CN108004529A - The composite material and its manufacture method of selective three-dimensional conductive layer are realized on flexible macromolecule base material - Google Patents

The composite material and its manufacture method of selective three-dimensional conductive layer are realized on flexible macromolecule base material Download PDF

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CN108004529A
CN108004529A CN201711422449.7A CN201711422449A CN108004529A CN 108004529 A CN108004529 A CN 108004529A CN 201711422449 A CN201711422449 A CN 201711422449A CN 108004529 A CN108004529 A CN 108004529A
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laser
composite material
base material
selective
conductive layer
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CN108004529B (en
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曹艳肖
兰修才
林云
唐勇
苏子凌
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China Bluestar Chengrand Research Institute of Chemical Industry Co Ltd
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China Bluestar Chengrand Research Institute of Chemical Industry Co Ltd
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    • 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
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • 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
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    • 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
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    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
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    • 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
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    • C23C18/1601—Process or apparatus
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    • C23C18/1646—Characteristics of the product obtained
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    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser
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    • 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
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    • 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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    • 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
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Abstract

The invention discloses the composite material and its manufacture method that selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, its raw material composition includes：Polymer base material, laser activation agent, inorganic roughening agent, dispersant, surface modifier, antioxidant, powder adhesive, pigments for whitening；Raw material is mixed in mixer, after double screw extruder extruding pelletization and injection molding, three-dimensional laser carving is carried out with laser selective, form the metallization rough surface of pit and/or void structure, plastic cement preparation is impregnated in strong acid or highly basic to implementing chemical plating after the further roughening treatment in surface again, so as to form the radio frequency electric component composite material with 3 D stereo circuit structure.Composite material high temperature resistant, the high humidity, coating are firmly combined with, flexible bent, so as to form 3-D solid structure antenna and the compliant member composite material wearable for intelligence in specific region by design requirement.Fabrication process condition of the present invention is easily-controllable at the same time, is easy to industrialization promotion implementation.

Description

The composite material and its system of selective three-dimensional conductive layer are realized on flexible macromolecule base material Make method
Technical field
The present invention relates to a kind of flexible macromolecule composite material and its manufacture method with three-dimensional conductive layer, and in particular to Be a kind of flexible three-dimensional conductive layer that heatproof, moisture-proof, coating are realized on insulating properties polymer base material and is firmly combined with Composite material and its manufacture method.The composite material can be formed 3-D solid structure conduction by design requirement in specific region Circuit, the compliant member wearable for antenna and intelligence.
Background skill is asked
With the highly integrated of electronic equipment, subminaturization and the fast development for transmitting high speed, microwave communication, microwave are facilitated Device and Microwave Net are grown rapidly to extra small, ultralight and ultra-thin direction.Wherein, one in electronics miniaturization it is great into Exhibition, is to three dimensional mold interconnecting（3D-MID）The utilization of technology, it can make the electric property of device and mechanical performance realize height Degree is integrated.Realize that the technique of this new technology is referred to as the direct circuit moulding process (Laser of laser Directstructuring, LDS).In the 1990s, M.Schumann and the R.Sauerbrey religion of RICE universities of the U.S. Award just report wavelength be 248nm KrF lasers equably irradiate polyimides（PI）With polyphenyl and miaow thiophene（PBI）It can make It is changed into conductor from insulator（Appl.Phys.Lett.l991,58(5),428-430；J.Appl.Phys.1993,73 (6), 3001-3006）.Palladium is dissolved in dimethylformamide by later someone, then it is coated on to frosting, then divided with standard Sub- laser is activated with wavelength 248nm, can make circuit structure regional metal, but is difficult to obtain firm binding force Precipitate metallic circuit（Galvanotechnin, nineteen ninety, volume 81, the l0 phases）.United States Patent (USP) US5599592A report by Sb2O3With thermoplastic resin it is compound after activated again with infrared laser, can produce the metal core easy to chemical plating, but its metal layer with Combination power between plastic basis material is weaker, and Sb2O3It is carcinogenic compound again, difficult large-scale production.US2004/0241422A and US7060421 is also reported the ABO of cupric, nickel, cobalt, iron etc. respectively2Type or AB2O4The spinel structure inorganic matter of type and heat Section bar is made after plastic resin is compound, then uses Ultra-Violet Laser again（Wavelength is 248nm or 308nm）Or infrared laser（Wavelength l, 064nm or 10,600nm）Activated, restore the metal crystal nuclei of simple substance, and form gold on plastic substrate by chemical plating Belong to layer, but the method requires equipment and the very tight TACT-CONSTRUCTION-RATES of operating procedure, and technique controlling difficulty is big.
The Chinese patent of publication number CN1234960A discloses a kind of compound suitable for LDS technologies, be by palladium diacetate with Aryl diketone organic ligand is coordinated the organic palladium complex solution of generation in dimethylformamide, then penetrates into fumed silicate The carrier granular of composition, then again with mixed with polymers through granulation, injection molding, finally coordinates organic palladium under laser irradiation Thing cracking discharges palladium metal core, then Surface of profile metal is melted into circuit structure with chemical plating.Although this method can make gold Belonging to circuit and substrate has stronger combination power, but expensive palladium diacetate then result in this technology cost it is higher.
The Chinese patent of publication number CN101859613A discloses a kind of modified oxalic acid diketone complex and thermoplastic resin And the compound of additive composition, but its emphasis refers to the improvement of LDS techniques.The China of publication number CN101747650A is specially Profit additionally provides a kind of plastics composite, its main ingredient is the combined oxidation of plastic basis material, catalyst and delafossite type structure Thing, available for promoting chemical plating.Recently, Wang Meng etc. reports the laser for the 1064nm wavelength launched with Nd/YAG lasers to poly- Mutual-phenenyl two acid bromide two alcohol ester（PBT）The surface of material carries out 3 D stereo irradiation, so that selective chemical plating can be realized（Tianjin College journal 2011,44 (ll), 1019-1023；Chinese laser, 2010,37 (12)；3155-3161).But above-mentioned patent and text Offer in disclosed technical solution and be directed to stringent process control condition, and it is more demanding to manufacturing equipment, thus be unfavorable for pushing away Wide production.
The content of the invention
It is contemplated that overcome drawbacks described above existing in the prior art, there is provided choosing is realized on a kind of flexible macromolecule base material The composite material and its manufacture method of selecting property three-dimensional conductive layer.The composite material is realized for one kind on insulating properties polymer base material 3 D stereo conductive layer, its high temperature resistant, high humidity, coating is firmly combined with, flexible bent, for manufactured 3-D solid structure Conducting wire has selectivity, while the composite material manufacturing technology condition is easily-controllable, not high to equipment requirement, is easy to industrialization and pushes away It is wide to implement.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
The composite material of selective three-dimensional conductive layer is realized on flexible macromolecule base material, the composition of raw material by weight ratio includes：
51.5-81 parts of polymer base material
5-10 parts of laser activation agent
Inorganic 10-30 parts of agent of roughening
0.2-1.2 parts of dispersant
0.3-1.6 parts of surface modifier
0.5-1.0 parts of antioxidant
0.5-1.0 parts of powder adhesive
0-10 parts of toner
The polymer base material is permittivity ε=1.9-2.5, dielectric loss tangent tg δ=1-3 × l0-3Insulating properties high score Sub- material, in powdery or granular.
Further, the polymer base material is selected from copolymer polypropylene（PPR）, homopolypropylene（PPH）, polytetrafluoroethylene (PTFE) （PTFE）, thermoplastic elastomer (TPE)（TPE, TPU etc.）, polyurethane termoplastic elastomer, high density polyethylene (HDPE)（HDPE）, Midst density gathers Ethene（MDPE）, linear low density polyethylene（LLDPE）, ultra high density polyethylene（SHDPE）, fiber glass reinforced polypropylene（GFR- PP）, ethylene-ethyl acrylate copolymer（EVA）Or ethylene-tetrafluoroethylene copolymer（ETFE）In one kind.
Further, the preferred copolymer polypropylene of the polymer base material（PPR）, homopolypropylene（PPH）.
The laser activation agent is following one kind or any two kinds of mixture：The copper chromite of spinel structure （CuCr2O4）, the copper titanate of perovskite structure（CuTiO3）, cupric phosphate（Cu3(PO4)2）, acid phosphate hydrogen copper（CuHPO4）, alkali Formula cupric phosphate（CuPO4OH）, stannic oxide（SnO2）Deng.
Further, the preferred copper chromite of laser activation agent（CuCr2O4）Or alkali formula cupric phosphate（CuPO4OH）Powder, Particle diameter is 200nm-2 μm.
The inorganic roughening agent is selected from precipitated calcium carbonate（Fine particle calcium carbonate）, powdered whiting（Coarse whiting）, calcium monohydrogen phosphate （CaHPO4）, calcium phosphate（Ca3(PO4)2）, calcium sulfate（CaSO4）, White Carbon black（SiO2）, kaolin one kind in talcum powder or appoints The mixture of two kinds of meaning, is the powder of 1.5 μm -20 μm of particle diameter.
Further, the preferred precipitated calcium carbonate of inorganic roughening agent or powdered whiting, or the two to be arbitrarily to compare The mixture of example.
The dispersant is selected from pectin, polyacrylamide, magnesium sulfate, one kind in perfluoro caprylic acid or methylcellulose.
The surface modifier is the titanate coupling agent of alcoxyl fundamental mode, is chosen in particular from Nanjing dawn chemical industry, model One kind in NDZ-101, NDZ-l02, NDZ-201, TC-l0l, TC-114.
Further, the preferred titanate coupling agent NDZ-101 of the surface modifier.
The antioxidant is selected from the combination of antioxidant 1010 and irgasfos 168.
Silicone oil or atoleine, preferred liquid paraffin may be selected in the powder adhesive.
Calcium sulfate, talcum powder, rutile type titanium white etc. may be selected in the toner.
Further, the preferred rutile type titanium white of the toner, such as 902 titanium dioxide of Dupont.
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on the flexible macromolecule base material is：By raw material Mixed in mixer, after double screw extruder extruding pelletization and injection molding, in three-dimensional laser carving equipment, by being previously entered CAD 3D structure circuit diagram, carry out three-dimensional laser carving, the surface crossed by superlaser laser carving, raw material point with laser selective What solution was formed includes the metallization rough surface of the pit and/or void structure including metallic element, what these were decomposed to form Ni metal2+, heavy copper and thick copper are realized by autocatalytic effect in chemical plating process, formed with 3 D stereo circuit structure Radio frequency electric component composite material, its concrete technology step are as follows：
（1）Raw material is mixed in mixer, then through double screw extruder extruding pelletization, obtains plastic grain material；Extrusion Process conditions are as follows：Screw speed is controlled in 200-500r/min, preferably 200r/min, each section of operation temperature：One area 180 DEG C -190 DEG C, two 200 DEG C -210 DEG C of areas, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 DEG C of areas, Six 200 DEG C -210 DEG C of areas, seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature；
（2）By step（1）It is plastic cement product that obtained particulate material, which adds injection molding in injection molding machine,；220 DEG C -240 of injection temperature DEG C, injection pressure 60MPa, 210 DEG C of nozzle temperature；
（3）By step（2）Obtained plastic cement product is put into the fixture of three-dimensional laser carving equipment, by being previously entered in 3D laser engraving machines CAD processing circuits figure carries out three-dimensional laser carving with laser；Laser output power is 3-12W, optical maser wavelength 1064nm, the laser carving time 0.2-0.3s, linear velocity 2000mm/s；
（4）Plastic cement product after laser carving is impregnated at least 30 minutes in acid or alkali, oil removing is carried out to its surface and surface is thick Change is handled, further to increase the adhesive force of the coat of metal；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 8-12min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 20- 25min；3rd step nickel plating technology, temperature control is in 80-81 DEG C, time 5-10min, formation metallization pattern, up to having three Tie up the radio frequency electric component composite material of stereo circuit structure.
The three-dimensional laser carving equipment choosing Germany Le Puke（German LPKF）The fusion2000 type 3D laser carvings of company's production Machine.
Step（3）In, the transmitting light source of the laser is Nd-YAG, i.e. neodymium-YBAG ytterbium aluminum garnet laser.
Under laser output power 3-12W, purpose of the laser carving time control in 0.2-0.3s is by the present invention, due to swashing The length of light irradiation time will influence the breaking degree of valence link, and the time is too short, and radiation energy is not enough to coordinate bond being broken；Time Long, then cross-linking radiation or decomposition occur for compound.
Step（4）In, the acid is the sulfuric acid of concentration 60wt%；The alkali is the sodium hydroxide or dense of concentration 40wt% Spend the potassium hydroxide of 40wt%.
Step（5）In, the copper liquid medicine is selected from the LDSization plating liquid medicine that U.S.'s Atotech or wheat dolantin produce.
For a better understanding of the technical solution of the present invention, the manufacturing theory of composite material of the present invention is further illustrated again It is as follows：
The present invention is by designed CAD circuit diagrams, on plastic surface, with fixed laser energy electing property laser carving, quilt The part that laser is irradiated to, 1-2 microns of deep high-molecular organic materials of plastic surface are carbonized or gasify, and expose Ni metal2+It is interior Core, during electroless copper, by distinctive autocatalytic effect, the metal copper ion in copper liquid medicine is selectively deposited on sharp The region that light laser carving is crossed, forms metallization coating, the region do not crossed by laser laser carving is then deposited without the coat of metal, so as to be formed The metallization circuit pattern of selectivity, is thus made the radio frequency electric component composite material with 3 D stereo circuit structure.
In order to protect copper plate not oxidized, usually also to be examined in copper plate plating nickel on surface or gold-plated for cost control Consider, be typically nickel plating.
Compared with prior art, the present invention has the following advantages and advantageous effects：
1st, the present invention mix through raw material, double-screw extruding pelletizing, after injection molding, the plastic cement product composite material is low in 3-12W Under the laser irradiation of power, easily on the surface of composite material by the relatively low Metal-Metal bond of bond energy in material composition, metal- Oxygen key, carbon-carbon bond etc. interrupt and destroy its sub-key Jie Ju, recombinate material internal, so that composite material surface shape As including amorphous carbon or micro crystal graphite, and the particulate of metal or metal oxide, and coexisted, made multiple with tufted structure The surface of condensation material forms and pit is distributed with（Micro- hole）And/or metallization and the roughening state of void structure；To make plastic cement system The conductive layer of part is more firm, by it in strong acid（The sulfuric acid of concentration 60wt%）Or highly basic（The sodium hydroxide or hydrogen-oxygen of concentration 40wt% Change potassium）Middle dipping at least 30 minutes, plastic cement article surface can be roughened again, meanwhile, laser high energy activation area internal cause material group The autolysis divided will be left behind more holes, the product of relatively non-roughening treatment, its specific surface area can increase by more than 10 times；Through Implement electroless plating again after crossing roughening treatment, you can acquisition high temperature resistant, high humidity, flexible, the bent conductive layer being firmly combined with, Answered so as to form 3-D solid structure antenna and the compliant member wearable for intelligence in specific region by design requirement Condensation material.
2nd, composite material of the present invention is a kind of 3 D stereo conductive layer realized on insulating properties polymer base material, its resistance to height Temperature, high humidity, coating is firmly combined with, flexible bent, has selection for the conducting wire of manufactured 3 D stereo circuit structure Property, while the composite material manufacturing technology condition is easily-controllable, and it is not high to equipment requirement, it is easy to industrialization promotion implementation.
Brief description of the drawings
Fig. 1 is composite products schematic diagram of the present invention.
Embodiment
The above of the present invention is described in further detail by the following examples.But this should not be interpreted as to this The scope for inventing above-mentioned theme is only limitted to following example.Without departing from the idea case in the present invention described above, according to ability The various replacements or change that domain ordinary technical knowledge and customary means are made, should all be included within the scope of the invention.
Embodiment 1~3
The composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, the composition of raw material by weight ratio is detailed It is shown in Table 1：
The raw material composition and ratio of 1 embodiment 1~3 of table
The copolymer polypropylene（PPR）It is translucent, selected from Qilu Petrochemical EPS30R polypropylene products；
The high density polyethylene (HDPE)（HDPE）, selected from 6098 polyethylene product of Qilu Petrochemical；
The copper chromite（CuCr2O4）For black powder, particle diameter is 200nm-2 μm；
The powdered whiting is the white powder of 1.5 μm -20 μm of particle diameter.
Embodiment 4
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, with embodiment 1 Raw material exemplified by, its processing step is as follows：
（1）By copper chromite, powdered whiting, titanate coupling agent, polyacrylamide, antioxidant 1010 and 168 combination, in Mixed 5 minutes in the high-speed mixer of rotating speed 300r/min, be sufficiently mixed uniformly, take out to powder material, it is spare；Poly- third will be copolymerized Alkene pellet is put into the low speed mixer of rotating speed 60r/min, adds atoleine, is stirred 10 minutes, then is mixed above-mentioned Powder, after rotating speed 60r/min stirring at low speed 30 minutes, takes out, spare；Above-mentioned mixed raw material is added into twin-screw extrusion Extruding pelletization in machine, screw speed control are respectively in 200r/min, each section of operation temperature：One 180 DEG C -190 DEG C of area, 2nd area 200 DEG C -210 DEG C, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 DEG C of areas, six 200 DEG C -210 DEG C of areas, Seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature, obtains plastic grain material；
（2）It is plastic cement product that particulate material is added injection molding in injection molding machine, 220 DEG C -240 DEG C of injection temperature；Injection pressure 60MPa；210 DEG C of nozzle temperature；
（3）By the CAD processing circuit figures being previously entered in 3D laser engraving machines, by plastic cement product laser output power 3-6W, laser The German Le Puke companies of wavelength 1064nm, linear velocity 2000mm/s（LPKF）Fusion2000 lasers, irradiate 0.2-0.3 seconds Three-dimensional laser carving is carried out, on plastic cement article surface, the surface crossed through high energy laser laser carving, what raw material decomposes were formed includes gold The metallization rough surface of pit and/or void structure including category element；
（4）Plastic cement product after laser carving is impregnated 30 minutes in the sulfuric acid of concentration 60wt%, oil removing and table are carried out to its surface Face roughening treatment, further to increase the adhesive force of the coat of metal；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 8-12min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 20- 25min；3rd step nickel plating technology, temperature control is in 80-81 DEG C, time 5-10min, formation metallization pattern, up to having three Tie up the radio frequency electric component composite material of stereo circuit structure.
Carry out the test of mechanical property, hot property and electrical property respectively to the composite material, test result refers to table 2~4：
2 mechanical experimental results of table
3 thermal performance test result of table
4 electric performance test result of table
It can be seen that from the test result of table 2, table 3, table 4：The composite material has feature performance benefit following prominent：
（1）With extraordinary toughness, elongation at break is more than 90%；
（2）Heat distortion temperature is fully able to the technological requirement for meeting 82 DEG C of chemical nickel plating highest more than 120 DEG C；
（3）With prominent electrical property, dielectric constant only 2.5, loss factor（1GHz）Only（1-2）×10-3, it is very beneficial for The transmission of high-frequency signal.
Embodiment 5~7
The composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, the composition of raw material by weight ratio is detailed It is shown in Table 5：
The raw material composition and ratio of 5 embodiment 5~7 of table
The copolymer polypropylene（PPR）It is translucent, selected from Qilu Petrochemical EPS30R polypropylene products；
The alkali formula cupric phosphate（CuPO4OH）For white powder, particle diameter is 200nm-2 μm；
The precipitated calcium carbonate is the white powder of 1.5 μm -20 μm of particle diameter；
The rutile type titanium white is 1.5 μm of -3 μm of white powders of particle diameter.
Embodiment 8
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, with embodiment 7 Raw material exemplified by, its processing step is as follows：
（1）By alkali formula cupric phosphate, precipitated calcium carbonate, rutile type titanium white, titanate coupling agent, magnesium sulfate, antioxidant 1010 Combination with 168, mixes 5 minutes in the high-speed mixer of rotating speed 300r/min, is sufficiently mixed uniformly, takes out to powder material, It is spare；Pellets of high density polyethylene is put into the low speed mixer of rotating speed 60r/min, adds silicone oil, stirred 10 minutes, then will The above-mentioned powder mixed, adds in rotating speed 60r/min low-speed mixers after stirring 30 minutes, takes out, spare；By above-mentioned mixing Raw material afterwards adds extruding pelletization in double screw extruder, and screw speed control is respectively in 200r/min, each section of operation temperature： One 180 DEG C -190 DEG C of area, two 200 DEG C -210 DEG C of areas, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 of areas DEG C, six 200 DEG C -210 DEG C of areas, seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature, obtains plastic grain material；
（2）It is plastic cement product that particulate material is added injection molding in injection molding machine, 220 DEG C -240 DEG C of injection temperature；Injection pressure 60MPa；210 DEG C of nozzle temperature；
（3）By the CAD processing circuit figures being previously entered in 3D laser engraving machines, by plastic cement product laser output power 6-9W, laser The German Le Puke companies of wavelength 1064nm, linear velocity 2000mm/s（LPKF）Fusion2000 lasers, irradiate 0.2-0.3 seconds Three-dimensional laser carving is carried out, on plastic cement article surface, the surface crossed through high energy laser laser carving, what raw material decomposes were formed includes gold The metallization rough surface of pit and/or void structure including category element；
（4）Plastic cement product after laser carving is impregnated 50 minutes in the sodium hydroxide of concentration 40wt%, oil removing is carried out to its surface With surface roughening treatment；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 8-12min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 20- 25min；3rd step nickel plating technology, temperature control is in 80-81 DEG C, time 5-10min, formation metallization pattern, up to having three Tie up the radio frequency electric component composite material of stereo circuit structure.
Carry out the test of mechanical property, hot property and electrical property respectively to the composite material, test result refers to table 6~8：
6 mechanical experimental results of table
7 thermal performance test result of table
8 electric performance test result of table
From table 6, table 7, table 8 test result from the point of view of, which has feature performance benefit following prominent：
（1）Compared with Example 1 compared with the composite material of the present embodiment also has extraordinary toughness, and elongation at break exceedes 78%, because of the addition of rutile-type pigments for whitening, the toughness of material is reduced, but tensile strength and modulus increase；
（2）Heat distortion temperature disclosure satisfy that the technological requirement of 82 DEG C of chemical nickel plating highest more than 90 DEG C；
（3）With prominent electrical property, dielectric constant only 2.6, loss factor（1GHz）Only（2-3）×10-3, it is very beneficial for The transmission of high-frequency signal.
Embodiment 9~11
The composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, the composition of raw material by weight ratio is detailed It is shown in Table 9：
The raw material composition and ratio of 9 embodiment 9~11 of table
The copolymer polypropylene（PPR）It is translucent, selected from Qilu Petrochemical EPS30R polypropylene products；
The alkali formula cupric phosphate（CuPO4OH）For white powder, particle diameter is 200nm-2 μm；
The powdered whiting is the white powder of 1.5 μm -20 μm of particle diameter；
The rutile type titanium white is 1.5 μm of -3 μm of white powders of particle diameter.
Embodiment 12
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, with embodiment 9 Raw material exemplified by, its processing step is as follows：
（1）By alkali formula cupric phosphate, precipitated calcium carbonate, rutile type titanium white, titanate coupling agent, perfluoro caprylic acid, antioxidant 1010 and 168 combination, mixes 5 minutes in the high-speed mixer of rotating speed 300r/min, is sufficiently mixed uniformly, takes to powder material Go out, it is spare；Pellets of high density polyethylene is put into the low speed mixer of rotating speed 60r/min, adds atoleine, stir 10 points Clock, then the above-mentioned powder mixed is added in rotating speed 60r/min low-speed mixers after stir 30 minutes, taking-up is spare；Will Above-mentioned mixed raw material adds extruding pelletization in double screw extruder, and screw speed control is in 200r/min, each section of operation temperature Degree is respectively：One 180 DEG C -190 DEG C of area, two 200 DEG C -210 DEG C of areas, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, 5th area 200 DEG C -210 DEG C, six 200 DEG C -210 DEG C of areas, seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature, obtains plastic grain material；
（2）It is plastic cement product that particulate material is added injection molding in injection molding machine, 220 DEG C -240 DEG C of injection temperature；Injection pressure 60MPa；210 DEG C of nozzle temperature；
（3）By the CAD processing circuit figures being previously entered in 3D laser engraving machines, by plastic cement product laser output power 9-12W, laser The German Le Puke companies of wavelength 1064nm, linear velocity 2000mm/s（LPKF）Fusion2000 lasers, irradiate 0.2-0.3 seconds Three-dimensional laser carving is carried out, on plastic cement article surface, the surface crossed through high energy laser laser carving, what raw material decomposes were formed includes gold The metallization rough surface of pit and/or void structure including category element；
（4）Plastic cement product after laser carving is impregnated 30 minutes in the sulfuric acid of concentration 60wt%, oil removing and table are carried out to its surface Face roughening treatment；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 8-12min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 20- 25min；3rd step nickel plating technology, temperature control is in 80-81 DEG C, time 5-10min, formation metallization pattern, up to having three Tie up the radio frequency electric component composite material of stereo circuit structure.
Carry out the test of mechanical property, hot property and electrical property respectively to the composite material, test result refer to table 10~ 12：
10 mechanical experimental results of table
11 thermal performance test result of table
12 electric performance test result of table
Test event Unit Testing standard Test result
Relative dielectric constant (1GHz) - IEC 60250 2.5
Loss factor (1GHz) - IEC 60250 1.8×10-3
Volume resistivity Ohm.m IEC 60093 ＞ 1.1E14
Surface resistivity Ohm IEC 60093 ＞ 1.2E16
From table 10, table 11, table 12 test result from the point of view of, which has feature performance benefit following prominent：
（1）Compared with Example 8 compared with the composite material of the present embodiment also has extraordinary toughness, and elongation at break exceedes 78%, and as the increase of roughening agent dosage, the toughness of material can decline；
（2）Heat distortion temperature disclosure satisfy that the technological requirement of 82 DEG C of chemical nickel plating highest more than 90 DEG C；
（3）With prominent electrical property, dielectric constant only 2.5, loss factor（1GHz）In 1.0-2.0 × 10-3, it is highly beneficial In the transmission of high-frequency signal.
Comparative example
To investigate influence of the inorganic roughening agent to coating adhesion after plastic cement product chemical plating, this comparative example uses the original in table 13 Expect composition and ratio manufacture composite material, and with embodiment 9 made from composite material contrasted, adhesive force presses ASTM D3359-97 standards are detected, and test result is as shown in table 14：
The raw material composition and ratio of 13 comparative example of table and embodiment 9
The composite material adhesive force of 14 comparative example of table and embodiment 9 compares
Detection object Adhesive force grade
Comparative example 1B
Embodiment 9 4B
, it is apparent that adding 10% from table 13~14（Minimum limit value）Inorganic roughening agent（By taking powdered whiting as an example） Embodiment 9, the adhesive force of coating is significantly better than without the comparative example for adding inorganic roughening agent after chemical plating, is roughened agent and plays Obviously act on.
Embodiment 13-20
The composition of raw material by weight ratio refers to table 15 below：
Raw material Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20
Polytetrafluoroethylene (PTFE) 55
Thermoplastic elastomer (TPE) 57.5
Polyurethane termoplastic elastomer 56
Medium density polyethylene 60
Linear low density polyethylene 59
Fiber glass reinforced polypropylene 55.5
Ethylene-ethyl acrylate copolymer（EVA） 58.5
Ethylene-tetrafluoroethylene copolymer（ETFE） 57
Copper titanate 6 3
Cupric phosphate 4 7 5
Acid phosphate hydrogen copper 1 8 5 10
Stannic oxide 6 5
Calcium carbonate
Calcium monohydrogen phosphate 15 10
Calcium phosphate 20 10 15
Calcium sulfate 5 2 20
White Carbon black 10 5
Kaolin 20 15 5
Talcum powder 20 15
Pectin 0.5 0.8 0.3 1.1 0.2
Methylcellulose 1.0 0.6 0.7
Titanate coupling agent NDZ-l02 1.2 1.5 1.6 0.7
Titanate coupling agent TC-l0l 0.3 0.5 0.6 0.9
Antioxidant 1010 and 168 combination 0.5 0.8 0.6 0.9 0.7 0.5 1.0 1.0
Atoleine 0.6 1.0 0.8 0.9
Silicone oil 0.5 0.7 1.0 0.5
Calcium sulfate 7 5 5 8
Talcum powder 10 6 10 9
Embodiment 21
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, with embodiment 14 Raw material exemplified by, its processing step is as follows：
（1）Raw material is mixed in mixer, then through double screw extruder extruding pelletization, obtains plastic grain material；Extrusion Process conditions are as follows：Screw speed is controlled in 300r/min, preferably 200r/min, each section of operation temperature：One area 180 DEG C -190 DEG C, two 200 DEG C -210 DEG C of areas, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 DEG C of areas, 6th area 200 DEG C -210 DEG C, seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature；
（2）By step（1）It is plastic cement product that obtained particulate material, which adds injection molding in injection molding machine, 220 DEG C -240 of injection temperature ℃；Injection pressure 60MPa；210 DEG C of nozzle temperature；
（3）By the CAD processing circuit figures being previously entered in 3D laser engraving machines, by plastic cement product laser output power 9-11W, laser The German Le Puke companies of wavelength 1064nm, linear velocity 2000mm/s（LPKF）Fusion2000 lasers, irradiate 0.2-0.3 seconds Three-dimensional laser carving is carried out, on plastic cement article surface, the surface crossed through high energy laser laser carving, what raw material decomposes were formed includes gold The metallization rough surface of pit and/or void structure including category element；
（4）Plastic cement product after laser carving is impregnated 30 minutes in the sodium hydroxide of concentration 40wt%, oil removing is carried out to its surface With surface roughening treatment；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 8min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 25min；3rd Nickel plating technology is walked, temperature control is in 80-81 DEG C, time 5min, formation metallization pattern, up to having 3 D stereo circuit structure Radio frequency electric component composite material.
Embodiment 22
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, with embodiment 16 Raw material exemplified by, its processing step is as follows：
（1）Raw material is mixed in mixer, then through double screw extruder extruding pelletization, obtains plastic grain material；Extrusion Process conditions are as follows：Screw speed is controlled in 400r/min, each section of operation temperature：One 180 DEG C -190 DEG C of area, 2nd area 200 DEG C -210 DEG C, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 DEG C of areas, six 200 DEG C -210 DEG C of areas, Seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature；
（2）By step（1）It is plastic cement product that obtained particulate material, which adds injection molding in injection molding machine, 220 DEG C -240 of injection temperature ℃；Injection pressure 60MPa；210 DEG C of nozzle temperature；
（3）By the CAD processing circuit figures being previously entered in 3D laser engraving machines, by plastic cement product laser output power 9-11W, laser The German Le Puke companies of wavelength 1064nm, linear velocity 2000mm/s（LPKF）Fusion2000 lasers, irradiate 0.2-0.3 seconds Three-dimensional laser carving is carried out, on plastic cement article surface, the surface crossed through high energy laser laser carving, what raw material decomposes were formed includes gold The metallization rough surface of pit and/or void structure including category element；
（4）Plastic cement product after laser carving is impregnated 45 minutes in the potassium hydroxide of concentration 40wt%, oil removing is carried out to its surface With surface roughening treatment；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 12min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 0min；3rd Nickel plating technology is walked, temperature control is in 80-81 DEG C, time 8min, formation metallization pattern, up to having 3 D stereo circuit structure Radio frequency electric component composite material.
Embodiment 23
The manufacture method of the composite material of selective three-dimensional conductive layer is realized on a kind of flexible macromolecule base material, with embodiment 19 Raw material exemplified by, its processing step is as follows：
（1）Raw material is mixed in mixer, then through double screw extruder extruding pelletization, obtains plastic grain material；Extrusion Process conditions are as follows：Screw speed is controlled in 500r/min, each section of operation temperature：One 180 DEG C -190 DEG C of area, 2nd area 200 DEG C -210 DEG C, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 DEG C of areas, six 200 DEG C -210 DEG C of areas, Seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature；
（2）By step（1）It is plastic cement product that obtained particulate material, which adds injection molding in injection molding machine, 220 DEG C -240 of injection temperature ℃；Injection pressure 60MPa；210 DEG C of nozzle temperature；
（3）By the CAD processing circuit figures being previously entered in 3D laser engraving machines, by plastic cement product laser output power 7-12W, laser The German Le Puke companies of wavelength 1064nm, linear velocity 2000mm/s（LPKF）Fusion2000 lasers, irradiate 0.2-0.3 seconds Three-dimensional laser carving is carried out, on plastic cement article surface, the surface crossed through high energy laser laser carving, what raw material decomposes were formed includes gold The metallization rough surface of pit and/or void structure including category element；
（4）Plastic cement product after laser carving is impregnated 30 minutes in the sulfuric acid of concentration 60wt%, oil removing and table are carried out to its surface Face roughening treatment；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 10min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 23min；The Three step nickel plating technologies, temperature control is in 80-81 DEG C, time 10min, formation metallization pattern, up to having 3 D stereo circuit The radio frequency electric component composite material of structure.
The test of mechanical property, hot property and electrical property is carried out respectively to the composite material of embodiment 21,22,23, is tested The results detailed in Table 16.
The performance of the composite material of 16 embodiment 21,22,23 of table
From the test result of table 16 it is known that composite material of the present invention has extraordinary toughness, elongation at break more than 110%, and Tensile strength and modulus page are higher；Heat distortion temperature disclosure satisfy that the technological requirement of 82 DEG C of chemical nickel plating highest more than 82 DEG C；Tool There are prominent electrical property, dielectric constant only 2.2, loss factor（1GHz）Only 2.4E-3, is very beneficial for the transmission of high-frequency signal.

Claims (10)

1. the composite material of selective three-dimensional conductive layer is realized on flexible macromolecule base material, it is characterised in that：Raw material is matched somebody with somebody by weight The composition of ratio includes：
51.5-81 parts of polymer base material
5-10 parts of laser activation agent
Inorganic 10-30 parts of agent of roughening
0.2-1.2 parts of dispersant
0.3-1.6 parts of surface modifier
0.5-1.0 parts of antioxidant
0.5-1.0 parts of powder adhesive
0-10 parts of toner.
2. realizing the composite material of selective three-dimensional conductive layer on flexible macromolecule base material according to claim 1, it is special Sign is：The polymer base material is permittivity ε=1.9-2.5, dielectric loss tangent tg δ=1-3 × l0-3Insulating properties it is high Molecular material, in powdery or granular；The polymer base material is selected from copolymer polypropylene, homopolypropylene, polytetrafluoroethylene (PTFE), heat Thermoplastic elastic, polyurethane termoplastic elastomer, high density polyethylene (HDPE), medium density polyethylene, linear low density polyethylene, superelevation One kind in density polyethylene, fiber glass reinforced polypropylene, ethylene-ethyl acrylate copolymer or ethylene-tetrafluoroethylene copolymer.
3. realizing the composite material of selective three-dimensional conductive layer on flexible macromolecule base material according to claim 1, it is special Sign is：The laser activation agent is following one kind or any two kinds of mixture：The copper chromite of spinel structure, calcium The copper titanate of perovskite like structure, cupric phosphate, acid phosphate hydrogen copper, alkali formula cupric phosphate, stannic oxide.
4. the composite material of selective three-dimensional conductive layer is realized on the flexible macromolecule base material according to claim 1 or 3, its It is characterized in that：The laser activation agent is copper chromite or alkali formula cupric phosphate powder, and particle diameter is 200nm-2 μm.
5. realizing the composite material of selective three-dimensional conductive layer on flexible macromolecule base material according to claim 1, it is special Sign is：The inorganic roughening agent is selected from precipitated calcium carbonate, powdered whiting, calcium monohydrogen phosphate, calcium phosphate, calcium sulfate, white carbon It is black, kaolin, one kind or any two kinds of mixture in talcum powder, be 1.5 μm -20 μm of particle diameter powder.
6. realizing the composite material of selective three-dimensional conductive layer on flexible macromolecule base material according to claim 1, it is special Sign is：The dispersant is selected from pectin, polyacrylamide, magnesium sulfate, one kind in perfluoro caprylic acid or methylcellulose.
7. realizing the composite material of selective three-dimensional conductive layer on flexible macromolecule base material according to claim 1, it is special Sign is：The surface modifier is the titanate coupling agent of alcoxyl fundamental mode, is chosen in particular from Nanjing dawn chemical industry, model NDZ- One kind in 101, NDZ-l02, NDZ-201, TC-l0l, TC-114.
8. realizing the composite material of selective three-dimensional conductive layer on flexible macromolecule base material according to claim 1, it is special Sign is：The antioxidant is selected from the combination of antioxidant 1010 and irgasfos 168；Described powder adhesive selection silicone oil or Atoleine；The pigments for whitening selection calcium sulfate, talcum powder, rutile type titanium white or anatase thpe white powder.
9. the manufacture of the composite material of selective three-dimensional conductive layer is realized on flexible macromolecule base material according to claim 1 Method, it is characterised in that：Raw material is mixed in mixer, after double screw extruder extruding pelletization and injection molding, three Tie up in laser carving equipment, by the circuit diagram for the CAD 3D structure being previously entered, three-dimensional laser carving is carried out with laser selective, by high energy The surface that laser laser carving is crossed, what raw material decomposes were formed includes the metallization of the pit and/or void structure including metallic element Rough surface, these Ni metals being decomposed to form2+, heavy copper and thick copper, shape are realized by autocatalytic effect in chemical plating process Into the radio frequency electric component composite material with 3 D stereo circuit structure.
10. the system of the composite material of selective three-dimensional conductive layer is realized on flexible macromolecule base material according to claim 9 Make method, it is characterised in that：Concrete technology step is as follows：
（1）Raw material is mixed in mixer, then through double screw extruder extruding pelletization, obtains plastic grain material；Extrusion Process conditions are as follows：Screw speed is controlled in 200-500r/min, preferably 200r/min, each section of operation temperature：One area 180 DEG C -190 DEG C, two 200 DEG C -210 DEG C of areas, three 200 DEG C -210 DEG C of areas, four 200 DEG C -210 DEG C of areas, five 200 DEG C -210 DEG C of areas, Six 200 DEG C -210 DEG C of areas, seven 180 DEG C -190 DEG C of areas, 200-210 DEG C of head temperature；
（2）By step（1）It is plastic cement product that obtained particulate material, which adds injection molding in injection molding machine,；220 DEG C -240 of injection temperature DEG C, injection pressure 60MPa, 210 DEG C of nozzle temperature；
（3）By step（2）Obtained plastic cement product is put into the fixture of three-dimensional laser carving equipment, by being previously entered in 3D laser engraving machines CAD processing circuits figure carries out three-dimensional laser carving with laser；Laser output power is 3-12W, optical maser wavelength 1064nm, the laser carving time 0.2-0.3s, linear velocity 2000mm/s；
（4）Plastic cement product after laser carving is impregnated at least 30 minutes in acid or alkali, oil removing is carried out to its surface and surface is thick Change is handled, further to increase the adhesive force of the coat of metal；
（5）Plastic cement product after roughening is put into electroless copper liquid medicine and carries out chemical plating, in chemical plating, the first step sinks coppersmith Skill, temperature control is in 50-52 DEG C, time 8-12min；Second step thickness process for copper, temperature control is in 60-65 DEG C, time 20- 25min；3rd step nickel plating technology, temperature control is in 80-81 DEG C, time 5-10min, formation metallization pattern, up to having three Tie up the radio frequency electric component composite material of stereo circuit structure；
Step（3）In, the transmitting light source of the laser is Nd-YAG, i.e. neodymium-YBAG ytterbium aluminum garnet laser；
Step（4）In, the acid is the sulfuric acid of concentration 60wt%；The alkali is the sodium hydroxide or concentration of concentration 40wt% The potassium hydroxide of 40wt%.
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