerses 60g/
L, pH=6, which (are adjusted) in potassium permanganate solution with the boric acid of 10g/L, to be handled about 1.5 minutes, through washing after processing completion,
It is spare.
The test of manganese dioxide adsorbance: taking one of processed glass fabric, contains 3% (volume with enough
Score) sulfuric acid and 3% (volume fraction) mixed solution of hydrogen peroxide elution substrate on manganese dioxide, calculate manganese dioxide and exist
Adsorbance (density) on glass fabric is 119.29 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified glass fibers
Wei Bu carries out electro-coppering, tests detection display by backlight, backlight level is up to 9.5 grades, electroplating effect TPstdValue is 90%, TPmin
Value is 76%.
Embodiment 3
Substrate surface modification: taking the epoxy resin base plate of two pieces of 1.6mm thickness, generates the aperture 0.2mm using laser on it
Through-hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then existing
At 35 DEG C, the aqueous solution sodium oleate for immersing 10g/L is handled about 1.5 minutes, after washing, at 80 DEG C, immerses 60g/L, pH
It is handled about 1.5 minutes in=6 (being adjusted with the boric acid of 10g/L) potassium permanganate solutions, it is standby through washing after processing completion
With.
The test of manganese dioxide adsorbance: handling one of above-mentioned epoxy resin base plate using 1 same procedure of embodiment,
Calculating adsorbance of the manganese dioxide on substrate is 64.47 μ g/cm2。
Electro-coppering: use the identical electrolytic copper plating solution of embodiment 1, under identical condition to another piece of modified substrate into
Row electro-coppering tests detection display by backlight, and backlight level is up to 9 grades, electroplating effect TPstdValue is 87%, TPminValue is
73%.
Embodiment 4
Substrate surface modification: the polyflon substrate of two pieces of 1.6mm thickness is taken, is generated on it using laser
The through-hole in the aperture 0.2mm and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing at
Reason, then at 60 DEG C, the AEO carboxylic acid sodium aqueous solution for immersing 0.1g/L is handled about 3 minutes, by washing
After processing, at 80 DEG C, 60g/L is immersed, pH=6 (is adjusted) in potassium permanganate solution with the boric acid of 10g/L and is handled about
It is 1.5 minutes, spare through washing after processing completion.
The test of manganese dioxide adsorbance: one of above-mentioned substrate is handled using 1 same procedure of embodiment, calculates two
The adsorbance of manganese oxide on it is 52.91 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified polytetrafluoro
Vinyl substrate carries out electro-coppering, finally, showing that backlight level is up to 9 grades, the electroplates in hole effect by backlight test detection
TPstdValue is 86%, TPminValue is 71%.
Embodiment 5
Substrate surface modification: taking the glass fabric of two pieces of 1.6mm thickness, generates the aperture 0.2mm using laser on it
Through-hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then 65
At DEG C, the laureth sodium sulfovinate aqueous solution for immersing 0.5g/L is handled about 50 seconds, after washing, at 80 DEG C, is immersed
60g/L, pH=6, which (are adjusted) in potassium permanganate solution with the boric acid of 10g/L, to be handled about 1.5 minutes, and processing passes through after completing
Washing, it is spare.
The test of manganese dioxide adsorbance: handling one of above-mentioned glass fabric using 1 same procedure of embodiment, counts
Calculating the adsorbance of manganese dioxide on it is 44.05 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified glass fibers
Wei Bu carries out electro-coppering, finally, showing that backlight level is up to 9 grades, the electroplates in hole effect TP by backlight test detectionstdValue is
85%, TPminValue is 70%.
Embodiment 6
Substrate surface modification: taking the epoxy resin base plate of two pieces of 1.6mm thickness, generates the aperture 0.2mm using laser on it
Through-hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then existing
At 70 DEG C, the lauryl sodium sulfate aqueous solution for immersing 20g/L is handled about 4 minutes, after washing, at 80 DEG C, is immersed
60g/L, pH=6, which (are adjusted) in potassium permanganate solution with the boric acid of 10g/L, to be handled about 1.5 minutes, and processing passes through after completing
Washing, it is spare.
The test of manganese dioxide adsorbance: one of epoxy resin after modifying is handled using 1 same procedure of embodiment
Substrate, calculating the adsorbance of manganese dioxide on it is 70.37 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified asphalt mixtures modified by epoxy resin
Aliphatic radical plate carries out electro-coppering, tests detection display by backlight, backlight level is up to 9.5 grades, the electroplates in hole effect TPstdValue is
88%, TPminValue is 73%.
Embodiment 7
Substrate surface modification: taking the ceramic substrate of two pieces of 1.6mm thickness, generates the logical of the aperture 0.2mm using laser on it
Hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then at 80 DEG C
Under, the hexadecanyl phosphate sodium water solution for immersing 15g/L is handled about 3.5 minutes, after washing, at 80 DEG C, is immersed
60g/L, pH=6, which (are adjusted) in potassium permanganate solution with the boric acid of 10g/L, to be handled about 1.5 minutes, and processing passes through after completing
Washing, it is spare.
The test of manganese dioxide adsorbance: one of above-mentioned substrate is handled using 1 same procedure of embodiment, calculates two
The adsorbance of manganese oxide on it is 63.12 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified ceramic base
Material carries out electro-coppering, finally, showing that backlight level is up to 9 grades, the electroplates in hole effect TP by backlight test detectionstdValue is
88%, TPminValue is 72%.
Embodiment 8
Substrate surface modification: taking the stone material substrate of two pieces of 1.6mm thickness, generates the logical of the aperture 0.2mm using laser on it
Hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then at 40 DEG C
Under, the sulfomethylated lignin aqueous acid for immersing 3g/L is handled about 3 minutes, after washing, at 80 DEG C, immerses 50g/L, pH=6
It is handled in (being adjusted with the boric acid of 10g/L) potassium permanganate solution about 1.5 minutes, it is spare through washing after processing completion.
The test of manganese dioxide adsorbance: one of substrate is handled using 1 same procedure of embodiment, calculates manganese dioxide
Adsorbance on it is 71.05 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified stone material base
Plate carries out electro-coppering, tests detection display by backlight, backlight level is up to 9.5 grades, the electroplates in hole effect TPstdValue is 88%,
TPminValue is 74%.
Embodiment 9
Substrate surface modification: taking the epoxy resin base plate of two pieces of 1.6mm thickness, generates the aperture 0.2mm using laser on it
Through-hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then existing
At 15 DEG C, the sodium gluconate aqueous solution for immersing 18g/L is handled about 5 minutes, after washing, at 80 DEG C, immerses 50g/L,
PH=6, which (is adjusted) in potassium permanganate solution with the boric acid of 10g/L, to be handled about 1.5 minutes, standby through washing after processing completion
With.
The test of manganese dioxide adsorbance: one of above-mentioned substrate is handled using 1 same procedure of embodiment, calculates two
Adsorbance of the manganese oxide on epoxy resin is 20.15 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified asphalt mixtures modified by epoxy resin
Rouge carries out electro-coppering, tests detection display by backlight, backlight level is up to 9 grades, electroplating effect TPstdValue is 81%, TPminValue is
68%.
Comparative example 10 (comparison of embodiment 5)
Substrate surface modification: taking the glass fabric of two pieces of 1.6mm thickness, generates the aperture 0.2mm using laser on it
Through-hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then 65
At DEG C, -7 aqueous solution of polyquaternium for immersing 0.5g/L is handled about 50 seconds, after washing, at 80 DEG C, immerses 60g/L, pH=6
It is handled in (being adjusted with the boric acid of 10g/L) potassium permanganate solution about 1.5 minutes, it is spare through washing after processing completion.
The test of manganese dioxide adsorbance: handling one of above-mentioned glass fabric using 1 same procedure of embodiment, counts
Calculating adsorbance of the manganese dioxide on glass fabric is 8.31 μ g/cm2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified glass fibers
Wei Bu carries out electro-coppering, tests detection display by backlight, backlight level is up to 8.5 grades, the electroplates in hole effect TPstdValue is 80%,
TPminValue is 44%.
Comparative example 11 (comparison of embodiment 7)
Substrate surface modification: taking the ceramic substrate of two pieces of 1.6mm thickness, generates the logical of the aperture 0.2mm using laser on it
Hole and 75 μm of dielectric thickness, the blind hole in 100 μm of apertures carries out processing same as below respectively: first through washing process, then at 80 DEG C
Under, the polychloride dimethyldiallylammonium aqueous solution for immersing 15g/L is handled about 3.5 minutes, after washing process, at 80 DEG C
Under, 60g/L is immersed, pH=6, which (is adjusted) in potassium permanganate solution with the boric acid of 10g/L, to be handled about 1.5 minutes, has been handled
Cheng Houjing washing, it is spare.
The test of manganese dioxide adsorbance: handling one of above-mentioned ceramic substrate using 1 same procedure of embodiment, calculates
The adsorbance of manganese dioxide on it is 12.76 μ g/cm out2。
Electro-coppering: the identical electrolytic copper plating solution of embodiment 1 is used, under identical condition to another piece of modified ceramic base
Plate carries out electro-coppering, tests detection display by backlight, backlight level is up to 9 grades, electroplating effect TPstdValue is 84%, TPminValue is
49%.
Interpretation of result:
Examples 1 to 9 is after handling insulating substrate using technical solution of the present invention, plating metal lining to be carried out, from knot
Fruit it is found that Examples 1 to 9 as the result is shown: by the substrate surface of the technology of the present invention modified to the adsorbance of manganese dioxide
It is all larger than 20 μ g/cm2, the backlight level of subsequent electro-coppering can reach 9 grades or more, TPstdValue is not less than 81%, TPminValue is equal
Not less than 68%.Illustrate using after technical solution of the present invention processing substrate, it is subsequent can obtain that thickness is uniform, backlight is good and
Be not in the copper electroplating layer for having extremely thin site in hole, ensure that the electric conductivity and stability of subsequent conditioning circuit plate.
Comparative example 10 and comparative example 11 are compared with embodiment 5 and embodiment 7 respectively, and difference is only that reality
Example 5 and 7 is applied to be handled using anionic compound, and comparative example 10 and comparative example 11 only use cationic compound
It is handled.The results show that the manganese dioxide adsorbance of the upper substrate of comparative example 10 and 11 only has 8.31 μ g/cm respectively2With
12.76μg/cm2Although the TP of the twostdIt is not less than 80%, but the TP of two comparative examplesminIt is 44% He respectively
49%, compared to the electro-coppering TP for the insulating substrate for using anionic compound to handle in embodiment 1-9min, numerical value has significantly
Gap.The TP of comparative example 10 and comparative example 11minInsulation base lower, that instruction sheet uses cationic compound to handle
Material, after subsequent electro-coppering, through-hole plating is in uneven thickness, and there are the thick relatively thin sites of copper, it cannot be guaranteed that the electric conductivity of circuit board
And stability.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of method of insulating substrate electroplating surface metal, which comprises the steps of:
Contact the insulating substrate surface with water soluble anion compound, to form modified surface；
The modified surface is contacted with the aqueous solution containing high manganese ion, to form titanium dioxide on the modified surface
Manganese adsorption layer；
Conductive polymer coating is formed in manganese dioxide absorption layer surface；
Metal layer is formed in the conductive polymer coating electroplating surface.
2. the method for insulating substrate electroplating surface metal according to claim 1, which is characterized in that the water-soluble yin from
Sub- compound is selected from one of sulfonate, carboxylate, sulfuric acid and phosphate ester salt or a variety of.
3. the method for insulating substrate electroplating surface metal according to claim 2, which is characterized in that
The sulfonate is selected from polybutadiene sulfonic acid sodium, neopelex, sodium cetanesulfonate, Sodium Allyl Sulfonate
It is one or more with lignin sulfonic acid；
The carboxylic acids is selected from enuatrol, sodium carboxymethylcellulose, sodium gluconate, AEO carboxylic acid sodium and hard
Resin acid sodium it is one or more；
The sulfuric acid be selected from laureth sodium sulfovinate, the one of lauryl sodium sulfate and lauramide sodium ethylsulfate
Kind is a variety of；
The phosphate ester salt is selected from hexadecanyl phosphate sodium, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium and aliphatic alcohol polyoxyvinethene phosphate
Potassium it is one or more.
4. the method for insulating substrate electroplating surface metal according to claim 1, which is characterized in that the water-soluble yin from
The concentration of sub- compound is 0.1g/L-20g/L.
5. the method for insulating substrate electroplating surface metal according to claim 1, which is characterized in that the manganese dioxide is inhaled
The density of attached layer is 20 μ g/cm2-120μg/cm2。
6. the method for insulating substrate electroplating surface metal according to claim 1-5, which is characterized in that the gold
The material for belonging to layer is selected from copper, gold, silver or nickel.
7. the method for insulating substrate electroplating surface metal according to claim 1-5, which is characterized in that described exhausted
Edge substrate is selected from plastics, resin, glass fibre, ceramics or stone material.
8. a kind of preparation method of printed wiring board, which is characterized in that including the described in any item insulating substrates of claim 1-7
The method of electroplating surface metal.
9. the printed wiring board that preparation method according to any one of claims 8 obtains.
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| CN110029382A (en) * | 2019-05-22 | 2019-07-19 | 电子科技大学 | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated |
| CN110117803A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | Potassium chloride is without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology |
| CN115110071A (en) * | 2022-07-29 | 2022-09-27 | 电子科技大学 | Pretreatment method for chemical plating of insulating substrate and chemical plating method |
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Cited By (5)
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| CN110117803A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | Potassium chloride is without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology |
| CN110029382A (en) * | 2019-05-22 | 2019-07-19 | 电子科技大学 | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated |
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| CN115110071B (en) * | 2022-07-29 | 2023-09-01 | 电子科技大学 | Method for treating insulating substrate before electroless plating and electroless plating method |
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| CN108977862B (en) | 2022-08-05 |
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