CN108004529B - Composite material for realizing selective three-dimensional conductive layer on flexible polymer substrate and manufacturing method thereof - Google Patents

Composite material for realizing selective three-dimensional conductive layer on flexible polymer substrate and manufacturing method thereof Download PDF

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CN108004529B
CN108004529B CN201711422449.7A CN201711422449A CN108004529B CN 108004529 B CN108004529 B CN 108004529B CN 201711422449 A CN201711422449 A CN 201711422449A CN 108004529 B CN108004529 B CN 108004529B
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temperature
composite material
laser
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copper
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CN108004529A (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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    • 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
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    • C23C18/38—Coating with copper
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    • C23C18/1601—Process or apparatus
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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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    • C23C18/1646—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
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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
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    • 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
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    • C08K3/20—Oxides; Hydroxides
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Abstract

The invention discloses a composite material for realizing a selective three-dimensional conducting layer on a flexible polymer substrate and a manufacturing method thereof, and the composite material comprises the following raw materials: the coating comprises a polymer substrate, a laser activator, an inorganic coarsening agent, a dispersing agent, a surface modifier, an antioxidant, a powder adhesive and a whitening pigment; mixing the raw materials in a mixer, extruding and granulating by a double-screw extruder, injection molding, selectively performing three-dimensional laser etching by using laser to form a metalized rough surface with a pit and/or cavity structure, soaking a plastic preparation in strong acid or strong alkali to further coarsen the surface, and performing chemical plating to form the radio frequency electronic component composite material with the three-dimensional circuit structure. The composite material is high temperature and high humidity resistant, the plating layer is firmly combined, and the composite material is flexible and bendable, so that a three-dimensional structure antenna can be formed in a specific area according to design requirements, and the composite material is used for intelligent wearable flexible part composite materials. Meanwhile, the manufacturing process condition of the invention is easy to control, and the invention is easy to be popularized and implemented industrially.

Description

Composite material for realizing selective three-dimensional conductive layer on flexible polymer substrate and manufacturing method thereof
Technical Field
the invention relates to a flexible polymer composite material with a three-dimensional conductive layer and a manufacturing method thereof, in particular to a composite material of a flexible and bendable three-dimensional conductive layer which realizes temperature resistance, moisture resistance and firm combination of a plating layer on an insulating polymer base material and a manufacturing method thereof. The composite material can form a three-dimensional structure conductive circuit in a specific area according to design requirements, and is used for antennas and intelligent wearable flexible parts.
Background of the invention
with the rapid development of high integration, microminiaturization and high transmission speed of electronic equipment, rapid development of microwave communication, microwave devices and microwave networks in the direction of ultra-small, ultra-light and ultra-thin is promoted. Among them, a significant advance in the miniaturization of electronic devices is the application of three-dimensional molded interconnect (3D-MID) technology, which enables high integration of the electrical and mechanical properties of the devices. A process of implementing this new technology is called Laser Direct Structuring (LDS). In the 90 s of the 20 th century, professors m.schumann and r.sauerbrey at RICE university reported that a KrF laser with a wavelength of 248nm could uniformly irradiate Polyimide (PI) and Polybenzothiazole (PBI) from an insulator to a conductor (appl.phys.lett.l 991,58(5), 428-430; j.appl.phys.1993,73(6), 3001-3006). Subsequently, palladium acetate was dissolved in dimethylformamide, coated on a plastic surface and activated with an excimer laser at a wavelength of 248nm to metallize the circuit structure areas, but it was difficult to obtain strongly bonded precipitated metal circuits (Galvanotechnin, 1990, volume 81,stage l 0). U.S. Pat. No. 4, 5599592A reports Sb2O3Compounding with thermoplastic resin and activating with infrared laser to produce metal core for chemical plating, and has weak binding force between metal layer and plastic base material and Sb2O3But also is a carcinogenic compound and is difficult to produce in large scale. US2004/0241422A and US7060421 also report to ABO containing copper, nickel, cobalt, iron, etc2type or AB2O4The spinel-structured inorganic matter is compounded with thermoplastic resin to form a section, then the section is activated by ultraviolet laser (with the wavelength of 248nm or 308 nm) or infrared laser (with the wavelength of l,064nm or 10,600 nm) to reduce metal crystal nuclei of simple substances, and a metal layer is formed on a plastic substrate by chemical plating, but the method requires very strict equipment and operation process and has great difficulty in process control.
Chinese patent publication No. CN1234960A discloses a composite suitable for LDS technology, which is prepared by coordinating palladium diacetate and an aryl diketone organic ligand in dimethylformamide to generate an organic palladium complex solution, then infiltrating the organic palladium complex solution into carrier particles composed of pyrolytic silicate, then mixing with a polymer, granulating, injection molding, finally cracking the organic palladium complex under laser irradiation to release palladium metal cores, and then metallizing the surface of the profile into a circuit structure by chemical plating. Although the method can make the metal circuit and the substrate have stronger bonding force, the expensive palladium diacetate causes higher cost of the technology.
Chinese patent publication No. CN101859613A discloses a composite of a modified oxalic acid diketone complex, a thermoplastic resin and additives, but the focus of the disclosure is to improve the LDS process. Chinese patent publication No. CN101747650A also provides a plastic composition, which mainly comprises a plastic substrate, a catalyst and a copper-iron-ore type composite oxide, and can be used for promoting electroless plating. Recently, Wangmeng et al reported that selective electroless plating can be achieved by three-dimensional irradiation of the surface of polybutylene terephthalate (PBT) material with laser of 1064nm wavelength emitted from Nd/YAG laser (Tianjin university Proc.2011, 44(ll), 1019-1023; China laser, 2010, 37 (12); 3155-3161). However, the technical solutions disclosed in the above patents and documents involve strict process control conditions and have high requirements for manufacturing equipment, which is not favorable for popularization and production.
disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a composite material for realizing a selective three-dimensional conductive layer on a flexible high polymer substrate and a manufacturing method thereof. The composite material is a three-dimensional conducting layer realized on an insulating polymer substrate, is high-temperature and high-humidity resistant, has firm plating layer combination, is flexible and bendable, has selectivity on a manufactured three-dimensional structure conducting circuit, is easy to control manufacturing process conditions, has low requirements on equipment and is easy to industrially popularize and implement.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate comprises the following raw materials in parts by weight:
51.5-81 parts of polymer base material
5-10 parts of laser activator
10-30 parts of inorganic coarsening agent
0.2 to 1.2 portions of dispersant
0.3 to 1.6 portions of surface modifier
0.5 to 1.0 portion of antioxidant
0.5 to 1.0 portion of powder adhesive
0 to 10 portions of toner
The polymer base material has a dielectric constant epsilon = 1.9-2.5 and a dielectric loss tangent tg =1-3 xL 0-3The insulating polymer material of (2) is in the form of powder or granules.
Further, the polymer base material is selected from one of polypropylene copolymer (PPR), polypropylene homopolymer (PPH), Polytetrafluoroethylene (PTFE), thermoplastic elastomer (TPE, TPU, etc.), polyurethane thermoplastic elastomer, High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Linear Low Density Polyethylene (LLDPE), ultrahigh density polyethylene (SHDPE), glass fiber reinforced polypropylene (GFR-PP), ethylene-ethyl acrylate copolymer (EVA) or ethylene-tetrafluoroethylene copolymer (ETFE).
further, the polymer base material is preferably a polypropylene copolymer (PPR) or a polypropylene homopolymer (PPH).
the laser activator is one or a mixture of any two of the following materials: copper chromite (CuCr) of spinel structure2O4) Perovskite-structured copper titanate (CuTiO)3) Copper phosphate (Cu)3(PO4)2) Acid form of copper hydrogen phosphate (CuHPO)4) Basic copper phosphate (CuPO)4OH), tin dioxide (SnO)2) And the like.
Further, the laser activator is preferably copper chromite (CuCr)2O4) Or basic copper phosphate (CuPO)4OH) powder with the particle size of 200nm-2 mu m.
The inorganic coarse agent is selected from light calcium carbonate (light calcium), heavy calcium carbonate (heavy calcium), and calcium hydrogen phosphate (CaHPO)4) Calcium phosphate (Ca)3(PO4)2) Calcium sulfate (CaSO)4) White carbon black (SiO)2) One or a mixture of any two of kaolin and talcum powder is powder with the particle size of 1.5-20 mu m.
further, the inorganic coarsening agent is preferably light calcium carbonate or heavy calcium carbonate or a mixture of the light calcium carbonate and the heavy calcium carbonate in any proportion.
The dispersing agent is selected from one of pectin, polyacrylamide, magnesium sulfate, perfluorooctanoic acid or methyl cellulose.
The surface modifier is an alkoxy titanate coupling agent, and is specifically selected from one of Nanjing eosin chemical engineering, model numbers NDZ-101, NDZ-l02, NDZ-201, TC-l0l and TC-114.
further, the surface modifier is preferably titanate coupling agent NDZ-101.
the antioxidant is selected from the group consisting of antioxidant 1010 and antioxidant 168.
The powder adhesive can be selected from silicone oil or liquid paraffin, preferably liquid paraffin.
The toner can be selected from calcium sulfate, talcum powder, rutile type titanium dioxide and the like.
further, the toner is preferably rutile type titanium dioxide, such as DuPont 902 titanium dioxide in the United states.
The manufacturing method of the composite material for realizing the selective three-dimensional conducting layer on the flexible high polymer substrate comprises the following steps: mixing the raw materials in a mixer, extruding and granulating by a double-screw extruder, injection molding, selectively performing three-dimensional laser etching on a three-dimensional laser etching device by using laser according to a circuit diagram of a CAD three-dimensional structure input in advance, decomposing the raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements, and decomposing the formed metal Cu2+In the chemical plating process, the copper deposition and the thick copper are realized through the autocatalysis effect to form the radio frequency electronic component composite material with the three-dimensional circuit structure, and the specific process steps are as follows:
(1) Mixing the raw materials in a mixer, and extruding and granulating by a double-screw extruder to obtain plastic granules; the extrusion process conditions were as follows: the rotating speed of the screw is controlled to be 200-500r/min, preferably 200r/min, and the operating temperature of each section is respectively as follows: the temperature of a first area is 180-190 ℃, the temperature of a second area is 200-210 ℃, the temperature of a third area is 200-210 ℃, the temperature of a fourth area is 200-210 ℃, the temperature of a fifth area is 200-210 ℃, the temperature of a sixth area is 200-210 ℃, the temperature of a seventh area is 180-190 ℃, and the temperature of a machine head is 200-210 ℃;
(2) Adding the granules prepared in the step (1) into an injection molding machine to be injection molded into a plastic part; the injection temperature is 220-240 ℃, the injection pressure is 60MPa, and the nozzle temperature is 210 ℃;
(3) Putting the plastic part prepared in the step (2) into a clamp of three-dimensional laser etching equipment, and performing three-dimensional laser etching by using laser according to a CAD processing circuit diagram input into a 3D laser etching machine in advance; the laser output power is 3-12W, the laser wavelength is 1064nm, the laser etching time is 0.2-0.3s, and the linear velocity is 2000 mm/s;
(4) Dipping the plastic part subjected to laser etching in acid or alkali for at least 30 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part to further increase the adhesive force of the metal coating;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 8-12 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ and the time is 20-25 min; and thirdly, nickel plating process, controlling the temperature at 80-81 ℃ for 5-10min, and forming a metallized pattern to obtain the radio frequency electronic component composite material with the three-dimensional circuit structure.
The three-dimensional laser etching equipment adopts a fusion2000 type 3D laser etching machine produced by German Lepu family (Germany LPKF).
In the step (3), the emitting light source of the laser is Nd-YAG, namely a neodymium-ytterbium aluminum garnet laser.
Under the condition that the laser output power is 3-12W, the laser etching time is controlled to be 0.2-0.3s, so that the breaking degree of valence bonds can be influenced due to the laser irradiation time, the time is too short, and the radiation energy is not enough to break the coordination bonds; if the time is too long, the compound is cross-linked or decomposed by irradiation.
In the step (4), the acid is sulfuric acid with the concentration of 60 wt%; the alkali is sodium hydroxide with the concentration of 40wt% or potassium hydroxide with the concentration of 40 wt%.
In the step (5), the copper liquid is selected from LDS chemical plating liquid produced by American Anmet or Maide.
In order to better understand the technical scheme of the invention, the manufacturing principle of the composite material of the invention is further explained as follows:
The invention uses fixed laser energy as selective laser carving on the surface of plastic according to designed CAD circuit diagram, the part irradiated by laser is carbonized or gasified to expose metal Cu2+the inner core is selectively deposited in the laser-etched area by the specific autocatalysis effect in the chemical copper plating process, so as to form a metalized coating, and no metal coating is deposited in the area which is not etched by the laser, so as to form a selective metalized circuit pattern, thereby preparing the three-dimensional circuit junctionA composite radio frequency electronic component is formed.
In order to protect the copper plating layer from oxidation, nickel plating or gold plating is also generally applied to the surface of the copper plating layer, and for cost control reasons, nickel plating is generally applied.
Compared with the prior art, the invention has the following advantages and beneficial technical effects:
1. After raw material mixing, twin-screw extrusion granulation and injection molding, the plastic part composite material is easily subjected to 3-12W low-power laser irradiation to break and destroy molecular bond structures of metal-metal bonds, metal-oxygen bonds, carbon-carbon bonds and the like with lower bond energy in raw material components on the surface of the composite material, so that recombination occurs inside the material, the surface of the composite material is formed to contain amorphous carbon or microcrystalline graphite and particles of metal or metal oxide, and the amorphous carbon or microcrystalline graphite and the metal or metal oxide coexist in a cluster structure, and the surface of the composite material is formed to be in a metallized and roughened state distributed with pits (micro pits) and/or cavity structures; in order to make the conductive layer of the plastic part firmer, the plastic part is soaked in strong acid (sulfuric acid with the concentration of 60 wt%) or strong base (sodium hydroxide or potassium hydroxide with the concentration of 40 wt%) for at least 30 minutes, the surface of the plastic part can be coarsened again, meanwhile, more holes are left in a laser high-energy activation area due to the self dissolution of material components, and the specific surface area of the plastic part can be increased by more than 10 times compared with the part which is not coarsened; and carrying out roughening treatment and then carrying out chemical plating to obtain the flexible and bendable conducting layer which is high temperature resistant, high humidity resistant and firm in combination, so that the three-dimensional structure antenna and the flexible part composite material for intelligent wearable can be formed in a specific area according to design requirements.
2. the composite material is a three-dimensional conducting layer realized on an insulating polymer substrate, is resistant to high temperature and high humidity, is firm in plating layer combination, flexible and bendable, has selectivity on a conducting circuit of a manufactured three-dimensional circuit structure, is easy to control manufacturing process conditions, has low requirements on equipment, and is easy to industrially popularize and implement.
Drawings
FIG. 1 is a schematic view of a composite product of the present invention.
Detailed Description
the present invention will be described in further detail with reference to examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. Various substitutions and alterations according to the general knowledge and conventional practice in the art are intended to be included within the scope of the present invention without departing from the technical spirit of the present invention as described above.
Examples 1 to 3
the composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate comprises the following raw materials in percentage by weight:
TABLE 1 raw material compositions and compounding ratios of examples 1-3
Said polypropylene copolymer (PPR) is translucent and is selected from the group consisting of ziphus EPS30R polypropylene products;
Said High Density Polyethylene (HDPE) is selected from the group consisting of the ziphus petrochemical 6098 polyethylene product;
The copper chromite (CuCr)2O4) Is black powder with the grain size of 200nm-2 mu m;
The heavy calcium carbonate is white powder with the particle size of 1.5-20 mu m.
Example 4
a manufacturing method of a composite material for realizing a selective three-dimensional conducting layer on a flexible high polymer substrate takes the raw materials in embodiment 1 as an example, and the manufacturing method comprises the following processing steps:
(1) Mixing the combination of copper chromite, heavy calcium carbonate, titanate coupling agent, polyacrylamide, antioxidant 1010 and antioxidant 168 in a high-speed mixer at the rotating speed of 300r/min for 5 minutes until powder materials are fully and uniformly mixed, and taking out for later use; putting the copolymerization polypropylene granules into a low-speed mixer with the rotating speed of 60r/min, adding liquid paraffin, stirring for 10 minutes, then stirring the mixed powder at the rotating speed of 60r/min for 30 minutes, and taking out for later use; adding the mixed raw materials into a double-screw extruder for extrusion granulation, controlling the rotating speed of a screw at 200r/min, and respectively controlling the operation temperature of each section as follows: the temperature of the first zone is 180-190 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 200-210 ℃, the temperature of the fourth zone is 200-210 ℃, the temperature of the fifth zone is 200-210 ℃, the temperature of the sixth zone is 200-210 ℃, the temperature of the seventh zone is 180-190 ℃, and the temperature of the machine head is 200-210 ℃ to obtain plastic granules;
(2) Adding the granules into an injection molding machine, and performing injection molding at 220-240 ℃ to form a plastic part; the injection pressure is 60 MPa; the nozzle temperature is 210 ℃;
(3) According to a CAD processing circuit diagram input into a 3D laser engraving machine in advance, irradiating a plastic workpiece for 0.2-0.3 second by using a German Lepucco company (LPKF) Fusion2000 laser with laser output power of 3-6W, laser wavelength of 1064nm and linear speed of 2000mm/s to perform three-dimensional laser engraving, and decomposing raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements on the surface of the plastic workpiece through the surface subjected to the high-energy laser engraving;
(4) Dipping the plastic part subjected to laser etching in sulfuric acid with the concentration of 60wt% for 30 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part to further increase the adhesive force of a metal coating;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 8-12 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ and the time is 20-25 min; and thirdly, nickel plating process, controlling the temperature at 80-81 ℃ for 5-10min, and forming a metallized pattern to obtain the radio frequency electronic component composite material with the three-dimensional circuit structure.
the composite material is respectively tested for mechanical property, thermal property and electrical property, and the test results are detailed in tables 2-4:
TABLE 2 mechanical Property test results
Table 3 thermal performance test results
table 4 electrical property test results
As can be seen from the test results of tables 2, 3, and 4: the composite material has the following outstanding performance advantages:
(1) Has very good toughness, and the elongation at break exceeds 90 percent;
(2) The thermal deformation temperature exceeds 120 ℃, and the process requirement of chemical nickel plating at the maximum temperature of 82 ℃ can be completely met;
(3) Has outstanding electrical properties, a dielectric constant of only 2.5, a loss tangent (1GHz) of only (1-2). times.10-3And is very beneficial to the transmission of high-frequency signals.
Examples 5 to 7
the composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate comprises the following raw materials in percentage by weight:
TABLE 5 raw material compositions and compounding ratios of examples 5 to 7
Said polypropylene copolymer (PPR) is translucent and is selected from the group consisting of ziphus EPS30R polypropylene products;
the basic copper phosphate (CuPO)4OH) is white powder with the particle size of 200nm-2μm;
The light calcium carbonate is white powder with the particle size of 1.5-20 mu m;
The rutile type titanium dioxide is white powder with the particle size of 1.5-3 mu m.
Example 8
A manufacturing method of a composite material for realizing a selective three-dimensional conductive layer on a flexible polymer substrate takes the raw materials in embodiment 7 as an example, and the manufacturing method comprises the following processing steps:
(1) mixing basic copper phosphate, light calcium carbonate, rutile type titanium dioxide, titanate coupling agent, magnesium sulfate, antioxidant 1010 and 168 in a high-speed mixer at the rotating speed of 300r/min for 5 minutes until powder materials are fully and uniformly mixed, and taking out for later use; putting the high-density polyethylene granules into a low-speed mixer with the rotating speed of 60r/min, adding silicone oil, stirring for 10 minutes, adding the mixed powder into a low-speed stirrer with the rotating speed of 60r/min, stirring for 30 minutes, and taking out for later use; adding the mixed raw materials into a double-screw extruder for extrusion granulation, controlling the rotating speed of a screw at 200r/min, and respectively controlling the operation temperature of each section as follows: the temperature of the first zone is 180-190 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 200-210 ℃, the temperature of the fourth zone is 200-210 ℃, the temperature of the fifth zone is 200-210 ℃, the temperature of the sixth zone is 200-210 ℃, the temperature of the seventh zone is 180-190 ℃, and the temperature of the machine head is 200-210 ℃ to obtain plastic granules;
(2) adding the granules into an injection molding machine, and performing injection molding at 220-240 ℃ to form a plastic part; the injection pressure is 60 MPa; the nozzle temperature is 210 ℃;
(3) irradiating a plastic part by using a laser of which the laser output power is 6-9W, the laser wavelength is 1064nm and the linear speed is 2000mm/s (LPKF) Fusion2000 laser of Germany Lepucco company (LPKF) for 0.2-0.3 second according to a CAD processing circuit diagram input into a 3D laser engraving machine in advance to perform three-dimensional laser engraving, and decomposing raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements on the surface of the plastic part through the surface subjected to the high-energy laser engraving;
(4) Immersing the laser-etched plastic part in sodium hydroxide with the concentration of 40wt% for 50 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 8-12 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ and the time is 20-25 min; and thirdly, nickel plating process, controlling the temperature at 80-81 ℃ for 5-10min, and forming a metallized pattern to obtain the radio frequency electronic component composite material with the three-dimensional circuit structure.
The composite material is respectively tested for mechanical property, thermal property and electrical property, and the test results are shown in tables 6-8:
TABLE 6 mechanical Property test results
Table 7 thermal performance test results
table 8 results of electrical property testing
from the test results in tables 6, 7, 8, the composite material has the following outstanding performance advantages:
(1) Compared with the embodiment 1, the composite material of the embodiment also has very good toughness, the elongation at break is more than 78 percent, and the addition of the rutile type whitening pigment reduces the toughness of the material, but the tensile strength and the modulus are improved;
(2) The thermal deformation temperature exceeds 90 ℃, and the process requirement of chemical nickel plating at the maximum temperature of 82 ℃ can be met;
(3) Has outstanding electrical properties, a dielectric constant of only 2.6, a loss tangent (1GHz) of only (2-3). times.10-3and is very beneficial to the transmission of high-frequency signals.
examples 9 to 11
the composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate comprises the following raw materials in percentage by weight:
TABLE 9 raw material compositions and compounding ratios of examples 9 to 11
said polypropylene copolymer (PPR) is translucent and is selected from the group consisting of ziphus EPS30R polypropylene products;
The basic copper phosphate (CuPO)4OH) is white powder with the particle size of 200nm-2μm;
The heavy calcium carbonate is white powder with the particle size of 1.5-20 mu m;
The rutile type titanium dioxide is white powder with the particle size of 1.5-3 mu m.
example 12
A method for manufacturing a composite material for realizing a selective three-dimensional conductive layer on a flexible polymer substrate, taking the raw materials in embodiment 9 as an example, the method comprises the following process steps:
(1) Mixing the combination of basic copper phosphate, light calcium carbonate, rutile type titanium dioxide, titanate coupling agent, perfluorooctanoic acid, antioxidant 1010 and 168 in a high-speed mixer at the rotating speed of 300r/min for 5 minutes until the powder materials are fully and uniformly mixed, and taking out for later use; putting the high-density polyethylene granules into a low-speed mixer with the rotating speed of 60r/min, adding liquid paraffin, stirring for 10 minutes, adding the mixed powder into a low-speed stirrer with the rotating speed of 60r/min, stirring for 30 minutes, and taking out for later use; adding the mixed raw materials into a double-screw extruder for extrusion granulation, controlling the rotating speed of a screw at 200r/min, and respectively controlling the operation temperature of each section as follows: the temperature of the first zone is 180-190 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 200-210 ℃, the temperature of the fourth zone is 200-210 ℃, the temperature of the fifth zone is 200-210 ℃, the temperature of the sixth zone is 200-210 ℃, the temperature of the seventh zone is 180-190 ℃, and the temperature of the machine head is 200-210 ℃ to obtain plastic granules;
(2) Adding the granules into an injection molding machine, and performing injection molding at 220-240 ℃ to form a plastic part; the injection pressure is 60 MPa; the nozzle temperature is 210 ℃;
(3) according to a CAD processing circuit diagram input into a 3D laser engraving machine in advance, irradiating a plastic workpiece for 0.2-0.3 second by using a German Lepucco company (LPKF) Fusion2000 laser with laser output power of 9-12W, laser wavelength of 1064nm and linear speed of 2000mm/s to perform three-dimensional laser engraving, and decomposing raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements on the surface of the plastic workpiece through the surface subjected to the high-energy laser engraving;
(4) dipping the plastic part subjected to laser etching in sulfuric acid with the concentration of 60wt% for 30 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 8-12 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ and the time is 20-25 min; and thirdly, nickel plating process, controlling the temperature at 80-81 ℃ for 5-10min, and forming a metallized pattern to obtain the radio frequency electronic component composite material with the three-dimensional circuit structure.
The composite material is respectively tested for mechanical property, thermal property and electrical property, and the test results are detailed in tables 10-12:
TABLE 10 mechanical Properties test results
TABLE 11 thermal Property test results
Table 12 results of electrical property testing
Test items Unit of Test standard Test results
Relative permittivity (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 the test results in tables 10, 11, 12, the composite material has the following outstanding performance advantages:
(1) compared with the embodiment 8, the composite material of the embodiment also has very good toughness, the elongation at break exceeds 78%, and the toughness of the material is reduced with the increase of the dosage of the coarsening agent;
(2) The thermal deformation temperature exceeds 90 ℃, and the process requirement of chemical nickel plating at the maximum temperature of 82 ℃ can be met;
(3) Has outstanding electrical properties, a dielectric constant of only 2.5 and a loss tangent (1GHz) of 1.0-2.0 × 10-3And is very beneficial to the transmission of high-frequency signals.
comparative example
In order to examine the influence of the inorganic coarsening agent on the adhesion of the coating of the plastic part after chemical plating, the comparative example uses the raw material composition and the proportion in the table 13 to manufacture the composite material, and compares the composite material with the composite material prepared in the example 9, the adhesion is detected according to the standard of ASTM D3359-97, and the test result is shown in the table 14:
TABLE 13 raw material composition and compounding ratio of comparative example and example 9
TABLE 14 comparison of adhesion of composites of comparative example and example 9
Detecting an object grade of adhesion
comparative example 1B
example 9 4B
As is apparent from tables 13 to 14, in example 9 in which 10% (minimum limit) of the inorganic roughening agent (in the case of heavy calcium carbonate) was added, the adhesion of the plated layer after electroless plating was significantly better than that of the comparative example in which no inorganic roughening agent was added, and the roughening agent exerted a very significant effect.
Examples 13 to 20
The compositions of the raw materials in weight ratio are detailed in the following table 15:
Raw materials example 13 Example 14 Example 15 Example 16 example 17 Example 18 Example 19 Example 20
polytetrafluoroethylene 55
thermoplastic elastomer 57.5
Polyurethane thermoplastic elastomer 56
Medium density polyethylene 60
Linear low density polyethylene 59
Glass fiber reinforced polypropylene 55.5
Ethylene-ethyl acrylate copolymer (EVA) 58.5
Ethylene-tetrafluoroethylene copolymer (ETFE) 57
Copper titanate 6 3
Copper phosphate 4 7 5
Acid form of copper hydrogen phosphate 1 8 5 10
Tin dioxide 6 5
Calcium carbonate
Calcium hydrogen phosphate 15 10
Calcium phosphate 20 10 15
Calcium sulfate 5 2 20
white carbon black 10 5
Kaolin clay 20 15 5
Talcum powder 20 15
pectin 0.5 0.8 0.3 1.1 0.2
Methyl cellulose 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
Combination of antioxidants 1010 and 168 0.5 0.8 0.6 0.9 0.7 0.5 1.0 1.0
liquid paraffin 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
Example 21
a method for manufacturing a composite material for realizing a selective three-dimensional conductive layer on a flexible polymer substrate, taking the raw materials in example 14 as an example, the method comprises the following process steps:
(1) mixing the raw materials in a mixer, and extruding and granulating by a double-screw extruder to obtain plastic granules; the extrusion process conditions were as follows: the screw rotation speed is controlled at 300r/min, preferably 200r/min, and the operating temperature of each section is respectively as follows: the temperature of a first area is 180-190 ℃, the temperature of a second area is 200-210 ℃, the temperature of a third area is 200-210 ℃, the temperature of a fourth area is 200-210 ℃, the temperature of a fifth area is 200-210 ℃, the temperature of a sixth area is 200-210 ℃, the temperature of a seventh area is 180-190 ℃, and the temperature of a machine head is 200-210 ℃;
(2) Adding the granules prepared in the step (1) into an injection molding machine to be molded into a plastic part by injection molding, wherein the injection molding temperature is 220-240 ℃; the injection pressure is 60 MPa; the nozzle temperature is 210 ℃;
(3) According to a CAD processing circuit diagram input into a 3D laser engraving machine in advance, irradiating a plastic workpiece for 0.2-0.3 second by using a German Lepucco company (LPKF) Fusion2000 laser with laser output power of 9-11W, laser wavelength of 1064nm and linear speed of 2000mm/s to perform three-dimensional laser engraving, and decomposing raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements on the surface of the plastic workpiece through the surface subjected to the high-energy laser engraving;
(4) Dipping the plastic part subjected to laser etching in sodium hydroxide with the concentration of 40wt% for 30 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 8 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ for 25 min; and thirdly, a nickel plating process is carried out, the temperature is controlled to be 80-81 ℃, the time is 5min, and a metallized pattern is formed, so that the radio frequency electronic component composite material with the three-dimensional circuit structure is obtained.
Example 22
A method for manufacturing a composite material for realizing a selective three-dimensional conductive layer on a flexible polymer substrate, taking the raw materials in example 16 as an example, the method comprises the following process steps:
(1) Mixing the raw materials in a mixer, and extruding and granulating by a double-screw extruder to obtain plastic granules; the extrusion process conditions were as follows: the rotating speed of the screw is controlled at 400r/min, and the operating temperature of each section is as follows: the temperature of a first area is 180-190 ℃, the temperature of a second area is 200-210 ℃, the temperature of a third area is 200-210 ℃, the temperature of a fourth area is 200-210 ℃, the temperature of a fifth area is 200-210 ℃, the temperature of a sixth area is 200-210 ℃, the temperature of a seventh area is 180-190 ℃, and the temperature of a machine head is 200-210 ℃;
(2) Adding the granules prepared in the step (1) into an injection molding machine to be molded into a plastic part by injection molding, wherein the injection molding temperature is 220-240 ℃; the injection pressure is 60 MPa; the nozzle temperature is 210 ℃;
(3) according to a CAD processing circuit diagram input into a 3D laser engraving machine in advance, irradiating a plastic workpiece for 0.2-0.3 second by using a German Lepucco company (LPKF) Fusion2000 laser with laser output power of 9-11W, laser wavelength of 1064nm and linear speed of 2000mm/s to perform three-dimensional laser engraving, and decomposing raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements on the surface of the plastic workpiece through the surface subjected to the high-energy laser engraving;
(4) Dipping the plastic part subjected to laser etching in potassium hydroxide with the concentration of 40wt% for 45 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part;
(5) placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 12 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ for 0 min; and thirdly, nickel plating process, controlling the temperature at 80-81 ℃ for 8min, and forming a metallized pattern to obtain the radio frequency electronic component composite material with the three-dimensional circuit structure.
example 23
A method for manufacturing a composite material for realizing a selective three-dimensional conductive layer on a flexible polymer substrate, taking the raw material in example 19 as an example, the method comprises the following process steps:
(1) mixing the raw materials in a mixer, and extruding and granulating by a double-screw extruder to obtain plastic granules; the extrusion process conditions were as follows: the rotating speed of the screw is controlled at 500r/min, and the operating temperature of each section is respectively as follows: the temperature of a first area is 180-190 ℃, the temperature of a second area is 200-210 ℃, the temperature of a third area is 200-210 ℃, the temperature of a fourth area is 200-210 ℃, the temperature of a fifth area is 200-210 ℃, the temperature of a sixth area is 200-210 ℃, the temperature of a seventh area is 180-190 ℃, and the temperature of a machine head is 200-210 ℃;
(2) Adding the granules prepared in the step (1) into an injection molding machine to be molded into a plastic part by injection molding, wherein the injection molding temperature is 220-240 ℃; the injection pressure is 60 MPa; the nozzle temperature is 210 ℃;
(3) Irradiating a plastic part by using a laser of which the laser output power is 7-12W, the laser wavelength is 1064nm and the linear speed is 2000mm/s (LPKF) Fusion2000 laser of Germany Lepucco company (LPKF) for 0.2-0.3 second according to a CAD processing circuit diagram input into a 3D laser engraving machine in advance to perform three-dimensional laser engraving, and decomposing raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements on the surface of the plastic part through the surface subjected to the high-energy laser engraving;
(4) dipping the plastic part subjected to laser etching in sulfuric acid with the concentration of 60wt% for 30 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 10 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ for 23 min; and thirdly, a nickel plating process is carried out, the temperature is controlled to be 80-81 ℃, the time is 10min, and a metallized pattern is formed, so that the radio frequency electronic component composite material with the three-dimensional circuit structure is obtained.
The composites of examples 21, 22 and 23 were tested for mechanical, thermal and electrical properties, respectively, and the results are detailed in Table 16.
TABLE 16 Properties of the composites of examples 21, 22, 23
from the test results in table 16, it can be seen that the composite material of the present invention has very good toughness, elongation at break exceeding 110%, and high tensile strength and modulus; the thermal deformation temperature exceeds 82 ℃, and the process requirement of chemical nickel plating at the maximum temperature of 82 ℃ can be met; has outstanding electrical performance, the dielectric constant is only 2.2, the loss factor (1GHz) is only 2.4E-3, and the transmission of high-frequency signals is greatly facilitated.

Claims (9)

1. The composite material for realizing the selective three-dimensional conducting layer on the flexible high polymer substrate is characterized in that: the raw materials comprise the following components in percentage by weight:
51.5-81 parts of polymer base material
5-10 parts of laser activator
10-30 parts of inorganic coarsening agent
0.2 to 1.2 portions of dispersant
0.3 to 1.6 portions of surface modifier
0.5 to 1.0 portion of antioxidant
0.5 to 1.0 portion of powder adhesive
0-10 parts of toner;
The inorganic coarsening agent is selected from one or a mixture of any two of light calcium carbonate, heavy calcium carbonate, calcium hydrophosphate, calcium phosphate, calcium sulfate, white carbon black, kaolin and talcum powder, and is powder with the particle size of 1.5-20 mu m;
The dispersing agent is selected from one of pectin, polyacrylamide, magnesium sulfate, perfluorooctanoic acid or methyl cellulose;
The powder adhesive is selected from silicone oil or liquid paraffin.
2. the composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate according to claim 1, wherein: the polymer base material has a dielectric constant epsilon = 1.9-2.5 and a dielectric loss tangent tg =1-3 xL 0-3The insulating polymer material of (2) is in the form of powder or granules; the polymer base material is selected from one of polypropylene copolymer, homo-polypropylene, polytetrafluoroethylene, thermoplastic elastomer, polyurethane thermoplastic elastomer, high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, ultrahigh-density polyethylene, glass fiber reinforced polypropylene, ethylene-ethyl acrylate copolymer or ethylene-tetrafluoroethylene copolymer.
3. The composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate according to claim 1, wherein: the laser activator is one or a mixture of any two of the following materials: copper chromite with a spinel structure, copper titanate with a perovskite structure, copper phosphate, copper hydrogen acid phosphate, copper hydroxide phosphate and tin dioxide.
4. The composite material for realizing a selective three-dimensional conductive layer on a flexible polymer substrate according to claim 1 or 3, wherein: the laser activator is copper chromite or basic copper phosphate powder, and the particle size is 200nm-2 mu m.
5. the composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate according to claim 1, wherein: the surface modifier is an alkoxy titanate coupling agent, and is specifically selected from one of Nanjing eosin chemical engineering, model numbers NDZ-101, NDZ-l02, NDZ-201, TC-l0l and TC-114.
6. The composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate according to claim 1, wherein: the antioxidant is selected from the group consisting of antioxidant 1010 and antioxidant 168.
7. The composite material for realizing the selective three-dimensional conductive layer on the flexible polymer substrate according to claim 1, wherein: the toner is selected from calcium sulfate, talcum powder, rutile type titanium dioxide or anatase type titanium dioxide.
8. the method of claim 1, wherein the method comprises the steps of: mixing the raw materials in a mixer, extruding and granulating by a double-screw extruder, injection molding, selectively performing three-dimensional laser etching on a three-dimensional laser etching device by using laser according to a circuit diagram of a CAD three-dimensional structure input in advance, decomposing the raw materials to form a metalized rough surface comprising pits and/or cavity structures containing metal elements, and decomposing the formed metal Cu2+and in the chemical plating process, copper deposition and thick copper are realized through the autocatalysis effect, and the radio frequency electronic component composite material with the three-dimensional circuit structure is formed.
9. the method according to claim 8, wherein the method comprises the steps of: the specific process steps are as follows:
(1) Mixing the raw materials in a mixer, and extruding and granulating by a double-screw extruder to obtain plastic granules; the extrusion process conditions were as follows: the rotating speed of the screw is controlled at 200-500r/min, and the operating temperature of each section is as follows: the temperature of a first area is 180-190 ℃, the temperature of a second area is 200-210 ℃, the temperature of a third area is 200-210 ℃, the temperature of a fourth area is 200-210 ℃, the temperature of a fifth area is 200-210 ℃, the temperature of a sixth area is 200-210 ℃, the temperature of a seventh area is 180-190 ℃, and the temperature of a machine head is 200-210 ℃;
(2) Adding the granules prepared in the step (1) into an injection molding machine to be injection molded into a plastic part; the injection temperature is 220-240 ℃, the injection pressure is 60MPa, and the nozzle temperature is 210 ℃;
(3) Putting the plastic part prepared in the step (2) into a clamp of three-dimensional laser etching equipment, and performing three-dimensional laser etching by using laser according to a CAD processing circuit diagram input into a 3D laser etching machine in advance; the laser output power is 3-12W, the laser wavelength is 1064nm, the laser etching time is 0.2-0.3s, and the linear velocity is 2000 mm/s;
(4) dipping the plastic part subjected to laser etching in acid or alkali for at least 30 minutes, and carrying out oil removal and surface roughening treatment on the surface of the plastic part to further increase the adhesive force of the metal coating;
(5) Placing the roughened plastic part into chemical copper plating chemical solution for chemical plating, wherein in the chemical plating, a first step copper deposition process is carried out, the temperature is controlled at 50-52 ℃, and the time is 8-12 min; the second step of thick copper process, the temperature is controlled at 60-65 ℃ and the time is 20-25 min; thirdly, nickel plating process, controlling the temperature at 80-81 ℃ for 5-10min, forming a metallized pattern, and obtaining the radio frequency electronic component composite material with the three-dimensional circuit structure;
In the step (3), the emitting light source of the laser is Nd-YAG, namely a neodymium-ytterbium aluminum garnet laser;
In the step (4), the acid is sulfuric acid with the concentration of 60 wt%; the alkali is sodium hydroxide with the concentration of 40wt% or potassium hydroxide with the concentration of 40 wt%.
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