CN111876759A - Method for manufacturing metal circuit on surface of plastic material - Google Patents
Method for manufacturing metal circuit on surface of plastic material Download PDFInfo
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- CN111876759A CN111876759A CN202010625533.4A CN202010625533A CN111876759A CN 111876759 A CN111876759 A CN 111876759A CN 202010625533 A CN202010625533 A CN 202010625533A CN 111876759 A CN111876759 A CN 111876759A
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- 239000004033 plastic Substances 0.000 title claims abstract description 145
- 229920003023 plastic Polymers 0.000 title claims abstract description 145
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 139
- 239000002184 metal Substances 0.000 title claims abstract description 139
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000007747 plating Methods 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 48
- 239000011159 matrix material Substances 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 29
- 238000007788 roughening Methods 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 230000001965 increasing effect Effects 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 8
- 230000008313 sensitization Effects 0.000 claims abstract description 8
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000010329 laser etching Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002991 molded plastic Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 6
- 238000011049 filling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010147 laser engraving Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 palladium ions Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention discloses a method for manufacturing a metal circuit on the surface of a plastic material, which comprises the following steps: the method comprises the steps of plastic matrix manufacturing, plastic matrix surface roughening treatment, plastic matrix surface sensitizing treatment, plastic matrix surface metal ion reduction and plastic matrix surface metal circuit deposition. The metal layer is plated on the plastic as a metal circuit by utilizing the steps, and the hydrophilicity difference between the circuit area and the non-circuit area is increased by coarsening the metal circuit area on the surface of the plastic, so that the problem of excessive plating between the circuits is greatly improved, the circuits with thinner requirements can be manufactured, and the manufacturing capability of the high-precision circuits is further improved. And the metal circuit area on the surface of the plastic is treated by the sensitization step, so that the binding force between the metal coating and the surface of the plastic can be improved, the high-temperature and high-humidity resistance can be obtained, the chemical plating manufacturability is improved, and the problem of difficult quality monitoring is solved.
Description
Technical Field
The invention relates to the technical field of metal circuit manufacturing, in particular to a method for manufacturing a metal circuit on the surface of a plastic material.
Background
With the development of 5G technology, many antennas need to be fabricated on the handset housing, i.e., metal traces are fabricated on plastic. Some plastics (namely LDS plastics) containing organic heavy metal complexes can be used for manufacturing precise metal circuits by means of laser engraving and chemical plating manufacturing technologies, although metal can be plated, the metal circuits which meet requirements cannot be stably obtained, the requirements on mobile phone antennas, vehicle-mounted antennas and base station antennas cannot be met, product diversity cannot be met, some precise metal circuits are manufactured on common plastics, palladium metal and compounds thereof are adopted, and the manufacturing cost of products is not low as the price of the palladium metal rises all the way.
Disclosure of Invention
The invention provides a method for manufacturing a metal circuit on the surface of a plastic material, aiming at the defects in the background technology.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for manufacturing a metal circuit on the surface of a plastic material comprises the following steps:
s1, manufacturing a plastic substrate, namely manufacturing a plastic substrate material with a set shape according to requirements;
s2, roughening the surface of the plastic matrix, namely roughening the area of the plastic matrix where the metal circuit is required to be deposited, so that the specific surface area of the plastic matrix where the metal circuit is required to be deposited is increased;
s3, performing surface sensitization treatment on the plastic matrix, namely sensitizing the area of the plastic matrix where the metal circuit needs to be deposited, and enhancing the hydrophilicity of the area of the plastic matrix where the metal circuit needs to be deposited, so that the area of the plastic matrix where the metal circuit needs to be deposited adsorbs metal ions;
s4, reducing metal ions on the surface of the plastic matrix, forming a metal simple substance on the plastic matrix through a reduction reaction, and depositing the metal simple substance in an area of the plastic matrix where a metal circuit needs to be deposited;
s5, depositing metal circuits on the surface of the plastic substrate, and further depositing metal in the areas of the plastic substrate where the metal circuits need to be deposited to form the metal circuits.
Further, in the step S3, the metal ions adsorbed on the plastic substrate are Pd2+。
Further, step S3 is preceded by a surface conditioning step, in which colloidal ions are adsorbed on the plastic substrate in the region where the metal circuit is to be deposited, so as to enhance the hydrophilicity of the surface of the plastic substrate in the region where the metal circuit is to be deposited, and increase the Pd resistance2+Adsorption of ions;
further, in the step S5, depositing copper or nickel metal for electroless plating in the area of the plastic substrate where the metal circuit is to be deposited; the chemical plating solution for nickel plating comprises the following components: ni+Any value between 3.5g and 5.5g/l of sodium hyposulfite and any value between 18g and 36g/l of sodium hyposulfite; the pH value of the chemical plating solution is any value between 8.5 and 10.5, the temperature is any value between 30 ℃ and 45 ℃, and the time is any value between 4min and 10 min.
Further, in the step S3, the metal ion adsorbed on the plastic substrate is Sn2+The chemical reaction in step S4 is Sn2++Ag+→Sn4++Ag。
Further, in the step of depositing the metal circuit on the surface of the plastic substrate in the step S5, the metal circuit is deposited in two steps, a pre-plating metal is deposited on the surface of the plastic substrate, and then a thick metal circuit layer is plated on the pre-plating metal.
Further, in the step S5, both the two steps of depositing the metal circuit on the surface of the plastic substrate are chemical plating, and the solution components for depositing the metal of the pre-plating layer are as follows: the content of copper ions is any value between 2.4g/L and 3.0g/L, the content of sodium hydroxide is any value between 4g/L and 6g/L, the content of formaldehyde is any value between 3g/L and 4.5g/L, the content of complexing agent is any value between 0.12mol/L and 0.16mol/L, the temperature of chemical plating is any value between 50 ℃ and 55 ℃, the deposition speed of chemical plating is any value between 4um/H and 6um/H, and the time of chemical plating is any value between 5min and 15 min; the solution for plating the thick metal circuit layer comprises the following components: the content of copper ions is any value between 2g/L and 2.6g/L, the content of sodium hydroxide is any value between 3.5g/L and 5g/L, the content of formaldehyde is any value between 3g/L and 4.5g/L, the content of complexing agent is any value between 0.12mol/L and 0.16mol/L, the temperature of chemical plating is any value between 45 ℃ and 55 ℃, and the deposition speed of the chemical plating is any value between 2.5um/H and 5 um/H.
Further, the plastic substrate surface roughening step in step S2 includes the following specific steps:
s21, mechanical roughening, namely performing laser etching treatment on the surface of the area of the plastic matrix where the metal circuit is required to be deposited by using pulse laser to roughen the surface of the plastic matrix to form convex particles;
s22, chemical roughening, namely soaking the area of the plastic matrix where the metal circuit is required to be deposited with NaOH solution, wherein the concentration of the NaOH solution is any value between 5g and 200g/l, the temperature is any value between 50 ℃ and 80 ℃, and the soaking time is any value between 20min and 50 min.
Further, before the chemical roughening step of step S22, an ultrasonic cleaning step is further included, in which an area of the plastic substrate subjected to laser etching by pulsed laser is ultrasonically cleaned, and residual debris left after firing by pulsed laser is removed.
Further, in the step of manufacturing the plastic substrate in step S1, the plastic substrate is injection molded, and the surface roughness of the injection molded plastic substrate is an arbitrary value between Rz5um-10 um.
The beneficial effects realized by the invention mainly comprise the following points: the metal layer is plated on the plastic as a metal circuit, and the hydrophilicity difference between the circuit area and the non-circuit area is increased by coarsening the metal circuit area on the surface of the plastic, so that the problem of excessive plating between the circuits is greatly improved, the circuits with thinner requirements can be manufactured, and the manufacturing capability of the high-precision circuits is further improved. And the metal circuit area on the surface of the plastic is treated by the sensitization step, so that the binding force between the metal coating and the surface of the plastic can be improved, the high-temperature and high-humidity resistance can be obtained, the chemical plating manufacturability is improved, and the problem of difficult quality monitoring is solved.
Drawings
FIG. 1 is a diagram illustrating the effect of a product after ultrasonic cleaning in a method for manufacturing a metal circuit on the surface of a plastic material according to an embodiment of the present invention;
FIG. 2 is a diagram illustrating the effect of the product after chemical roughening in the method for manufacturing a metal circuit on the surface of a plastic material according to the embodiment of the invention;
FIG. 3 is a diagram illustrating the effect of the copper-plated product in the method for manufacturing metal lines on the surface of a plastic material according to the embodiment of the present invention;
FIG. 4 is a diagram illustrating the effect of the product after ultrasonic cleaning in the method for manufacturing a metal circuit on the surface of a plastic material according to the second embodiment of the present invention;
FIG. 5 is a diagram illustrating the effect of the product after chemical roughening in the method for manufacturing a metal circuit on the surface of a plastic material according to the second embodiment of the present invention;
fig. 6 is a diagram illustrating the effect of the product after copper plating is completed in the method for manufacturing metal circuits on the surface of the plastic material according to the second embodiment of the present invention.
The drawings are for illustrative purposes only and are not to be construed as limiting the patent; for the purpose of better illustrating the embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted; the same or similar reference numerals correspond to the same or similar parts; the terms describing positional relationships in the drawings are for illustrative purposes only and are not to be construed as limiting the patent.
Detailed Description
In order to facilitate understanding for those skilled in the art, the present invention will be described in further detail with reference to the accompanying drawings and examples.
Example one
A method for manufacturing a metal circuit on the surface of a plastic material is characterized by comprising the following steps:
s1, manufacturing a plastic substrate, namely manufacturing a plastic substrate material with a set shape according to requirements; the plastic substrate can be formed by injection molding, and the surface roughness of the injection molded plastic substrate is any value between Rz5um and 10 um. The shape and roughness of the plastic substrate can be controlled by the injection mold.
S2, roughening the surface of the plastic matrix, namely roughening the area of the plastic matrix where the metal circuit is required to be deposited, so that the specific surface area of the plastic matrix where the metal circuit is required to be deposited is increased; the plastic matrix surface roughening treatment step comprises the following specific steps:
s21, mechanical roughening, namely performing laser etching treatment on the surface of the area of the plastic matrix where the metal circuit is required to be deposited by using pulse laser to enable the surface of the plastic matrix to be cauterized and roughened to form convex particles; taking pure PC black pigment as an example, the pulsed laser can be adjusted according to the following table I, and plastic substrates made of other materials can also be adjusted according to the following table I.
Table one: example one parameter of pulse laser etching and roughening treatment of metal line region
| Front side | Hole site | |
| Power (w) | 10～20 | 10～16 |
| Frequency (KHZ) | 20～40 | 20～30 |
| Speed (mm/s) | 2000～3500 | 3000～4000 |
| Filling space/mm | 0.08～0.3 | 0.03～0.05 |
| Filling mode | Filling of # word | Filling of # word |
Referring to the table I, the laser etching power of the front surface of the area of the plastic substrate surface needing to deposit the metal circuit is 10W-20W, the frequency is 20 KHZ-40 KHZ, the speed is 2000 mm/s-3500 mm/s, the distance between adjacent laser etching grooves is 0.08 mm-0.3 mm, the laser etching power of the hole part is 10W-16W, the frequency is 20 KHZ-30 KHZ, the speed is 3000 mm/s-4000 mm/s, the distance between adjacent laser etching grooves is 0.03 mm-0.05 mm, the front surface of the area needing to deposit the metal circuit and the laser etching grooves of the hole part are filled with # characters, namely a plurality of parallel grooves are respectively etched horizontally and vertically.
S22, chemical roughening, namely soaking the area of the plastic matrix where the metal circuit is required to be deposited with NaOH solution, wherein the concentration of the NaOH solution is any value between 5g and 200g/l, the temperature is any value between 50 ℃ and 80 ℃, and the soaking time is any value between 20min and 50 min. The chemical roughening enables the specific surface area of the surface particles protruding from the laser etching roughened area to be increased by more than hundreds of times than that of the non-laser etching area, contact points with strong alkali/oxide are greatly increased, the more base points for breaking bonds/oxidizing are, the more the protruding particles form hydrophilic particles by hydrophobic particles, and the adsorption of palladium ions is enabled. The plastic substrate after chemical roughening is shown in fig. 2, and it can be seen that the hydrophilicity of the region of the plastic substrate where the metal circuit needs to be deposited is greatly increased.
An ultrasonic cleaning step is also included before the chemical coarsening step of the step S22, the area carved by the pulse laser on the plastic matrix is cleaned by ultrasonic, and the residual scraps left after the pulse laser firing are removed; the area of the plastic substrate after ultrasonic cleaning, where the metal circuit is required to be deposited, is shown in fig. 1, and it can be seen that the area of the plastic substrate, where the metal circuit is required to be deposited, has slight hydrophilicity.
S3, a surface conditioning step, wherein the surface conditioning step adsorbs colloidal ions to the area of the plastic substrate where the metal circuit is required to be deposited, and enhances the hydrophilicity of the surface of the area of the plastic substrate where the metal circuit is required to be deposited, thereby increasing the Pd resistance2+The adsorptivity of (a); the colloidal ion may be a gel-like ion commonly used in the art.
S4, surface sensitization of the plastic substrate, namely, sensitization of the area of the plastic substrate where the metal circuit is required to be deposited, and enhancement of hydrophilicity of the area of the plastic substrate where the metal circuit is required to be deposited, so that metal ions are adsorbed on the area of the plastic substrate where the metal circuit is required to be deposited, and the metal ions adsorbed on the plastic substrate are Pd2+. The solution adopted by the sensitization treatment is Pd2+Concentration of 30-70 ppm, H+The concentration is between 0.5ml/l and 3ml/l, the solution temperature is between 20 ℃ and 40 ℃, and the soaking time is between 5min and 15 min.
S5, reducing metal ions on the surface of the plastic substrate, and carrying out reduction reaction on Pd on the plastic substrate2+And the metal Pd simple substance is formed by reduction and is deposited in the area of the plastic substrate where the metal circuit is required to be deposited, so that the metal circuit can be conveniently manufactured by further deposition. Reduction of Pd2+The reducing agent of (b) may be a conventional reducing agent, for example, a formaldehyde solution.
S6, depositing metal circuits on the surface of the plastic substrate, and further depositing metal in the areas of the plastic substrate where the metal circuits need to be deposited to form the metal circuits. Depositing copper or nickel for chemical plating in the area of the plastic matrix where the metal circuit is required to be deposited; the chemical plating solution for nickel plating comprises the following components: the Ni + content is between 3.5g and 5.5g/l, and the sodium hyposulfite content is between 18g and 36 g/l; the pH value of the chemical plating solution is any value between 8.5 and 10.5, the temperature is any value between 30 ℃ and 45 ℃, and the time is any value between 4min and 10 min. The area of the plastic substrate where the metal circuit needs to be deposited can also be plated with deposited metal copper, a chemical plating solution commonly used in chemical copper plating in the prior art can be adopted, and the effect graph after copper plating is shown in fig. 3.
The embodiment plates metal on plastics as the metal circuit, increases circuit district and non-circuit district hydrophilicity difference through the alligatoring in plastic surface metal circuit district, improves the excessive problem of plating that exists between the circuit greatly for can make the circuit of thinner requirement, high accuracy circuit preparation ability further promotes. And the metal circuit area on the surface of the plastic is treated by the sensitization step, so that the binding force between the metal coating and the surface of the plastic can be improved, the high-temperature and high-humidity resistance can be obtained, the chemical plating manufacturability is improved, and the problem of difficult quality monitoring is solved.
Example two
The method for fabricating a metal circuit on a surface of a plastic material in this embodiment is generally the same as that in the first embodiment, and the differences will be described below, and the same parts refer to the first embodiment and will not be described herein again.
Steps S1 and S2 are the same as in the first embodiment, and the surface conditioning step of embodiment S3 is not used in this embodiment. The effect diagram of the product after ultrasonic cleaning is shown in fig. 4, and the metal circuit area on the surface of the plastic substrate has slight hydrophilicity; the effect diagram of the product after chemical roughening is shown in fig. 5, and the hydrophilicity of the metal circuit area on the surface of the plastic matrix is greatly increased.
In the embodiment of the metal ion reduction on the surface of the plastic substrate in step S4, the metal ion adsorbed on the plastic substrate is Sn2+In step S5, Sn is passed through by using Ag + solution2+Reducing Ag + into Ag simple substance, and carrying out chemical reaction to obtain Sn2++Ag+→Sn4++Ag。
In the step of depositing the metal circuit on the surface of the plastic substrate in the step of S6, the metal circuit in the step of depositing the metal circuit on the surface of the plastic substrate is deposited in two steps, a pre-plating metal is deposited on the surface of the plastic substrate, and then a thick metal circuit layer is plated on the pre-plating metal, wherein both steps are chemical plating. The solution for depositing the pre-plating metal comprises the following components: the content of copper ions is any value between 2.4g/L and 3.0g/L, the content of sodium hydroxide is any value between 4g/L and 6g/L, the content of formaldehyde is any value between 3g/L and 4.5g/L, the content of complexing agent is any value between 0.12mol/L and 0.16mol/L, the temperature of chemical plating is any value between 50 ℃ and 55 ℃, the deposition speed of chemical plating is any value between 4um/H and 6um/H, and the time of chemical plating is any value between 5min and 15 min. The solution for plating the thick metal circuit layer comprises the following components: the content of copper ions is any value between 2g/L and 2.6g/L, the content of sodium hydroxide is any value between 3.5g/L and 5g/L, the content of formaldehyde is any value between 3g/L and 4.5g/L, the content of complexing agent is any value between 0.12mol/L and 0.16mol/L, the temperature of chemical plating is any value between 45 ℃ and 55 ℃, and the deposition speed of the chemical plating is any value between 2.5um/H and 5 um/H. In the embodiment, the metal circuit is deposited in two steps, so that the precision of circuit deposition is better, and the precision of the circuit can be improved. The effect of the product after copper plating is shown in fig. 6, and a layer of copper is formed on the surface of the product.
Through the first embodiment and the second embodiment, the method for manufacturing the metal circuit on the surface of the plastic material with palladium and the method for manufacturing the metal circuit on the surface of the plastic material without palladium are respectively provided, the metal circuit on the surface of the plastic material without palladium can be manufactured, and the metal circuit can be selected according to the control requirement of the production cost.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for manufacturing a metal circuit on the surface of a plastic material is characterized by comprising the following steps:
s1, manufacturing a plastic substrate, namely manufacturing a plastic substrate material with a set shape according to requirements;
s2, roughening the surface of the plastic matrix, namely roughening the area of the plastic matrix where the metal circuit is required to be deposited, so that the specific surface area of the plastic matrix where the metal circuit is required to be deposited is increased;
s3, performing surface sensitization treatment on the plastic matrix, namely sensitizing the area of the plastic matrix where the metal circuit needs to be deposited, and enhancing the hydrophilicity of the area of the plastic matrix where the metal circuit needs to be deposited, so that the area of the plastic matrix where the metal circuit needs to be deposited adsorbs metal ions;
s4, reducing metal ions on the surface of the plastic matrix, forming a metal simple substance on the plastic matrix through a reduction reaction, and depositing the metal simple substance in an area of the plastic matrix where a metal circuit needs to be deposited;
s5, depositing metal circuits on the surface of the plastic substrate, and further depositing metal in the areas of the plastic substrate where the metal circuits need to be deposited to form the metal circuits.
2. The method for manufacturing metal circuits on the surface of plastic material according to claim 1, wherein the method comprises the following steps: in the step S3, the metal ions adsorbed on the plastic substrate are Pd2+。
3. The method for manufacturing metal circuits on the surface of plastic material according to claim 2, wherein: the step S3 is preceded by a surface conditioning step, wherein the surface conditioning step adsorbs colloidal ions to the area of the plastic substrate where the metal circuit is to be deposited, so as to enhance the hydrophilicity of the surface of the area of the plastic substrate where the metal circuit is to be deposited and increase the Pd resistance2+Adsorption of ions.
4. The method for manufacturing metal circuits on the surface of plastic material according to claim 3, wherein: in the step S5, depositing copper or nickel in the plastic substrate in the area where the metal circuit is to be deposited; the chemical plating solution for nickel plating comprises the following components: ni+Any value between 3.5g and 5.5g/l of sodium hyposulfite and any value between 18g and 36g/l of sodium hyposulfite; the pH value of the chemical plating solution is any value between 8.5 and 10.5, the temperature is any value between 30 ℃ and 45 ℃, and the time is any value between 4min and 10 min.
5. The method for manufacturing metal circuits on the surface of plastic material according to claim 1, wherein the method comprises the following steps: in the step S3, the metal ions adsorbed on the plastic substrate are Sn2+The chemical reaction in step S4 is Sn2++Ag+→Sn4++Ag。
6. The method for manufacturing metal circuits on the surface of plastic material according to claim 5, wherein: in the step of depositing the metal circuit on the surface of the plastic substrate in the step S5, the metal circuit is deposited in two steps, namely, a pre-plating metal is deposited on the surface of the plastic substrate, and then a thick metal circuit layer is plated on the pre-plating metal.
7. The method for manufacturing metal circuits on the surface of plastic material according to claim 6, wherein: in the step S5, both the steps of depositing the metal circuit on the surface of the plastic substrate are chemical plating, and the solution components for depositing the metal of the pre-plating layer are as follows: the content of copper ions is any value between 2.4g/L and 3.0g/L, the content of sodium hydroxide is any value between 4g/L and 6g/L, the content of formaldehyde is any value between 3g/L and 4.5g/L, the content of complexing agent is any value between 0.12mol/L and 0.16mol/L, the temperature of chemical plating is any value between 50 ℃ and 55 ℃, the deposition speed of chemical plating is any value between 4um/H and 6um/H, and the time of chemical plating is any value between 5min and 15 min; the solution for plating the thick metal circuit layer comprises the following components: the content of copper ions is any value between 2g/L and 2.6g/L, the content of sodium hydroxide is any value between 3.5g/L and 5g/L, the content of formaldehyde is any value between 3g/L and 4.5g/L, the content of complexing agent is any value between 0.12mol/L and 0.16mol/L, the temperature of chemical plating is any value between 45 ℃ and 55 ℃, and the deposition speed of the chemical plating is any value between 2.5um/H and 5 um/H.
8. The method for manufacturing metal circuits on the surface of plastic material according to any of claims 1 to 7, wherein: the plastic substrate surface roughening treatment step in step S2 includes the following specific steps:
s21, mechanical roughening, namely performing laser etching treatment on the surface of the area of the plastic matrix where the metal circuit is required to be deposited by using pulse laser to roughen the surface of the plastic matrix to form convex particles;
s22, chemical roughening, namely soaking the area of the plastic matrix where the metal circuit is required to be deposited with NaOH solution, wherein the concentration of the NaOH solution is any value between 5g and 200g/l, the temperature is any value between 50 ℃ and 80 ℃, and the soaking time is any value between 20min and 50 min.
9. The method for manufacturing metal circuits on the surface of plastic material according to claim 8, wherein: and an ultrasonic cleaning step is also included before the chemical coarsening step of the step S22, the area etched by the pulse laser on the plastic substrate is cleaned by ultrasonic, and the residual scraps left after the pulse laser is burnt are removed.
10. The method for manufacturing metal circuits on the surface of plastic material according to any of claims 1 to 7, wherein: in the step of manufacturing the plastic substrate in the step S1, the plastic substrate is subjected to injection molding, and the surface roughness of the injection molded plastic substrate is an arbitrary value between Rz5um and 10 um.
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