CN105543813A - Method for producing precise metal circuit on plastic surface - Google Patents
Method for producing precise metal circuit on plastic surface Download PDFInfo
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- CN105543813A CN105543813A CN201610114515.3A CN201610114515A CN105543813A CN 105543813 A CN105543813 A CN 105543813A CN 201610114515 A CN201610114515 A CN 201610114515A CN 105543813 A CN105543813 A CN 105543813A
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- plastic substrate
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- plastic
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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
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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
- C23C18/1601—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
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
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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
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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
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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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
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
Abstract
The invention provides a method for producing a precise metal circuit on a plastic surface. The method comprises steps as follows: Step 1, a plastic base body is provided, and powdery precipitation type silica is mixed and distributed in the plastic base body; Step 2, laser irradiates a preset surface circuit zone on the plastic base body, so that the surface circuit zone is burnt and roughened, and bulging silica particles are formed in the roughened surface; Step 3, the plastic base body treated in the Step 2 is subjected to chemical plating pretreatment, active chemical groups for adsorbing chemical plating catalysts are produced on exposed surfaces of the bulging silica particles, and the chemical plating catalysts are attached to the surface circuit zone of silica having the active chemical groups; Step 4, the surface circuit zone of the base body treated in the Step 3 is subjected to chemical plating of underlying metal through a reaction of a chemical plating agent with the chemical plating catalysts; Step 5, the surface of the underlying metal is subjected to chemical plating or electroplating with a thick metal layer until the preset thickness is reached, and the metal circuit is formed finally.
Description
Technical field
The present invention relates to the preparation method of metallic circuit, particularly, relate to a kind of method that frosting makes precision metallic circuit.
Background technology
Precision metallic circuit can be produced by laser ablation and chemical plating metal manufacturing technology at frosting.This manufacturing technology is highly suitable on complex-curved frosting and makes fine metal circuit, in application antenna for mobile phone.
Conventional plastics variety such as the surface of polycarbonate plastic can not metals on direct electroless plating, and need to change plastic nature, such as appropriate palladium metal particle is enclosed on surface, treated plastics just can plate metal.
Metallic circuit on antenna for mobile phone has two features, and one is that requirement wire sizes is accurate, and two is that circuit is distributed on plastic stent different surfaces usually, and these surfaces are not usually at grade.
Make precision metallic line area at above-mentioned frosting, have three public technologies at present:
Technology one:
At its patent " circuit structure on non-conductive solid support material, particularly fine circuitry structure, and manufacture method " mention in CN1234960A: " the method is characterized in that: a kind of nonconducting organic heavy metal complex-bound is on the carrier granule of microporous or micro-rough, be blended in solid support material and go the carrier granule in the region of circuit structure will be produced, with or described particle be incorporated into and be attached on appended solid support material, electromagnetism uv-radiation is optionally applied on the solid support material that will produce in the region of circuit structure, thus due to ablation, carrier granule come out and discharge heavy metal core by the cracking of accompanying heavy metal complex, there is metallization formation circuit structure by chemical reduction in described region subsequently ".
Technology two:
Mention in its patent " a kind of preparation method of plastics and a kind of plastics " CN102071424B: " moulding plastics matrix; containing electroless plating promotor in plastic substrate; the selection area of laser needle to surface of plastic matrix irradiates, and then electroless copper or nickel form metal level at surface of plastic matrix.", " described electroless plating promotor is the compound shown in formula I or II; AMxByOz .... formula I, wherein ... M is positive trivalent metallic element A ' M ' mOn .... formula II, wherein ... M ' is selected from the one in Cr, Mo, W, Se, Te, Po.
Technology three:
In its patent " manufacture method of conductor track structure " mentions at application materials CN101873766A: " a. injection moulding adopts common plastics ABS, extrudes ABS plastic goods, b with extrusion machine.Laser treatment, with laser radiation at ABS plastic product surface, realizes the difference in irradiation area and non-irradiated region, forms micro-rough, have the surface of microvoid structure, c at material surface.Chemical activation, according to material surface structure, configuration palladium solution or silver-colored solution, a certain amount of precious metal atom of irradiation area surface adsorption, as the basis of selective chemical plating, d.The ABS plastic goods of above-mentioned process are put into common chemical reduction copper plating solution, are realized selective metallization film, e by selective metallization.Conductor rail is formed, and according to the needs of conductor rail, adopts chemical reduction method or electrolytic process metallized film to be thickeied the thickness needed ".Described chemical activation processes step is as follows: " a. degreasing 5 ~ 10min, b. at 40 DEG C ~ 60 DEG C temperature wash 1 ~ 2 time, and c. invades 3 ~ 5min in advance, and d. activates 3 ~ 6min, e. washing 1 ~ 2 time ".
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of method that frosting makes precision metallic circuit.
Make the method for precision metallic circuit according to a kind of frosting provided by the invention, comprising:
Step 1, provides a plastic substrate, and in described plastic substrate, mixed distribution has Powdered surface to have the Precipitated silicon dioxide of a large amount of crackle;
Step 2, with the surface lines district that laser radiation plastic substrate is preset, makes described surface lines district burn alligatoring, and the surface of alligatoring forms the silica dioxide granule protruded;
Step 3, plastic substrate after described step 2 being processed carries out electroless plating pre-treatment, make the exposed surface of the silica dioxide granule of described protrusion generate the active chemical group plating catalyzer for absorption, and add attachedization plating catalyzer in the surface lines district of the silicon-dioxide with described active chemical group; The silica sphere protruded generates the active chemical group of a large amount of adsorbable chemical plating catalyst after suitable chemical oxidation, but not the logicalnot circuit district frosting that laser ablation is crossed is still to changing the very weak inert condition of plating Catalyst Adsorption, the land that follow-up change plating catalyzer meeting selective adsorption is crossed at laser ablation;
Step 4, described in the plastic substrate of the reaction of plating catalyzer by electroless plating liquid and describedization after step 3 processes, surface lines districtization plates underlying metal;
Step 5, at described underlying metal surface plating or plating thick metal level to preset thickness, finally forms metallic circuit.
As a kind of prioritization scheme, electroless plating pre-treatment described in step 3 comprises:
Step 311, carries out ultrasonic cleaning, the detritus stayed after removing surperficial calcination to the surface of plastic matrix after step 2 processes;
Step 312, carries out chemical oxidation reaction process with oxygenant to described surface lines district and makes the exposed surface of described Precipitated silicon dioxide generate the active chemical group plating catalyzer for absorption;
Step 313, the surface lines district after step 312 processes carries out successively add palladium, palladium reduction, is formed described in one deck change plating catalyzer on the surface of alligatoring with the silica sections with described active chemical group.
As a kind of prioritization scheme, electroless plating pre-treatment described in step 3 comprises:
Step 321, the plastic substrate after step 2 being processed immerses in the liquid containing plastics swelling agent and/or oxygenant and does matting, and plastics swelling agent remains for helping to remove the plastics being attached to silica sphere herein,
Step 322, then immersion does chemical oxidation containing in the liquid of oxygenant,
Step 323, carries out adding palladium, palladium reduction activation process then,
Step 324, immerses plastic substrate in deionized water and washes.
As a kind of prioritization scheme, be specially with the surface lines district that laser radiation plastic substrate is preset described in step 2: with pre-set velocity, the focus of laser beam is moved along described surface lines district, make the described surface lines district of illuminated mistake burn alligatoring.
As a kind of prioritization scheme, described laser is infrared laser, or green glow, or UV-light.
As a kind of prioritization scheme, described laser is pulse laser.
As a kind of prioritization scheme, described thick metal layers is copper, or nickel, or palladium, or gold, or silver.
As a kind of prioritization scheme, described underlying metal is copper, or nickel.
As a kind of prioritization scheme, described Precipitated silicon dioxide content is 0.8 ~ 4wt%.
As a kind of prioritization scheme, described plastic substrate is thermoplastics or the thermosetting resin that mixed distribution has Powdered Precipitated silicon dioxide.
Compared with prior art, the present invention has following beneficial effect:
The present invention adds the line areas efficient adsorptionization plating catalyzer of the favourable laser ablation of silicon-dioxide one in the material of plastic substrate, because the present invention's silicon-dioxide used is sedimentation type, the surface of its individual particle itself is with a large amount of crackles, the silica particle sizes that the present invention selects is very little, but its specific surface area is comparatively large, after chemical oxidation, absorptionization plating catalyzer is very capable; Two is that silicon dioxide ratio plastics are easily oxidized, and can realize large quantization plating catalyzer on line areas strong adsorption that laser ablation crosses but not line areasization plating catalyzer is weak attachment can be plated catalyzer effect by the selective adsorptionization water-washed away after suitable chemical oxidation; Three is matrix strengths that silicon-dioxide enhances plastic substrate and line areas, provides condition for metal plating is combined with the brute force of plastic substrate; Four is the tiny silicon-dioxide energy fining metal coating spreading in surface, line areas, for the bonding strength and high-temp resisting high-humidity resisting performance improving coating and plastics provides condition.The present invention greatly strengthen the adhesive ability to changing coated coating by the active chemical group for absorption plating catalyzer that silicon-dioxide oxidation generates, in prior art one, in two, also mentioning of having is added with silicon-dioxide, they are in order to help dispersion laser promoting agent, laser active agent in their plastics is removed, and the silicon-dioxide in them cannot plate metal by the method for technology one or two, and it is because method of the present invention is added with chemical pre-treatment that the present invention can plate metal.The specific surface area that invention increases the coarse surface of silicon-dioxide is larger than the specific surface area only caused by laser ablation in prior art, and the silicon-dioxide protruded after laser burn makes its adhesive ability stronger.
By laser alligatoring surface of plastic matrix line areas, make land inner and outer surface layers form produce notable difference, retain laser treatment circuit and relatively easily obtain accurate-size, amendment size ratio is easier to, and easily realizes the advantage of automatic production in enormous quantities.
Make full use of the characteristic of nonmetallic inorganic thing silicon-dioxide, by its exploitation frosting metallic circuit preparing process, improve the bonding force on metal plating and plastic surface, obtain higher high-temp resisting high-humidity resisting performance, improve the manufacturability of electroless plating pre-treatment, solve the problem of quality monitoring difficulty.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, obviously, accompanying drawing in the following describes is only some embodiments of the present invention, for those skilled in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.In accompanying drawing:
Fig. 1 is the method steps that a kind of frosting makes precision metallic circuit.
Embodiment
Hereafter in the mode of specific embodiment, the present invention is described in detail by reference to the accompanying drawings.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that the embodiment that can also use other, or the amendment on structure and function is carried out to the embodiment enumerated herein, and can not depart from the scope and spirit of the present invention.
Make in the embodiment of the method for precision metallic circuit at a kind of frosting provided by the invention, as shown in Figure 1, comprising:
Step 1, provides a plastic substrate, and in described plastic substrate, mixed distribution has pulverous Precipitated silicon dioxide; Described Precipitated silicon dioxide content is 0.8 ~ 4%w/w.Described plastic substrate is thermoplastics or the thermosetting resin that mixed distribution has Powdered Precipitated silicon dioxide.The distribution of Precipitated silicon dioxide powder of the present invention in plastic substrate can be that to be uniformly distributed also can be near surface dense distribution, in order to simplify making processes, is preferably uniformly distributed.Present invention utilizes the resistant to elevated temperatures characteristic of silicon-dioxide, in laser burn, parts of plastics is around burnt minimizing, leaves the projection one by one in the silicon-dioxide formation microtexture of not burnt by high temperature.In the present embodiment, plastic substrate can be plate shape also can be other polymorphic structures.
Step 2, with the surface lines district that laser radiation plastic substrate is preset, makes described surface lines district burn alligatoring, and the surface of alligatoring forms the silica dioxide granule protruded; The coarse surface of the plastic substrate that the present embodiment is formed not only has the alligatoring that in prior art, parts of plastics is formed by calcination, also has the silicon-dioxide highlighted, thus the specific surface area of increasing plating catalyzer attachment surface.
Step 3, plastic substrate after described step 2 being processed carries out electroless plating pre-treatment, make the exposed surface of the silica dioxide granule of described protrusion generate the active chemical group plating catalyzer for absorption, and add attachedization plating catalyzer in the surface lines district of the silicon-dioxide with described active chemical group; The silicon-dioxide with described active chemical group has stronger adsorptive power to change plating catalyzer, can more in depth in conjunction with describedization plating catalyzer.The silica sphere protruded generates the active chemical group of a large amount of adsorbable chemical plating catalyst after suitable chemical oxidation, but not the logicalnot circuit district frosting that laser ablation is crossed is still to changing the very weak inert condition of plating Catalyst Adsorption, the land that follow-up change plating catalyzer meeting selective adsorption is crossed at laser ablation;
Step 4, described in the plastic substrate of the reaction of plating catalyzer by electroless plating liquid and describedization after step 3 processes, surface lines districtization plates underlying metal; Described underlying metal is copper, or nickel.
Step 5, at described underlying metal surface plating or plating thick metal level to preset thickness, finally forms metallic circuit.Described thick metal layers is copper, or nickel, or palladium, or gold, or silver.
Described Precipitated silicon dioxide is commonly called as white carbon black, and also known as silicate hydrate, light silicon dioxide, chemical expression is generally write as mSiO
2nH
2o, outward appearance is the amorphous powder of white high dispersing, and there is a large amount of crackle on surface, and proportion is 2.319 ~ 2.653, and fusing point is 1750 DEG C.Water insoluble and the most acid of Precipitated silicon dioxide, can become the particulate of gathering after absorbing moisture in atmosphere.Precipitated silicon dioxide can be dissolved in caustic soda and hydrofluoric acid, and stablize other pharmaceutical chemicals, high temperature resistantly not decompose, do not burn, have very high electrical insulating property, porousness, internal surface area is large.
Protruded the silicon-dioxide revealed after laser burn and increase after oxidation the specific surface area of self in the present embodiment, thus strengthen silicon-dioxide oxidation products to the adhesive ability changing coated coating, the two object is different with effect.In the present embodiment, silica oxides specific surface area only causes the specific surface area of alligatoring larger by laser ablation than in prior art, and the silicon-dioxide protruded can plate catalyzer and is deeply combined with adding attached change, thus the metallic traces making the present embodiment finally be formed has stronger adhesive ability, the ability of its high temperature resistance high pressure is greatly improved.
As a kind of embodiment of step 3, described electroless plating pre-treatment comprises:
Step 311, carries out ultrasonic cleaning, the detritus stayed after removing surperficial calcination to the surface of plastic matrix after step 2 processes;
Step 312, carries out chemical oxidation reaction process with oxygenant to described surface lines district and makes the exposed surface of described Precipitated silicon dioxide generate the active chemical group plating catalyzer for absorption;
Step 313, the surface lines district after step 312 processes carries out successively add palladium, palladium reduction, is formed described in one deck change plating catalyzer on the surface of alligatoring with the silica sections with described active chemical group.
As the embodiment of another kind of step 3, described electroless plating pre-treatment comprises:
Step 321, the plastic substrate after step 2 being processed immerses in the liquid containing plastics swelling agent and/or oxygenant and does matting, and plastics swelling agent remains for helping to remove the plastics being attached to silica sphere herein
Step 322, then immersion does chemical oxidation containing in the liquid of oxygenant,
Step 323, carries out adding palladium, palladium reduction activation process then,
Step 324, immerses plastic substrate in deionized water and washes.
As a kind of embodiment, be specially with the surface lines district that laser radiation plastic substrate is preset described in step 2: with pre-set velocity, the focus of laser beam is moved along described surface lines district, make the described surface lines district of illuminated mistake burn alligatoring.
As a kind of embodiment, described laser is infrared laser, or green glow, or UV-light.
As another kind of embodiment, described laser is pulse laser.
Compare the technology of three described in background technology, bonding strength between the metallic circuit that surface of plastic matrix precision metallic circuit manufacturing method of the present invention is made and plastic substrate is high, high-temp resisting high-humidity resisting performance is high, the silicon-dioxide added is little compared with metal mixture to plastics Color influences, and silicon-dioxide commercially has the source of goods, stay-in-grade supply of commodities.
Manufacturing technology of the present invention comprises: 1, be mixed into and be dispersed in plastic raw materials by suitable sedimentation type SiO2; 2, plastic substrate can adopt conventional injection moulding to make; 3, with the laser ablation surface of plastic matrix line areas of IR ~ UV frequency range of appropriate energy and kinematic parameter, surface of plastic matrix proterties is changed formation coarse surface; 4, the plastic substrate crossed of laser treatment is through plating front chemical pre-treatment, enough change plating catalyzer are adsorbed in surface lines district, before described plating chemical treatment comprise ultrasonic cleaning, chemical oxidation, add palladium, reduction, the processing step such as washing, before adding palladium, form described active chemical group by chemical oxidation by the silicon-dioxide that coarse surface protrudes, this active chemical group plates catalyzer and has stronger adsorptive power with changing; 5, first plate end copper in plastic immersion electroless copper liquid, then proceeding to is plated thick copper liquid or the change thick nickel liquid of plating or plates out satisfactory metallic circuit in changing liquids such as plating thick golden liquid.
Different being of the technology of the present invention and three technology existing in background technology and common plastics part metallizing circuit:
1, the plastic material of plastic substrate appended by metallic circuit is different.Containing different metal mixtures in the plastics of technology one, two, directly can cause electroless copper etc. and generate metallic circuit; The additive that electroless plating occurs is not caused in technology three plastics; Have in plastics of the present invention and indirectly silicon-dioxide can occur initiation plating.
2, electroless plating method for generation is caused different.Technology one, two utilizes laser ablation frosting line areas, and the metal mixture on laser beam energy decomposition plastics surface is metallics, and in the copper facing of plastic stent immersionization, nickel, golden liquid, metal ion is deposited directly on metallics, generates metallic circuit; And after technology three and the technology of the present invention utilize laser ablation frosting line areas, before plastic stent immerses the electroless copper identical with technology one or two, nickel, golden liquid metallizing circuit, need to do the front chemical pre-treatment of plating, palladium metal particle enough in the absorption of line areas.
3, before the plating that the technology of the present invention is used with technology three, chemical pre-treatment is different, and each step object of process caused because plastic substrate is different namely, medicine liquid ingredient are inevitable different.The micro-rough body structure surface of the technology of the present invention laser ablation line areas fills the air Precipitated silicon dioxide in a large number and technology three does not have.First, Precipitated silicon dioxide self is with there being a large amount of crackle, and it evenly distributes with filling the air, and greatly increases micro-rough structural rate surface-area, improves it and changes plating catalyst metal palladium particle ability to arrange jobs, fining metal coating, quickeningization plating speed; Secondly, silicon-dioxide is more oxidizable compared with the parts of plastics of inert polymer resin, allows to reduce chemical oxidation intensity, widens the difference of the inside and outside absorptionization plating in line areas catalyzer, is beneficial to technology controlling and process; Finally, silicon-dioxide energy reinforced plastics microcosmic alligatoring structure its own mechanical intensity, strengthens the bonding strength of thick metal layers and plastic substrate.
The surface grafting that before plating of the present invention, chemical pre-treatment borrows chemical oxidation step that silicon-dioxide is oxidized to be formed absorptionization can plate the active group of catalyst metal palladium particle, then appropriate change plating catalyzer is adsorbed onto in line areas adding in palladium, reduction, water-washing step, for subsequent chemistry copper facing, nickel, gold are ready.And technology three needs to invade in advance etc. in step by the molten frosting that splits of chemical liquid, reach the specific surface area object increasing micro-rough structure, reach in the molten micro-rough body structure surface grafting active group object split by chemical oxidation, in the absorption of line areas, change plating catalyst metal palladium particle by activation.
Be below two concrete embodiments of the method:
Embodiment 1:
1, by the sedimentation type SiO of 0.4wt% or 2wt%
2be mixed in black PC plastic raw materials;
2, injection moulding obtains metallic circuit support plastic substrate;
3, focus on frosting line areas by the pulsed infrared laser beam of 2W, 1064nm, 80Hz, and move laser beam with 2000m/s speed, form the surface be made up of micro-rough structure in the ablation of surface lines district;
4, plastic substrate takes turns doing ultrasonic cleaning, washing, chemical oxidation, washes, adds the chemical pre-treatments such as palladium, reduction, washing, only plates catalyzer at the surface lines district internal adsorption of plastic substrate to enough changes;
5, do copper at the bottom of electroless plating, continue the thick copper of plating or thick nickel or thick gold etc. on end copper surface, plate metallic circuit at surface of plastic matrix thus;
6, finally clean, dry, packaging final prod.
The metallic circuit obtained can reliably be tested by 85 ° of hot and humid hundred lattice that add of X85RHX120H.
Embodiment 2:
1, by 0.8wt% sedimentation type SiO
2be mixed in white PC plastics or PA raw material;
2, injection moulding obtains metallic circuit support plastic substrate;
3, with the green laser of suitable energy or ultraviolet (UV) laser beam focus in frosting line areas, with the mobile laser beam of suitable speed and pad parameter, go out the surface be made up of micro-rough structure in the ablation of surface lines district;
4, plastic substrate is taken turns doing to ultrasonic cleaning, washing, chemical oxidation, washes, adds the chemical pre-treatments such as palladium, reduction, washing, only plate catalyzer at plastic surface lines district internal adsorption to enough changes;
5, do copper at the bottom of electroless plating, continue the thick copper of plating or thick nickel or thick gold etc. on end copper surface, plate metallic circuit at surface of plastic matrix thus;
6, finally clean, dry, packaging final prod.
The main improvement of this patent is:
1, evenly fill the air in plastic raw materials and be dispersed with SiO
2; Injection-moulded plastic support; The laser beam ablation surface lines district of suitable energy, makes the surface in its whole surface lines district be made up of micro-rough structure; By chemical pre-treatment at surface lines district internal adsorptionization plating catalyzer, institute's adsorbization plating catalytic amount is unlikely to cause and seriously excessively plates generation in surface lines the district outside; Electroless plating underlying metal, change plating or plating thicken metallic circuit.
Silicon-dioxide contained by plastic raw materials is the sedimentation type SiO that there is the bigger serface of crackle on surface
2, content 0.8 ~ 4wt%.Also include in raw material and SiO is provided
2evenly fill the air distribution, SiO is provided
2with the additive that Plastic Resin is effectively combined, as silane coupling agent etc.Plastic raw materials comprises conventional thermoplastics and thermosetting resin.
Sedimentation type SiO is mixed in plastic substrate
2effect:
The line areas efficient adsorptionization plating catalyzer of one favourable laser ablation, because the present invention's silicon-dioxide used is sedimentation type, the surface of its individual particle itself is with a large amount of crackles, the silica particle sizes that the present invention selects is very little, but its specific surface area is comparatively large, after chemical oxidation, absorptionization plating catalyzer is very capable;
Two is that silicon dioxide ratio plastics are easily oxidized, large quantization plating catalyzer on line areas strong adsorption that laser ablation crosses can be realized after suitable chemical oxidation but not line areasization plating catalyzer is that weak attachment can be water-washed away, thus form the effect that selective adsorptionization plates catalyzer;
Three is matrix strengths that silicon-dioxide enhances plastic substrate and line areas, provides condition for metal plating is combined with the brute force of plastic substrate;
Four is the tiny silicon-dioxide energy fining metal coating spreading in surface, line areas, for the bonding strength and high-temp resisting high-humidity resisting performance improving coating and plastics provides condition.
2, the plastics forming technique making the plastic stent that metallic circuit depends on comprises the various common plastics moulding process such as injection moulding, extrusion molding.
3, the laser in described ablative plastic surface lines district comprises infrared, green glow, UV, wavelength period pulse laser.
4, describedization treatment before plating comprise immerse containing ultrasonic wave or containing plastics swelling agent, oxygenant liquid in clean, removal plastics remain, then chemical oxidation is done with the liquid containing oxygenant, then to add the activation treatment such as palladium, palladium reduction containing doing in chemical catalyst such as ionic palladium liquid, wash in last deionized water.
5, plastic substrate plating thick metal layers comprises electroless plating or electro-coppering, nickel, palladium, gold and silver etc., and plating underlying metal comprises first chemistry end copper or end nickel.
The foregoing is only preferred embodiment of the present invention, those skilled in the art know, without departing from the spirit and scope of the present invention, can carry out various change or equivalent replacement to these characteristic sum embodiments.In addition, under the teachings of the present invention, can modify to adapt to concrete situation and material to these characteristic sum embodiments and can not the spirit and scope of the present invention be departed from.Therefore, the present invention is not by the restriction of specific embodiment disclosed herein, and the embodiment in the right of all the application of falling into all belongs to protection scope of the present invention.
Claims (10)
1. frosting makes a method for precision metallic circuit, it is characterized in that, comprising:
Step 1, provides a plastic substrate, and in described plastic substrate, mixed distribution has pulverous Precipitated silicon dioxide;
Step 2, with the surface lines district that laser radiation plastic substrate is preset, makes described surface lines district burn alligatoring, and the surface of alligatoring forms the silica dioxide granule protruded;
Step 3, plastic substrate after described step 2 being processed carries out electroless plating pre-treatment, make the exposed surface of the silica dioxide granule of described protrusion generate the active chemical group plating catalyzer for absorption, and add attachedization plating catalyzer in the surface lines district of the silicon-dioxide with described active chemical group;
Step 4, described in the plastic substrate of the reaction of plating catalyzer by electroless plating liquid and describedization after step 3 processes, surface lines districtization plates underlying metal;
Step 5, at described underlying metal surface plating or plating thick metal level to preset thickness, finally forms metallic circuit.
2. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, electroless plating pre-treatment described in step 3 comprises:
Step 311, carries out ultrasonic cleaning, the detritus stayed after removing surperficial calcination to the surface of plastic matrix after step 2 processes;
Step 312, carries out chemical oxidation reaction process with oxygenant to described surface lines district and makes the exposed surface of described Precipitated silicon dioxide generate the active chemical group plating catalyzer for absorption;
Step 313, the surface lines district after step 312 processes carries out successively add palladium, palladium reduction, is formed described in one deck change plating catalyzer on the surface of alligatoring with the silica sections with described active chemical group.
3. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, electroless plating pre-treatment described in step 3 comprises:
Step 321, the plastic substrate after step 2 being processed immerses in the liquid containing plastics swelling agent and/or oxygenant and does matting,
Step 322, then immersion does chemical oxidation containing in the liquid of oxygenant,
Step 323, carries out adding palladium, palladium reduction activation process then,
Step 324, immerses plastic substrate in deionized water and washes.
4. a kind of frosting according to claim 1 makes the method for precision metallic circuit, it is characterized in that, be specially with the surface lines district that laser radiation plastic substrate is preset described in step 2: with pre-set velocity, the focus of laser beam is moved along described surface lines district, make the described surface lines district of illuminated mistake burn alligatoring.
5. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, described laser is infrared laser, or green glow, or UV-light.
6. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, described laser is pulse laser.
7. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, described thick metal layers is copper, or nickel, or palladium, or gold, or silver.
8. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, described underlying metal is copper, or nickel.
9. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, described Precipitated silicon dioxide content is 0.8 ~ 4wt%.
10. a kind of frosting according to claim 1 makes the method for precision metallic circuit, and it is characterized in that, described plastic substrate is thermoplastics or the thermosetting resin that mixed distribution has Powdered Precipitated silicon dioxide.
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| CN106102309A (en) * | 2016-07-13 | 2016-11-09 | 吕铁铮 | The method that plastic circuit is prepared in Galvanic reaction is carried out with silicon powder |
| CN108950526A (en) * | 2018-08-27 | 2018-12-07 | 合肥学院 | A method of the high-resolution metallized polymeric substrate based on chemical plating |
| CN110544817A (en) * | 2018-05-29 | 2019-12-06 | 西安美频电子科技有限公司 | Weldable metalized injection-molded antenna oscillator |
| CN111463564A (en) * | 2020-03-05 | 2020-07-28 | 上海阿莱德实业股份有限公司 | Preparation method of plastic antenna oscillator with high coating bonding strength |
| CN111805091A (en) * | 2020-06-09 | 2020-10-23 | 深圳市信维通信股份有限公司 | LAP laser etching process |
| CN112981379A (en) * | 2020-10-21 | 2021-06-18 | 东莞小禹科技有限公司 | Plastic part processing method |
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| CN104451615A (en) * | 2013-09-17 | 2015-03-25 | 比亚迪股份有限公司 | Surface treatment method for chemical plating activator, chemical plating activator, application thereof, polymer product and surface metallization method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106102309A (en) * | 2016-07-13 | 2016-11-09 | 吕铁铮 | The method that plastic circuit is prepared in Galvanic reaction is carried out with silicon powder |
| CN110544817A (en) * | 2018-05-29 | 2019-12-06 | 西安美频电子科技有限公司 | Weldable metalized injection-molded antenna oscillator |
| CN108950526A (en) * | 2018-08-27 | 2018-12-07 | 合肥学院 | A method of the high-resolution metallized polymeric substrate based on chemical plating |
| CN111463564A (en) * | 2020-03-05 | 2020-07-28 | 上海阿莱德实业股份有限公司 | Preparation method of plastic antenna oscillator with high coating bonding strength |
| CN111463564B (en) * | 2020-03-05 | 2022-05-31 | 上海阿莱德实业股份有限公司 | Preparation method of plastic antenna oscillator with high coating bonding strength |
| CN111805091A (en) * | 2020-06-09 | 2020-10-23 | 深圳市信维通信股份有限公司 | LAP laser etching process |
| CN112981379A (en) * | 2020-10-21 | 2021-06-18 | 东莞小禹科技有限公司 | Plastic part processing method |
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| CN105543813B (en) | 2018-07-31 |
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