CN111172521A - Method for metallizing surface of liquid crystal high molecular polymer - Google Patents
Method for metallizing surface of liquid crystal high molecular polymer Download PDFInfo
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- CN111172521A CN111172521A CN202010009453.6A CN202010009453A CN111172521A CN 111172521 A CN111172521 A CN 111172521A CN 202010009453 A CN202010009453 A CN 202010009453A CN 111172521 A CN111172521 A CN 111172521A
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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Abstract
The invention relates to a method for metallizing the surface of a liquid crystal high molecular polymer. The method comprises the following steps: pretreating a liquid crystal high molecular polymer matrix; immersing the pretreated liquid crystal high molecular polymer matrix into pre-roughening solution, stirring, and performing pre-roughening treatment; immersing the liquid crystal high molecular polymer matrix subjected to the pre-roughening treatment into roughening liquid, stirring, and roughening; carrying out post-treatment on the coarsened liquid crystal high molecular polymer matrix; the pre-coarsening liquid comprises a first solvent and a pre-coarsening agent with the concentration of 150g/L-650 g/L; the coarsening liquid comprises a second solvent and a coarsening agent with the concentration of 25ml/L-300 ml/L. The metal layer formed by the method has good adhesiveness with LCP matrix, no bubble is generated after baking for 1 hour at 260 ℃, no peeling is generated after the baking is carried out at the interval of 1mm in a check test, and no peeling phenomenon is generated after the glue is glued in the check.
Description
Technical Field
The invention relates to the field of plastic materials, in particular to a method for metalizing the surface of a liquid crystal high polymer.
Background
The liquid crystal high molecular polymer is LCP plastic material for short, is a novel high molecular material, has excellent heat resistance and forming processing performance, has an abnormal regular fibrous structure, special performance, high product strength, not inferior to metal and ceramic, has the advantages of good mechanical property, dimensional stability, optical property, electrical property, chemical resistance, flame retardance, processability, good heat resistance, lower thermal expansion coefficient and the like, and is widely applied to the fields of electronic, electric, optical fiber, automobile, space navigation and the like such as quick connectors, coils, switches, sockets, pump parts, valve parts, automobile fuel peripheral parts, containers for electronic furnaces and the like.
However, the liquid crystal polymer has excellent chemical resistance, and it is difficult to metallize the surface thereof by electroless plating. Moreover, the liquid crystal polymer and the metal conductor layer have insufficient adhesion or affinity, and most of the existing surface metallization processes of Liquid Crystal Polymer (LCP) materials are to implant metal on the surface of the LCP material, and then perform related solution-type electroplating or directly perform surface metallization by vacuum electroplating, which has two problems: firstly, the surface metallization cost is high, and secondly, the workpiece with a complex structure is difficult to carry out metallization treatment.
Disclosure of Invention
Based on the method, the metal layer formed by the method has good adhesion with an LCP substrate, no foaming exists when the LCP substrate is baked at 260 ℃ for 1 hour, no peeling exists when the LCP substrate is tested at a distance of 1mm, and no peeling phenomenon exists after the LCP substrate is glued. The method can be directly carried out in solution without planting metal on the surface of the LCP matrix material in advance, realizes the metallization of the surface of a workpiece with a complex structure, and reduces the manufacturing cost of the LCP material workpiece.
The specific technical scheme is as follows:
a method for metalizing the surface of a liquid crystal high polymer comprises the following steps:
pretreating a liquid crystal high molecular polymer matrix;
immersing the pretreated liquid crystal high molecular polymer matrix into pre-roughening solution, stirring, and performing pre-roughening treatment;
immersing the liquid crystal high molecular polymer matrix subjected to the pre-roughening treatment into roughening liquid, stirring, and roughening;
carrying out post-treatment on the coarsened liquid crystal high molecular polymer matrix;
the pre-coarsening liquid comprises a pre-coarsening agent with the concentration of 150g/L-650 g/L;
the coarsening liquid comprises a coarsening agent with the concentration of 25ml/L-300 ml/L.
Compared with the prior art, the invention has the following beneficial effects:
the method for metallizing the surface of the liquid crystal high molecular polymer carries out pre-roughening and roughening treatment on the pretreated liquid crystal high molecular polymer substrate. After pre-roughening treatment is carried out on the pre-roughening liquid with specific concentration, the pre-roughening liquid permeates into LCP gaps, fillers such as silicate and glass fibers and part of LCP are corroded to form a suitable rough surface, and a implantation place is provided for subsequent metal ion embedding. Meanwhile, coarsening treatment is carried out by coarsening liquid with specific concentration, LCP is further subjected to chain scission, groups such as ammonium salt, sulfonate, carboxyl or hydroxyl and the like are generated during chain scission, chemical adsorption groups are provided for subsequent metal adsorption, and finally the effect of improving the binding force between metal and LCP base material is achieved through close matching of the two process steps. The metal layer formed by the method has good adhesiveness with LCP matrix, no bubble is generated when the metal layer is baked at high temperature of 260 ℃, no peeling is generated when the space is tested by 1mm grid, and no peeling phenomenon is generated after the adhesion is tested by the grid. In addition, the method for metallizing the LCP surface does not need to plant metal on the surface of the LCP matrix material in advance, the whole process is carried out in solution, the metallizing of the surface of a workpiece with a complex structure can be realized, and the manufacturing cost of the LCP material workpiece is reduced.
Drawings
FIG. 1 is a schematic diagram of the Baige test of example 1;
FIG. 2 is a schematic diagram of the Baige test of example 2;
FIG. 3 is an enlarged view of the surface of the plating layer of example 3;
FIG. 4 is a schematic surface view of a fabricated LCP plastic part of comparative example 1;
FIG. 5 is a schematic of a hundred grid test of comparative example 2;
FIG. 6 is an enlarged view of the surface of the plating layer of comparative example 3;
fig. 7 is a schematic diagram of a comparative example 4-hundred grid test.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A method for metalizing the surface of a liquid crystal high polymer is characterized by comprising the following steps:
pretreating a liquid crystal high molecular polymer matrix;
immersing the pretreated liquid crystal high molecular polymer matrix into pre-roughening solution, stirring, and performing pre-roughening treatment;
immersing the liquid crystal high molecular polymer matrix subjected to the pre-roughening treatment into roughening liquid, stirring, and roughening;
carrying out post-treatment on the coarsened liquid crystal high molecular polymer matrix;
the pre-coarsening liquid comprises a pre-coarsening agent with the concentration of 150g/L-650 g/L;
the coarsening liquid comprises a coarsening agent with the concentration of 25ml/L-300 ml/L.
In some preferred embodiments, the pre-roughening solution comprises a pre-roughening agent having a concentration of 300g/L to 600 g/L;
the coarsening liquid comprises a coarsening agent with the concentration of 50ml/L-200 ml/L.
In some preferred embodiments, the pre-roughening solution comprises a pre-roughening agent having a concentration of 300g/L to 600g/L and water;
the coarsening liquid comprises a coarsening agent with the concentration of 50ml/L-200ml/L, sulfuric acid with the concentration of 50ml/L-300ml/L and water.
Preferably, the pre-coarsening agent is prepared from the following raw materials in percentage by weight:
50-80% of alkaline compound, 1-15% of oxidizing compound, 1-10% of fluoride, 1-15% of complexing agent and 0.1-10% of surfactant;
the alkaline compound is selected from one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide;
the oxidizing compound is selected from one or more of sodium persulfate, potassium persulfate, sodium perborate, potassium perborate, sodium hypochlorite and potassium hypochlorite;
the fluoride is selected from one or more of sodium fluoride, potassium fluoride, sodium hydrogen fluoride, potassium hydrogen fluoride, ammonium hydrogen fluoride, fluoborate and ammonium fluoride;
the complexing agent is selected from one or more of EDTA, citrate, polyethylene polyamine and organic phosphonate;
the surfactant is selected from one or more of dodecyl benzene sulfonate, dodecyl sulfate, dodecyl benzene sulfate, alkyl polyoxyethylene ether, naphthalene sulfonic acid formaldehyde polymer, polyethylene glycol, fatty glyceride, fatty sorbitan ester, polysorbate and the like.
The coarsening agent is selected from one or more of aqueous solution of hydrogen peroxide, aqueous solution of permanganate, aqueous solution of persulfate and aqueous solution of perborate.
As can be appreciated, the concentration of solute in the coarsening agent is 400 to 800 g/L.
Preferably, the pre-coarsening agent is an SF-LCP pre-coarsening agent which can be purchased from New Material science and technology, Inc. of Guangzhou Sanfu; the coarsening agent is an SF-LCP coarsening agent which can be purchased from Guangzhou Sanfu new material science and technology GmbH.
In some preferred embodiments, the temperature of the pre-roughening treatment is 50-90 ℃, and the treatment time is 2-20 min;
the temperature of the roughening treatment is 25-55 ℃, and the treatment time is 2-20 min.
Preferably, the agitation treatment is mechanical agitation or sonication.
After the pre-coarsening treatment is carried out on the liquid crystal high polymer base material after the pre-treatment by the pre-coarsening liquid with specific concentration, the pre-coarsening liquid permeates into LCP gaps, and then fillers such as silicate, glass fiber and the like and part of LCP are corroded to form a suitable rough surface, thereby providing a landing place for the subsequent metal ion inlaying. Meanwhile, coarsening treatment is carried out by coarsening liquid with specific concentration, LCP is further subjected to chain scission, groups such as ammonium salt, sulfonate, carboxyl or hydroxyl and the like are generated during chain scission, chemical adsorption groups are provided for subsequent metal adsorption, and finally the effect of improving the binding force between metal and LCP base material is achieved through close matching of the two process steps.
As can be appreciated, the step of pre-processing includes:
carrying out oil removal treatment on the liquid crystal high polymer matrix;
carrying out bulking treatment on the deoiled liquid crystal high molecular polymer matrix;
and carrying out hydrophilic treatment on the bulked liquid crystal high polymer matrix.
In some preferred embodiments, the step of degreasing comprises:
and immersing the liquid crystal high polymer matrix into deoiling liquid, wherein the treatment temperature is 10-60 ℃, and the treatment time is 2-20 min.
The deoiling liquid comprises a solvent, acid with the concentration of 30ml/L-400ml/L and a deoiling agent with the concentration of 10ml/L-100 ml/L.
It can be understood that, when the oil removing treatment is performed, a treatment mode of soaking, mechanical stirring while soaking, or ultrasonic treatment while soaking can be adopted.
Preferably, the degreasing fluid comprises water, concentrated sulfuric acid with the concentration of 30ml/L-400ml/L and SF-LCP degreasing agent with the concentration of 10ml/L-100 ml/L.
The SF-LCP degreasing agent is prepared by compounding a complexing agent, an emulsifier, a penetrating agent, an adsorbent, an oil-in-water type surfactant and water, and can be purchased from Guangzhou Sanfu new material science and technology GmbH. The acid cleaning agent is matched with acid for use, so that oil stains such as release agent, sweat stain, putty and the like on the surface of the LCP substrate can be removed, and the surface of the LCP substrate is exposed.
It is understood that after the oil removal, the next process is performed after the oil is cleaned by flowing water, and a clean surface is provided for the next process.
In some preferred embodiments, the step of leavening comprises:
and immersing the deoiled liquid crystal high molecular polymer into swelling liquid, wherein the treatment temperature is 40-80 ℃, and the treatment time is 2-20 min.
The leavening liquid comprises a solvent and a leavening agent with the concentration of 100ml/L-500 ml/L.
It is understood that the puffing treatment may be carried out by soaking, mechanical stirring while soaking, or ultrasonic treatment while soaking.
Preferably, the leavening liquid comprises water and SF-DC01 leavening agent with a concentration of 100ml/L to 500 ml/L.
The SF-DC01 leavening agent is available from Guangzhou Sanfu New Material science and technology GmbH.
The swelling treatment can swell, soften and remove glue residue and corrosion on the surface of the LCP substrate, and provides an expanded surface for the subsequent pre-roughening and roughening procedures of the LCP substrate.
It will be appreciated that after the leavening process has been completed, the next process step is performed after rinsing with a running water rinse to provide a clean surface for the next process step.
In some preferred embodiments, the step of hydrophilizing comprises:
immersing the bulked liquid crystal high molecular polymer into hydrophilic liquid, wherein the treatment temperature is 40-80 ℃, and the treatment time is 2-20 min.
The hydrophilic liquid comprises a solvent and a hydrophilic agent with the concentration of 100ml/L-500 ml/L.
It is understood that the hydrophilic treatment may be carried out by soaking, mechanical stirring while soaking, or ultrasonic treatment while soaking.
Preferably, the hydrophilic liquid comprises water and an SF-LCP hydrophilic agent at a concentration of 100ml/L to 500 ml/L.
The SF-LCP hydrophilizing agent can be purchased from Guangzhou Sanfu new material science and technology GmbH.
The swelling agent on the LCP substrate can be removed by hydrophilic treatment, and the hydrophilic agent is remained on the surface of the substrate, so that the substrate is hydrophilic, the hydrophilic LCP substrate surface is provided for the subsequent pre-roughening procedure, and the pre-roughening solution can conveniently permeate into gaps on the surface of the substrate.
It is understood that after the hydrophilic treatment is finished, the surface is cleaned by flowing water and then the next process is performed to provide a clean surface for the next process.
It will be appreciated that the post-processing step comprises:
pre-dipping the coarsened liquid crystal high molecular polymer matrix;
performing activation treatment on the liquid crystal high polymer matrix subjected to the pre-soaking treatment;
performing dispergation treatment on the activated liquid crystal high polymer matrix;
and chemically plating the dispergated liquid crystal high molecular polymer matrix.
In some preferred embodiments, the step of pre-dipping comprises:
and immersing the coarsened liquid crystal high molecular polymer into the pre-immersion liquid, wherein the treatment temperature is 15-45 ℃, and the treatment time is 1-10 min.
Preferably, the pre-immersion liquid is hydrochloric acid aqueous solution with the concentration of 200ml/L-450 ml/L.
It is understood that the pre-dipping treatment may be performed by dipping, mechanical stirring while dipping, or ultrasonic treatment while dipping.
The presoaking treatment can discharge coarsening liquid in LCP gaps, convert generated amine salt into hydrochloric acid amine salt, convert generated sulfonate and carboxylate into sulfonic acid and carboxylic acid, prevent impurities from being brought into the subsequent activation process, and prolong the service life of activation.
It is understood that after the pre-dip treatment is finished, the flow water is used for cleaning, and then the next process is carried out, so that a clean surface is provided for the next process.
In some preferred embodiments, the step of activating treatment comprises:
and immersing the liquid crystal high molecular polymer matrix subjected to the pre-soaking treatment into a palladium activating solution, wherein the treatment temperature is 25-45 ℃, and the treatment time is 1-10 min.
The palladium activating solution comprises a solvent, hydrochloric acid with the concentration of 200ml/L-450ml/L, stannous chloride with the concentration of 1g/L-10g/L and a palladium activating agent with the concentration of 2ml/L-50 ml/L.
It is understood that the activation treatment may be carried out by soaking, mechanical stirring while soaking, or ultrasonic treatment while soaking.
Preferably, the palladium activating solution comprises water, hydrochloric acid with the concentration of 200ml/L-450ml/L, stannous chloride with the concentration of 1g/L-10g/L and SF-636 palladium activating agent with the concentration of 2ml/L-50 ml/L.
The SF-636 palladium activator is commercially available from Guangzhou Sanfu New Material science and technology, Inc.
During the activation treatment, the colloid palladium is implanted and adsorbed on the rough and active surface formed by pre-roughening and roughening so as to provide catalytic active substances and crystal nuclei for subsequent metal deposition.
It will be appreciated that after the activation is completed, the next process is performed after the substrate is cleaned by running water to provide a clean surface for the next process.
In some preferred embodiments, the step of disperging comprises:
and immersing the activated liquid crystal high molecular polymer matrix into a degumming solution, wherein the treatment temperature is 25-45 ℃, and the treatment time is 20-180 s.
The dispergation liquid comprises a solvent and dispergation salt with the concentration of 50g/L-200g/L
It can be understood that the degumming treatment may be performed by soaking, mechanical stirring while soaking, or ultrasonic treatment while soaking.
Preferably, the dispergation solution comprises water and SF-639 dispergation salt at a concentration of 50g/L to 200 g/L.
The SF-639 debonder salt is available from Guangzhou Sanfu New Material science and technology, Inc.
During the peptizing treatment, the bivalent tin colloid layer around the colloid palladium is removed, and palladium atoms are exposed to become a catalytic core and a crystal nucleus for the subsequent metal deposition.
It can be understood that after the dispergation treatment is finished, the next process is performed after the dispergation treatment is cleaned by flowing water, and a clean surface is provided for the next process.
In some preferred embodiments, the step of electroless plating includes:
and immersing the dispergated liquid crystal high molecular polymer substrate into plating solution, adjusting the pH value to 9-13, and treating at 30-50 ℃ for 20-40 min.
The plating solution is selected from at least one of a copper-containing plating solution, a nickel-containing plating solution, a silver-containing plating solution and a gold-containing plating solution.
It is understood that the electroless plating may be carried out by mechanical stirring.
In the chemical plating process, metal ions in the plating solution are reduced to metal atoms on palladium atomic nuclei under the catalytic action of the palladium atoms, and the metal atoms continuously grow in formed crystal nuclei, and finally a metal layer is formed on the surface of the LCP substrate. The LCP can also play a role in providing conductors and adsorption points for subsequent plating of other metal coatings, and the performances of conductivity, welding and the like of the LCP are improved.
Preferably, the plating solution is a copper plating solution and comprises a solvent, an electroless copper plating metal supplement with the concentration of 30ml/L-100ml/L and an electroless copper plating cylinder opener with the concentration of 100ml/L-300 ml/L.
Further preferably, the plating solution comprises water, SF-DC161A electroless copper plating metal supplement with the concentration of 30ml/L-100ml/L, and SF-DC161M electroless copper plating bath opener with the concentration of 100ml/L-300 ml/L.
The SF-DC161A electroless copper metal supplement is available from Sanfu New materials science and technology, Inc., Guangzhou.
The SF-DC161M electroless copper plating jar opener is available from Guangzhou Sanfu New Material science and technology, Inc.
The following is a further description with reference to specific examples.
Example 1
The present embodiment provides a method for surface metallization of LCP, which includes the following steps:
oil removal: immersing an LCP substrate into degreasing liquid, and mechanically stirring for 10min at 40 ℃, wherein the degreasing liquid comprises a proper amount of water and 50ml/L of sulfuric acid 200ml/L, SF-LCP degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, standing and soaking for 10min at 60 ℃, wherein the leavening liquid comprises a proper amount of water and 300ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, and mechanically stirring at 60 ℃ for 10min, wherein the hydrophilic liquid comprises a proper amount of water and 300ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Pre-coarsening: immersing the LCP substrate subjected to hydrophilic treatment into pre-roughening solution, and carrying out ultrasonic treatment for 10min at 80 ℃, wherein the pre-roughening solution comprises a proper amount of water and 450g/L of SF-LCP pre-roughening agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the pre-coarsening-treated LCP substrate into coarsening liquid, and mechanically stirring the substrate for 10min at the temperature of 45 ℃, wherein the coarsening liquid comprises a proper amount of water and 200ml/L, SF of sulfuric acid-200 ml/L of LCP coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: immersing the coarsened LCP substrate into a hydrochloric acid aqueous solution with the concentration of 350ml/L, standing and immersing for 3min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 5min at 35 ℃, wherein the palladium activating solution comprises a proper amount of water, 350ml/L of hydrochloric acid, 5g/L of stannous chloride and 10ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 100g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 160ml/L of SF-DC161A electroless copper plating metal supplement agent 60ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
The LCP plastic parts with copper layers obtained above were baked at 260 ℃ for 1 hour, and no blistering was observed.
The LCP parts with copper layers produced above were subjected to a hundred grid test, the test results being shown in figure 1. It is observed that the test of the grid interval of 1mm has no peeling, and the viscose glue after the grid interval has no peeling.
Example 2
This example provides a method for surface metallization of LCP, which is different from example 1 in that the process parameters of degreasing, bulking, hydrophilic, pre-roughening, pre-dipping, activating, dispergating and electroless plating are different from example 1, and the specific steps are as follows:
oil removal: immersing the LCP substrate into degreasing liquid, and carrying out ultrasonic treatment for 8min at 30 ℃, wherein the degreasing liquid comprises a proper amount of water and 150ml/L, SF-100 ml/L sulfuric acid degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, and carrying out ultrasonic treatment for 5min at 50 ℃, wherein the leavening liquid contains a proper amount of water and 350ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, standing and soaking for 10min at 60 ℃, wherein the hydrophilic liquid comprises a proper amount of water and 400ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Pre-coarsening: immersing the LCP substrate subjected to hydrophilic treatment into pre-roughening solution, and carrying out ultrasonic treatment for 5min at 80 ℃, wherein the pre-roughening solution comprises a proper amount of water and 550g/L of SF-LCP pre-roughening agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the pre-coarsening-treated LCP substrate into coarsening liquid, and mechanically stirring the substrate for 10min at 55 ℃, wherein the coarsening liquid comprises a proper amount of water and 100ml/L, SF-50 ml/L of sulfuric acid-LCP coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: the coarsened LCP substrate is immersed into a hydrochloric acid aqueous solution with the concentration of 200ml/L and mechanically stirred for 5min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 8min at the temperature of 30 ℃, wherein the palladium activating solution comprises a proper amount of water, 300ml/L of hydrochloric acid, 3g/L of stannous chloride and 20ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 150g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 150ml/L of SF-DC161A electroless copper plating metal supplement agent 50ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
The LCP plastic parts with copper layers obtained above were baked at 260 ℃ for 1 hour, and no blistering was observed.
The LCP parts with copper layers produced above were subjected to a hundred grid test, the test results being shown in figure 2. It is observed that the test of the grid interval of 1mm has no peeling, and the viscose glue after the grid interval has no peeling.
Example 3
This example provides a method for surface metallization of LCP, which is different from example 2 in that the concentrations of the pre-coarsening agent and the coarsening agent are different from example 2, and the specific steps are as follows:
oil removal: immersing the LCP substrate into degreasing liquid, and carrying out ultrasonic treatment for 8min at 30 ℃, wherein the degreasing liquid comprises a proper amount of water and 150ml/L, SF-100 ml/L sulfuric acid degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, and carrying out ultrasonic treatment for 5min at 50 ℃, wherein the leavening liquid contains a proper amount of water and 350ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, standing and soaking for 10min at 60 ℃, wherein the hydrophilic liquid comprises a proper amount of water and 400ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Pre-coarsening: immersing the LCP substrate subjected to hydrophilic treatment into pre-roughening solution, and carrying out ultrasonic treatment for 5min at 80 ℃, wherein the pre-roughening solution comprises a proper amount of water and 350g/L of SF-LCP pre-roughening agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the pre-coarsening-treated LCP substrate into coarsening liquid, and mechanically stirring the substrate for 10min at 55 ℃, wherein the coarsening liquid comprises a proper amount of water and 300ml/L, SF-160 ml/L of sulfuric acid as a coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: the coarsened LCP substrate is immersed into a hydrochloric acid aqueous solution with the concentration of 200ml/L and mechanically stirred for 5min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 8min at the temperature of 30 ℃, wherein the palladium activating solution comprises a proper amount of water, 300ml/L of hydrochloric acid, 3g/L of stannous chloride and 20ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 150g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 150ml/L of SF-DC161A electroless copper plating metal supplement agent 50ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
The enlarged surface of the plating layer of the LCP plastic part with the copper layer is shown in figure 3, and as can be seen from figure 3, grooves are left at the positions of the original glass fibers, which shows that the glass fibers on the LCP substrate are processed, and the plating effect is good.
Comparative example 1
The comparative example provides a method for surface metallization of LCP, which is different from the example 2 in that the process parameters of pre-roughening and roughening are different from the example 2, and the specific steps are as follows:
oil removal: immersing the LCP substrate into degreasing liquid, and carrying out ultrasonic treatment for 8min at 30 ℃, wherein the degreasing liquid comprises a proper amount of water and 150ml/L, SF-100 ml/L sulfuric acid degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, and carrying out ultrasonic treatment for 5min at 50 ℃, wherein the leavening liquid contains a proper amount of water and 350ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, standing and soaking for 10min at 60 ℃, wherein the hydrophilic liquid comprises a proper amount of water and 400ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Pre-coarsening: immersing the LCP substrate subjected to hydrophilic treatment into pre-roughening solution, standing and immersing for 20min at 80 ℃, wherein the pre-roughening solution comprises a proper amount of water and 120g/L of SF-LCP pre-roughening agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the pre-coarsened LCP substrate into coarsening liquid, and mechanically stirring the substrate for 20min at 55 ℃, wherein the coarsening liquid comprises a proper amount of water and 50ml/L, SF-20 ml/L of sulfuric acid coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: the coarsened LCP substrate is immersed into a hydrochloric acid aqueous solution with the concentration of 200ml/L and mechanically stirred for 5min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 8min at the temperature of 30 ℃, wherein the palladium activating solution comprises a proper amount of water, 300ml/L of hydrochloric acid, 3g/L of stannous chloride and 20ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 150g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 150ml/L of SF-DC161A electroless copper plating metal supplement agent 50ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
The LCP plastic parts with copper layers produced as described above showed significant flaking after electroless copper plating, as shown in FIG. 4. It is noted that the pre-roughening and roughening processes described above do not successfully metallize the LCP surface. The selection of the parameters of the pre-roughening process and the roughening process plays a very important role in determining whether the LCP surface can be successfully metalized.
Comparative example 2
The comparative example provides a method for surface metallization of LCP, which is different from the example 2 in that the process parameters of pre-roughening and roughening are different from the example 2, and the specific steps are as follows:
oil removal: immersing the LCP substrate into degreasing liquid, and carrying out ultrasonic treatment for 8min at 30 ℃, wherein the degreasing liquid comprises a proper amount of water and 150ml/L, SF-100 ml/L sulfuric acid degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, and carrying out ultrasonic treatment for 5min at 50 ℃, wherein the leavening liquid contains a proper amount of water and 350ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, standing and soaking for 10min at 60 ℃, wherein the hydrophilic liquid comprises a proper amount of water and 400ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Pre-coarsening: immersing the LCP substrate subjected to hydrophilic treatment into pre-roughening solution, standing and immersing for 3min at 80 ℃, wherein the pre-roughening solution comprises a proper amount of water and 150g/L of SF-LCP pre-roughening agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the pre-coarsened LCP substrate into coarsening liquid, standing and soaking for 3min at 55 ℃, wherein the coarsening liquid comprises a proper amount of water and 100ml/L, SF-60 ml/L sulfuric acid as a coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: the coarsened LCP substrate is immersed into a hydrochloric acid aqueous solution with the concentration of 200ml/L and mechanically stirred for 5min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 8min at the temperature of 30 ℃, wherein the palladium activating solution comprises a proper amount of water, 300ml/L of hydrochloric acid, 3g/L of stannous chloride and 20ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 150g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 150ml/L of SF-DC161A electroless copper plating metal supplement agent 50ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
The LCP plastic parts with copper layers obtained above were baked at 260 ℃ for 1 hour, and no blistering was observed.
The LCP parts with copper layers produced above were subjected to a hundred grid test, the test results being shown in figure 5. Slight peeling was observed after hundred grids in the viscose test. It is shown that when the concentrations of the pre-coarsening agent and the coarsening agent in the pre-coarsening treatment process and the coarsening treatment process are low, if the pre-coarsening agent and the coarsening agent are only stood for soaking, the adhesion between the subsequent LCP base material and the metal plating layer is also influenced to a certain extent.
Comparative example 3
The comparative example provides a method for surface metallization of LCP, which is different from the method in example 3 in that the process parameters of pre-roughening and roughening are different from those in example 3, and the specific steps are as follows:
oil removal: immersing the LCP substrate into degreasing liquid, and carrying out ultrasonic treatment for 8min at 30 ℃, wherein the degreasing liquid comprises a proper amount of water and 150ml/L, SF-100 ml/L sulfuric acid degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, and carrying out ultrasonic treatment for 5min at 50 ℃, wherein the leavening liquid contains a proper amount of water and 350ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, standing and soaking for 10min at 60 ℃, wherein the hydrophilic liquid comprises a proper amount of water and 400ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Pre-coarsening: immersing the LCP substrate subjected to hydrophilic treatment into pre-roughening solution, standing and immersing for 20min at 80 ℃, wherein the pre-roughening solution comprises a proper amount of water and 150g/L of SF-LCP pre-roughening agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the pre-coarsened LCP substrate into coarsening liquid, standing and soaking for 20min at 55 ℃, wherein the coarsening liquid comprises a proper amount of water and 100ml/L, SF-60 ml/L sulfuric acid as a coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: the coarsened LCP substrate is immersed into a hydrochloric acid aqueous solution with the concentration of 200ml/L and mechanically stirred for 5min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 8min at the temperature of 30 ℃, wherein the palladium activating solution comprises a proper amount of water, 300ml/L of hydrochloric acid, 3g/L of stannous chloride and 20ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 150g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 150ml/L of SF-DC161A electroless copper plating metal supplement agent 50ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
The enlarged surface of the coating of the LCP plastic part with the copper layer is shown in FIG. 6, and comparing with FIGS. 3 and 6, it can be seen that the glass fibers on the LCP substrate in FIG. 6 are not treated (the straight line with green light is the glass fibers), and the subsequent continuous metal plating has the undesirable phenomena of foaming and the like.
Comparative example 4
The comparative example provides a method for metallizing the surface of LCP, which is different from the method in example 1 in that the pre-roughening treatment is not carried out, and the roughening treatment is directly carried out after the hydrophilic treatment, and the specific steps are as follows:
oil removal: immersing an LCP substrate into degreasing liquid, and mechanically stirring for 10min at 40 ℃, wherein the degreasing liquid comprises a proper amount of water and 50ml/L of sulfuric acid 200ml/L, SF-LCP degreasing agent. And (5) entering the next working procedure after cleaning.
Bulking: immersing the deoiled LCP substrate into a leavening liquid, standing and soaking for 10min at 60 ℃, wherein the leavening liquid comprises a proper amount of water and 300ml/L of SF-DC01 leavening agent. And (5) entering the next working procedure after cleaning.
And (3) hydrophilic: immersing the bulked LCP substrate into hydrophilic liquid, and mechanically stirring at 60 ℃ for 10min, wherein the hydrophilic liquid comprises a proper amount of water and 300ml/L of SF-LCP hydrophilic agent. And (5) entering the next working procedure after cleaning.
Coarsening: immersing the LCP substrate subjected to hydrophilic treatment into a roughening solution, and mechanically stirring for 10min at 45 ℃, wherein the roughening solution comprises a proper amount of water and 200ml/L, SF-200 ml/L sulfuric acid-LCP coarsening agent. And (5) entering the next working procedure after cleaning.
Pre-dipping: immersing the coarsened LCP substrate into a hydrochloric acid aqueous solution with the concentration of 350ml/L, standing and immersing for 3min at the temperature of 35 ℃. And (5) entering the next working procedure after cleaning.
And (3) activation: immersing the LCP substrate after the pre-dipping treatment into a palladium activating solution, and mechanically stirring for 5min at 35 ℃, wherein the palladium activating solution comprises a proper amount of water, 350ml/L of hydrochloric acid, 5g/L of stannous chloride and 10ml/L of SF-636 palladium activating agent. And (5) entering the next working procedure after cleaning.
And (3) gel releasing: and (3) immersing the activated LCP substrate into dispergation liquid, and slowly and mechanically stirring for 30s at 35 ℃, wherein the dispergation liquid contains a proper amount of water and 100g/L of SF-639 dispergation salt. And (5) entering the next working procedure after cleaning.
Chemical copper plating: and immersing the peptized LCP substrate into a plating solution, and stirring for 30min at 40 ℃, wherein the plating solution contains a proper amount of water and 160ml/L of SF-DC161A electroless copper plating metal supplement agent 60ml/L, SF-DC161M electroless copper plating bath opener, so that the surface metallization of the LCP substrate is completed.
As shown in figure 7, the LCP plastic part prepared by the process has a white original color of the LCP substrate, and as can be seen from figure 7, a large white area still exists on the LCP plastic part, which indicates that the area is not successfully plated with a copper layer and indicates that the pre-roughening treatment has an important influence on whether the surface metallization of the LCP substrate is finished.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for metalizing the surface of a liquid crystal high polymer is characterized by comprising the following steps:
pretreating a liquid crystal high molecular polymer matrix;
immersing the pretreated liquid crystal high molecular polymer matrix into pre-roughening solution, stirring, and performing pre-roughening treatment;
immersing the liquid crystal high molecular polymer matrix subjected to the pre-roughening treatment into roughening liquid, stirring, and roughening;
carrying out post-treatment on the coarsened liquid crystal high molecular polymer matrix;
the pre-coarsening liquid comprises a pre-coarsening agent with the concentration of 150g/L-650 g/L;
the coarsening liquid comprises a coarsening agent with the concentration of 25ml/L-300 ml/L.
2. The method for metallizing the surface of a liquid crystal high molecular polymer according to claim 1, wherein the pre-roughening solution comprises a pre-roughening agent in a concentration of 300g/L to 600g/L and water;
the coarsening liquid comprises a coarsening agent with the concentration of 50ml/L-200ml/L, sulfuric acid with the concentration of 50ml/L-300ml/L and water.
3. The method for metallizing the surface of a liquid crystal high molecular polymer according to claim 1, wherein the pre-roughening agent is prepared from the following raw materials in percentage by weight:
50-80% of alkaline compound, 1-15% of oxidizing compound, 1-10% of fluoride, 1-15% of complexing agent and 0.1-10% of surfactant;
the alkaline compound is selected from one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide;
the oxidizing compound is selected from one or more of sodium persulfate, potassium persulfate, sodium perborate, potassium perborate, sodium hypochlorite and potassium hypochlorite;
the fluoride is selected from one or more of sodium fluoride, potassium fluoride, sodium hydrogen fluoride, potassium hydrogen fluoride, ammonium hydrogen fluoride, fluoborate and ammonium fluoride;
the complexing agent is selected from one or more of EDTA, citrate, polyethylene polyamine and organic phosphonate;
the surfactant is selected from one or more of dodecyl benzene sulfonate, dodecyl sulfate, dodecyl benzene sulfate, alkyl polyoxyethylene ether, naphthalene sulfonic acid formaldehyde polymer, polyethylene glycol, fatty glyceride, fatty sorbitan ester, polysorbate and the like.
4. The method for metallizing the surface of a liquid crystal high molecular polymer according to claim 1, wherein the roughening agent is one or more selected from the group consisting of an aqueous solution of hydrogen peroxide, an aqueous solution of permanganate, an aqueous solution of persulfate, and an aqueous solution of perborate.
5. The method for metallizing the surface of a liquid crystal high molecular polymer according to claim 1, wherein the temperature of the pre-roughening treatment is 50-90 ℃ and the treatment time is 2-20 min;
the temperature of the roughening treatment is 25-55 ℃, and the treatment time is 2-20 min.
6. The method for metallizing the surface of a liquid crystal polymer according to any one of claims 1 to 5, wherein the pretreatment comprises:
carrying out oil removal treatment on the liquid crystal high polymer matrix;
carrying out bulking treatment on the deoiled liquid crystal high molecular polymer matrix;
and carrying out hydrophilic treatment on the bulked liquid crystal high polymer matrix.
7. The method for metallizing the surface of a liquid crystal polymer according to claim 6, wherein the step of degreasing comprises: immersing the liquid crystal high molecular polymer matrix into deoiling liquid, wherein the treatment temperature is 10-60 ℃, and the treatment time is 2-20 min; the deoiling liquid comprises a solvent, acid with the concentration of 30ml/L-400ml/L and a deoiling agent with the concentration of 10ml/L-100 ml/L; and/or the presence of a catalyst in the reaction mixture,
the step of leavening comprises: immersing the deoiled liquid crystal high molecular polymer into swelling liquid, wherein the treatment temperature is 40-80 ℃, and the treatment time is 2-20 min; the leavening liquid comprises a solvent and a leavening agent with the concentration of 100ml/L-500 ml/L; and/or the presence of a catalyst in the reaction mixture,
the hydrophilic treatment step comprises: immersing the bulked liquid crystal high molecular polymer into a hydrophilic liquid, wherein the treatment temperature is 40-80 ℃, and the treatment time is 2-20 min; the hydrophilic liquid comprises a solvent and a hydrophilic agent with the concentration of 100ml/L-500 ml/L.
8. The method for metallizing the surface of a liquid crystal polymer according to any one of claims 1 to 5, wherein the post-treatment comprises:
pre-dipping the coarsened liquid crystal high molecular polymer matrix;
performing activation treatment on the liquid crystal high polymer matrix subjected to the pre-soaking treatment;
performing dispergation treatment on the activated liquid crystal high polymer matrix;
and chemically plating the dispergated liquid crystal high molecular polymer matrix.
9. The method for metallizing the surface of a liquid crystal polymer according to claim 8, wherein the pre-dipping step comprises: immersing the coarsened liquid crystal high molecular polymer into hydrochloric acid water solution with the concentration of 200ml/L-450ml/L, wherein the treatment temperature is 15-45 ℃, and the treatment time is 1min-10 min; and/or the presence of a catalyst in the reaction mixture,
the step of activating treatment comprises: immersing the liquid crystal high molecular polymer matrix subjected to the pre-soaking treatment in a palladium activating solution, wherein the treatment temperature is 25-45 ℃, and the treatment time is 1-10 min; the palladium activating solution comprises a solvent, hydrochloric acid with the concentration of 200ml/L-450ml/L, stannous chloride with the concentration of 1g/L-10g/L and a palladium activating agent with the concentration of 2ml/L-50 ml/L; and/or the presence of a catalyst in the reaction mixture,
the step of dispergation treatment comprises the following steps: immersing the activated liquid crystal high molecular polymer into a degumming solution, wherein the treatment temperature is 25-45 ℃, and the treatment time is 20-180 s; the dispergation liquid comprises a solvent and dispergation salt with the concentration of 50g/L-200 g/L; and/or the presence of a catalyst in the reaction mixture,
the electroless plating step comprises: immersing the dispergated liquid crystal high molecular polymer substrate into plating solution, adjusting the pH value to 9-13, the treatment temperature to 30-50 ℃, and the treatment time to 20-40 min; the plating solution is selected from at least one of a copper-containing plating solution, a nickel-containing plating solution, a silver-containing plating solution and a gold-containing plating solution.
10. The method for metallizing the surface of a liquid crystal high molecular polymer as recited in claim 9, wherein said plating solution comprises a solvent and an electroless copper metal replenisher at a concentration of 30ml/L to 100ml/L, an electroless copper opener at a concentration of 100ml/L to 300 ml/L.
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| CN105839106A (en) * | 2016-05-27 | 2016-08-10 | 宣城托新表面处理有限公司 | Refined surface treatment technology for automotive decorative part |
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| CN105839106A (en) * | 2016-05-27 | 2016-08-10 | 宣城托新表面处理有限公司 | Refined surface treatment technology for automotive decorative part |
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