CN103525154B - A kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper and technique - Google Patents
A kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper and technique Download PDFInfo
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- CN103525154B CN103525154B CN201310454344.5A CN201310454344A CN103525154B CN 103525154 B CN103525154 B CN 103525154B CN 201310454344 A CN201310454344 A CN 201310454344A CN 103525154 B CN103525154 B CN 103525154B
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Abstract
A kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper and technique, the present invention relates to a kind of surface of plastic matrix process coating used and utilize it to carry out surface-treated method, the present invention will solve existing employing paint method to make plastic workpiece surface having have the technical problem of lack of homogeneity of the low and dope layer of bonding force opening plating difficulty, layers of copper and dope layer of the electroless copper of the method for catalytic activity.After this coating is mixed by biological binder solution, metal-salt, metal chelating agent, wetting agent and deionized water, then with to obtain behind pH adjusting agent regulator solution pH to 6 ~ 9.The technique of pre-treatment: after electrochemical deoiling process is carried out to surface of plastic matrix, ionic metal coating is coated in plastic basis material surface, then oven drying at low temperature, obtain the coating that build is 0.1 ~ 1 micron, complete the pre-treatment of plastic substrate chemical plating copper, the method opens plating soon, and coating uniform, can be used for electroless plating field.
Description
Technical field
The present invention relates to a kind of surface of plastic matrix process coating used and utilize it to carry out surface-treated method, particularly relate to a kind of surface of plastic matrix electroless copper pre-treatment coating used and utilize it to carry out the technique of electroless copper pre-treatment.
Background technology
Plastics have compared with high impact strength, the lot of advantages such as corrosion-resistant, processing forming good, and quality is light, can have many advantages such as conductive and heat-conductive magnetic conduction, ornamental, weldability after plastics metalizing concurrently.Plastics metalizingly at present mainly contain copper facing, nickel plating, silver-plated, gold-plated, plating palladium etc.Plastics copper facing application relates to many fields such as engineering plastics, printed board, electronics finishing.The equipment costs such as plastics copper facing mainly comprises Physical and chemical method, Physical such as ion sputtering are expensive, and bonding force has problem, have dimensional requirement to process workpiece.And chemical method does not affect by these, chemical method mainly comprises plastics Direct Electroplating and electroless plating.Electroless plating is also electroless plating, and be a kind of chemical reaction process of autocatalysis, it does not need additional power source, is a kind of process utilizing reductive agent in plating solution to carry out reducing metal ion.The matrix of electroless plating needs catalytic activity, and namely workpiece surface must have the metal inducement material of energy redox agent.Will realize plastics part electroless copper key is thus in pre-treatment, make plastic workpiece surface having have catalytic activity.Paint method is wherein adopted to make plastic workpiece surface having have the method for catalytic activity to be by paint at plastic workpiece surface after treatment, workpiece surface is made to have catalytic activity, such as application number method disclosed in the Chinese patent of 201210287898.6 is mixed with urethane resin by ionic palladium to make coating activation solution, be coated in plastic workpiece surface, again the temperature baking of 150 ~ 200 DEG C, then electroless copper.But this method Problems existing is exactly the oven dry of this coating, and rear surface presents hydrophobicity, and chemical copper plating solution is the aqueous solution, and due to the existence of interfacial tension, what must affect electroless copper opens plating; The introducing of certain thickness resin glue simultaneously, because this resin glue has the thermal expansivity different from matrix, the bonding force of layers of copper and dope layer can be made to reduce, printed board or optical material etc. are not suitable for adopting this method to thermal expansivity or the strict material of stability requirement.Application number is propose at organic non-conductive matrix surface coated with conductive coating in the Chinese patent of 201110314195.3, baking-curing afterwards, then takes mechanical polishing destruction hydrophobicity to expose active site, then electroless copper.In the method, mechanical polishing exposes the homogeneity very difficult control of method for polishing of active site, especially for irregular workpiece.
Summary of the invention
The present invention will solve existing employing paint method to make plastic workpiece surface having have the technical problem of lack of homogeneity of the low and dope layer of bonding force opening plating difficulty, layers of copper and dope layer of the electroless copper of the method for catalytic activity, and provides a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper and technique.
After a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper of the present invention is mixed by the deionized water of the biological binder solution of 5 ~ 20 parts, the metal-salt of 0.01 ~ 5 part, the metal chelating agent of 1 ~ 10 part, the wetting agent of 0.1 ~ 1 part and 65 ~ 90 parts by ratio of weight and the number of copies, then with obtaining behind pH adjusting agent regulator solution pH to 6 ~ 9;
Wherein said biological binder solution is made up of the deionized water of the biological binding agent monomer of 0.5 ~ 15 part, the oxygenant of 0.1 ~ 5 part, the pH buffer reagent of 0.5 ~ 5 part, the silane coupling agent of 0.1 ~ 1 part and 75 ~ 95 parts by ratio of weight and the number of copies;
Wherein biological binding agent monomer is a kind of or wherein several combination in dopamine hydrochloride, noradrenalin, 5-hydroxydopamine, Droxidopa, alpha-methyldopa amine, dextrorotation DOPA, levodopa, alpha-methyldopa and nitro Dopamine HCL;
The preparation method of the above-mentioned ionic metal coating for the pre-treatment of plastic substrate chemical plating copper carries out according to the following steps:
One, the deionized water of the biological binder solution of 5 ~ 20 parts, the metal-salt of 0.01 ~ 5 part, the metal chelating agent of 1 ~ 10 part, the wetting agent of 0.1 ~ 1 part and 65 ~ 90 parts is taken by ratio of weight and the number of copies;
Two, the deionized water of 2/3 is poured in container, add metal chelating agent and be stirred to dissolving;
Three, under whipped state, metal-salt is joined in container, after to be dissolved, add biological binder solution;
Four, under whipped state, wetting agent is joined in container, after stirring, remaining deionized water is poured in container, then stir;
Five, under whipped state, add pH adjusting agent, regulate pH to 6 ~ 9, continue to stir 12h, obtain the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper.
Utilize the above-mentioned ionic metal coating for the pre-treatment of plastic substrate chemical plating copper to carry out the technique of plastic substrate chemical plating copper pre-treatment, specifically carry out according to the following steps:
One, electrochemical deoiling process is carried out to surface of plastic matrix;
Plastic substrate used is general engineering plastics or pcb substrate, and engineering plastics are acrylonitrile-butadiene-styrene (ABS) plastics (ABS) plastics, polyimide (PI) plastics, polyethylene terephthalate (PET); Pcb substrate is epoxy resin glass-fiber-plate (FR-4), Kapton (PI), polyethylene terephthalate (PET) film;
Surface of plastic matrix is specifically immersed in the electrochemical deoiling liquid of 60 ~ 80 DEG C by electrochemical deoiling process soaks 3 ~ 5min; Wherein electrochemical deoiling liquid is that one or more in 30-~ 60g/L sodium hydroxide, 15 ~ 30g/L sodium carbonate and 20 ~ 35g/L tertiary sodium phosphate are added to the water the solution obtained;
Two, the ionic metal coating being used for the pre-treatment of plastic substrate chemical plating copper is coated in the plastic basis material surface processed through step one, then be dry 0.5 ~ 5min under the condition of 25 ~ 65 DEG C in temperature, obtain on plastic basis material surface the coating that build is 0.1 ~ 1 micron, complete the pre-treatment of plastic substrate chemical plating copper.
Advantage of the present invention be in particular in following some:
1, highly versatile is good with various plastic substrate bonding force.Have employed the biological binding agent containing catechol structure in coating described in this technique, the binding agent of this catechol structure derives from biological mussel mucus, can adhere to almost any plastic substrate.Compared with the process of conventional ion metal activation, the reactive force between the coating of this art breading and matrix is chemical bond and an active non-anchor effect, therefore the electroless copper binding force of cladding material obtained is very high.
2, technique is simple.
1) compared with coating catalytic coatings technique, coating dry film thickness, at Nano grade, without the need to high temperature sintering, only needs low-temperature short-time to dry;
2) compared with coating catalytic coatings technique, dry rear surface and still present wetting ability, therefore expose catalytic activity point without the need to aftertreatment (as polishing), there is not the interfacial tension problem with chemical copper plating solution, dope layer is even, opens plating easily, is also suitable for plastic substrate in irregular shape.
3) compared with conventional activation liquid technique, without chemical roughen step, avoid and use environmentally harmful coarsening solution, environmentally friendly;
4) without chemical reduction step.Compared with conventional ion metal activation method, eliminate the step obtaining electroless plating catalysed particulate with reductive agent reduction, but directly utilize the reductive agent in chemical copper plating solution to generate catalyticing metal particle, then continue the copper facing of catalytic chemistry plating process implementation.
3, good stability.
With conventional plastic absorption method with apply the catalytic solution that Coating Method adopts and compare, metal ion exists with ionic condition in coating, and metal can with the catechol structure in biological binding agent and nitrogen-atoms valence link, therefore described ionic metal paint stability is fine.
In a word, the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper of the present invention has versatility widely to plastic substrate, and good with plastic substrate bonding force, stability is fine; Wetting ability is strong, and metal exists with ionic state, without the need to high temperature sintering, and the catalytic performance only needing low-temperature short-time to dry just to have had and apply rear surface total hydrophilic, not Presence of an interface strain problem; Do not limit by base shape.Plastic substrate only needs the steps such as oil removing, coating, low-temperature short-time oven dry just can carry out electroless plating, can save traditional chemical roughen, and whole treatment process is simple, environmentally friendly; Self reductive agent of chemical plating solution is directly utilized to reduce, without the need to increasing reduction step as ionic metal activation solution in the past.Can obtain by the technique of cheap and simple environmental protection the electroless copper metal plating that bonding force is good, outward appearance is good at surface of plastic matrix by the method.
Accompanying drawing explanation
Fig. 1 is 400 times of optical microscope photographs of the layers of copper of embodiment 1PI plastics strip;
Fig. 2 is 400 times of optical microscope photographs of the layers of copper on the epoxy resin glass-fiber-plate FR-4 surface of embodiment 2;
Fig. 3 is 400 times of optical microscope photographs of the layers of copper on the ABS plastic plate surface of embodiment 3;
Fig. 4 is 400 times of optical microscope photographs of the layers of copper on the PET plate surface of embodiment 4.
Embodiment
Embodiment one: after a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper of present embodiment is mixed by the deionized water of the biological binder solution of 5 ~ 20 parts, the metal-salt of 0.01 ~ 5 part, the metal chelating agent of 1 ~ 10 part, the wetting agent of 0.1 ~ 1 part and 65 ~ 90 parts by ratio of weight and the number of copies, then with obtaining behind pH adjusting agent regulator solution pH to 6 ~ 9; Biological binder solution is made up of the deionized water of the biological binding agent monomer of 0.5 ~ 15 part, the oxygenant of 0.1 ~ 5 part, the pH buffer reagent of 0.5 ~ 5 part, the silane coupling agent of 0.1 ~ 1 part and 75 ~ 95 parts by ratio of weight and the number of copies; Wherein biological binding agent monomer is a kind of or wherein several combination in dopamine hydrochloride, noradrenalin, 5-hydroxydopamine, Droxidopa, alpha-methyldopa amine, dextrorotation DOPA, levodopa, alpha-methyldopa and nitro Dopamine HCL.
The biological binding agent monomer of present embodiment all has catechol structure.
Embodiment two: present embodiment and embodiment one are a kind of or wherein several combination in clorox, potassium permanganate, oxygen, ammonium persulphate and sodium peroxide unlike the oxygenant in biological binder solution; Other is identical with embodiment one.
When oxygenant is composition, each oxygenant is by any combination.
Embodiment three: present embodiment and embodiment one or two are borax, sodium-acetate, tris hydrochloride or SODIUM PHOSPHATE, MONOBASIC unlike the pH buffer reagent in biological binder solution; Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are a kind of or wherein several combination in KH550, KH792, KH560 and KH602 unlike silane coupling agent in biological binder solution; Other is identical with one of embodiment one to three.
When silane coupling agent is composition, each silane coupling agent is by any combination.
The effect that silane coupling agent is is mainly the bonding force improved with matrix.
Embodiment five: one of present embodiment and embodiment one to four are as follows unlike the preparation method of biological binder solution:
A, take the deionized water of the biological binding agent monomer of 0.5 ~ 15 part, the oxygenant of 0.1 ~ 5 part, the pH buffer reagent of 0.5 ~ 5 part, the silane coupling agent of 0.1 ~ 1 part and 75 ~ 95 parts by ratio of weight and the number of copies;
B, the deionized water of 2/3 is poured in encloses container, add pH buffer reagent and be stirred to dissolving, and then add biological binding agent monomer, be stirred to monomer and all dissolve;
C, under agitation, oxygenant to be joined in encloses container, then temperature be warming up to 45 ~ 50 DEG C by normal temperature and keep reaction 20 ~ 24h;
D, silane coupling agent is joined in encloses container, continue at 45 ~ 50 DEG C and keep reaction 20 ~ 24h;
E, remaining deionized water is poured in encloses container, stir, obtain biological binder solution.
Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are palladium salt, silver salt, nickel salt or mantoquita unlike described metal-salt; Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment and embodiment six are a kind of or wherein several combination in Palladous chloride, palladous sulfate and palladium unlike described palladium salt; Other is identical with embodiment six.
When in present embodiment, palladium salt is composition, various palladium salt is by any combination.
Embodiment eight: present embodiment and embodiment six are a kind of or wherein several combination in Silver Nitrate, silver fluoride and silver perchlorate unlike described silver salt; Other is identical with embodiment six.
When in present embodiment, silver salt is composition, various silver salt is by any combination.
Embodiment nine: present embodiment and embodiment six are a kind of or wherein several combination in nickelous chloride, nickel sulfamic acid, single nickel salt, nickel acetate and basic nickel carbonate unlike described nickel salt; Other is identical with embodiment six.
When in present embodiment, nickel salt is composition, various nickel salt is by any combination.
Embodiment ten: present embodiment and embodiment six are a kind of or wherein several combination in copper sulfate, cupric nitrate and cupric chloride unlike described mantoquita; Other is identical with embodiment six.
When in present embodiment, mantoquita is composition, various mantoquita is by any combination.
Embodiment 11: one of present embodiment and embodiment one to ten are thanomin, quadrol, sodium ethylene diamine tetracetate and N unlike metal chelating agent, a kind of or wherein several combination in N, N'N'-tetra-(2-hydroxypropyl) quadrol; Other is identical with one of embodiment one to ten.
When in present embodiment, metal chelating agent is composition, each metal chelating agent is by any combination.
Embodiment 12: one of present embodiment and embodiment one to ten one are a kind of or wherein several combination in sodium lauryl sulphate, sodium laurylsulfonate and sodium cetanesulfonate unlike wetting agent; Other is identical with one of embodiment one to ten one.
When in present embodiment, wetting agent is composition, each wetting agent is by any combination.
Embodiment 13: one of present embodiment and embodiment one to ten two are ammoniacal liquor, hydrochloric acid or sulfuric acid unlike pH adjusting agent; Other is identical with one of embodiment one to ten two.
Embodiment 14: the preparation method of the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in embodiment one carries out according to the following steps:
One, the deionized water of the biological binder solution of 5 ~ 20 parts, the metal-salt of 0.01 ~ 5 part, the metal chelating agent of 1 ~ 10 part, the wetting agent of 0.1 ~ 1 part and 65 ~ 90 parts is taken by ratio of weight and the number of copies;
Two, the deionized water of 2/3 is poured in container, add metal chelating agent and be stirred to dissolving;
Three, under whipped state, metal-salt is joined in container, after to be dissolved, add biological binder solution;
Four, under whipped state, wetting agent is joined in container, after stirring, remaining deionized water is poured in container, then stir;
Five, under whipped state, add pH adjusting agent, regulate pH to 6 ~ 9, continue to stir 12h, obtain the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper.
Embodiment 15: utilize the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in embodiment one to carry out the technique of plastic substrate chemical plating copper pre-treatment, specifically carry out according to the following steps:
One, electrochemical deoiling process is carried out to surface of plastic matrix;
Two, the ionic metal coating being used for the pre-treatment of plastic substrate chemical plating copper is coated in the plastic basis material surface processed through step one, then be dry 0.5 ~ 5min under the condition of 25 ~ 65 DEG C in temperature, obtain on plastic basis material surface the coating that build is 0.1 ~ 1 micron, complete the pre-treatment of plastic substrate chemical plating copper.
Embodiment 16: present embodiment and embodiment 15 are general engineering plastics or pcb substrate unlike described plastic substrate.Other are identical with embodiment 15.
Embodiment 17: present embodiment and embodiment 15 or 16 are acrylonitrile-butadiene-styrene (ABS) plastics (ABS) plastics unlike engineering plastics, polyimide (PI) plastics, polyethylene terephthalate (PET); Pcb substrate is epoxy resin glass-fiber-plate (FR-4), Kapton (PI), polyethylene terephthalate (PET) film.Other are identical with embodiment 15 or 16.
Embodiment 18: surface of plastic matrix is specifically immersed in the electrochemical deoiling liquid of 60 ~ 80 DEG C unlike electrochemical deoiling process by present embodiment and embodiment 15 or 16 soaks 3 ~ 5min; Wherein electrochemical deoiling liquid is that one or more in 30-~ 60g/L sodium hydroxide, 15 ~ 30g/L sodium carbonate and 20 ~ 35g/L tertiary sodium phosphate are added to the water the solution obtained.Other are identical with embodiment 15 or 16.
With the beneficial effect of the present invention of case verification below:
The process of the test of example 1 the present embodiment 1 is as follows:
One, prepare the biological binder solution of Dopamine HCL, its preparation method is as follows:
A, take the deionized water of the dopamine hydrochloride of 5.5 parts, the ammonium persulphate of 3 parts, the tris hydrochloride of 1 part, the Silane coupling agent KH550 of 0.5 part and 90 parts by ratio of weight and the number of copies;
B, the deionized water of 2/3 is poured in encloses container, add tris hydrochloride and be stirred to dissolving, and then add dopamine hydrochloride, be stirred to dopamine hydrochloride and all dissolve;
C, under agitation, ammonium persulphate to be joined in encloses container, then temperature be warming up to 50 DEG C by normal temperature and keep reaction 24h;
D, Silane coupling agent KH550 is joined in encloses container, continue at 50 DEG C and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stir, obtain the biological binder solution of Dopamine HCL.
Two, the biological binder solution of the Dopamine HCL utilizing step one to synthesize is for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, and concrete preparation method is as follows:
F, take the deionized water of the biological binder solution of Dopamine HCL of 10 parts, the Palladous chloride of 0.05 part, the sodium ethylene diamine tetracetate of 5 parts, the sodium lauryl sulphate of 0.1 part and 84 parts by ratio of weight and the number of copies;
G, the deionized water of 2/3 is poured in container, add metal chelating agent sodium ethylene diamine tetracetate and be stirred to dissolving;
H, under whipped state, Palladous chloride to be joined in container, after to be dissolved, add the biological binder solution of Dopamine HCL;
I, under whipped state, sodium lauryl sulphate to be joined in container, after stirring, remaining deionized water is poured in container, then stir;
J, under whipped state, add ammoniacal liquor, regulate pH to 8, continue to stir 12h, obtain the palladium ion metallic paint for the pre-treatment of plastic substrate chemical plating copper.
Three, carry out the pre-treatment of flexible printed circuit special PI plastic substrate chemical plating copper with the palladium ion metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2 synthesis, its concrete technology step is as follows:
K, by special for flexible printed circuit PI plastics, be cut into 2 × 2cm
2, thickness 0.1 centimetre test piece, putting into electrochemical deoiling liquid, is under the condition of 65 DEG C in temperature, soak 4min; After taking out, distilled water cleaning, dries up; Wherein electrochemical deoiling liquid obtains after being added to the water by the sodium carbonate of 40g/L sodium hydroxide and 25g/L;
L, be immersed in the PI plastics processed through step one for the pre-treatment of plastic substrate chemical plating copper palladium ion metallic paint in soak 2min, then sample is taken out, at 50 DEG C, dry 2min, obtain the PI plastics test piece with ionic palladium dope layer that build is 0.5 micron; (can by x-ray fluorescence spectrometry, selected palladium is internal standard element, sets up thickness-palladium content typical curve)
Four, electroless copper is carried out in the PI plastics test piece prepared in step 3, specific as follows:
M, by the concentration of copper sulfate be 0.04mol/L, the concentration of Seignette salt is 0.2mol/L, the concentration of sodium hydroxide is 0.25mol/L, the concentration of 37% formaldehyde is 10mL/L, the concentration of MBT is that copper sulfate, Seignette salt, sodium hydroxide, 37wt% formaldehyde and MBT add in deionized water by 0.2mg/L, stir, obtain chemical copper plating solution;
N, the test piece of PI plastics put into the chemical copper plating solution of 40 DEG C, plating 1h, obtains layers of copper at PI plastics strip, completes electroless copper.
In step 3, build utilizes x-ray fluorescence spectrometry, and selected palladium is internal standard element, sets up thickness-palladium content typical curve, then according to the palladium content of dry film, calculates build.
In step 4, the sedimentation velocity of electroless copper is at 2 ~ 3 μm/h.
Coating deposition rate is at 1-3 μm/h.
The process of the test of example 2 the present embodiment 2 is as follows:
One, prepare the biological binder solution of levodopa, its preparation method is as follows:
A, take the deionized water of the levodopa of 5 parts, the clorox of 2 parts, the borax of 2 parts, 1 part silane coupling agent KH560 and 90 part by ratio of weight and the number of copies;
B, the deionized water of 2/3 is poured in encloses container, add borax and be stirred to dissolving, and then add levodopa, be stirred to levodopa and all dissolve;
C, under agitation, clorox to be joined in encloses container, after clorox dissolves, temperature is warming up to 50 DEG C by normal temperature and keeps reaction 24h;
D, silane coupling agent KH560 is joined in encloses container, continue at 50 DEG C and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stir, obtain the biological binder solution of levodopa.
Two, the biological binder solution of the levodopa utilizing step one to synthesize is for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, and concrete preparation method is as follows:
F, take the deionized water of the biological binder solution of levodopa of 15 parts, the Silver Nitrate of 0.1 part, the quadrol of 5 parts, the sodium lauryl sulphate of 1 part and 78 parts by ratio of weight and the number of copies;
G, the deionized water of 2/3 is poured in container, add metal chelating agent quadrol and be stirred to dissolving;
H, under whipped state, Silver Nitrate to be joined in container, after to be dissolved, add the biological binder solution of levodopa;
I, under whipped state, sodium lauryl sulphate to be joined in container, after stirring, remaining deionized water is poured in container, then stir;
J, under whipped state, add sulfuric acid, regulate pH to 6, continue to stir 12h, obtain the silver ions metallic paint for the pre-treatment of plastic substrate chemical plating copper.
Three, carry out the pre-treatment of rigid printed board base material epoxy resin glass-fiber-plate FR-4 basal body chemical plating copper with the silver ions metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2 synthesis, its concrete technology step is as follows:
K, by rigid printed board base material epoxy resin glass-fiber-plate FR-4, be cut into 2 × 2cm
2, thickness 0.1 centimetre test piece, putting into electrochemical deoiling liquid, is under the condition of 60 DEG C in temperature, soak 3min; After taking out, distilled water cleaning, dries up; Wherein electrochemical deoiling liquid obtains after being added to the water by the sodium carbonate of 30g/L sodium hydroxide and 25g/L;
L, be immersed in the epoxy resin glass-fiber-plate processed through step one for the pre-treatment of plastic substrate chemical plating copper silver ions metallic paint in soak 2min, then sample is taken out, at 50 DEG C, dry 2min, obtain the epoxy resin glass-fiber-plate with ionic silver dope layer that build is 0.5 micron;
Four, the epoxy resin glass-fiber-plate prepared in step 3 carries out electroless copper, specific as follows:
M, by the concentration of copper sulfate be 0.04mol/L, the concentration of Seignette salt is 0.2mol/L, the concentration of sodium hydroxide is 0.25mol/L, the concentration of 37% formaldehyde is 10mL/L, the concentration of MBT is that copper sulfate, Seignette salt, sodium hydroxide, 37wt% formaldehyde and MBT add in deionized water by 0.2mg/L, stir, obtain chemical copper plating solution;
N, the test piece of epoxy resin glass-fiber-plate put into the chemical copper plating solution of 40 DEG C, plating 1h, obtains layers of copper on epoxy resin glass-fiber-plate surface, completes electroless copper.
In step 3, build utilizes x-ray fluorescence spectrometry, and selected silver is internal standard element, sets up thickness-silver content typical curve, then according to the silver content of dry film, calculates build.
In step 4, the sedimentation velocity of electroless copper is at 2 ~ 3 μm/h.
The process of the test of example 3 the present embodiment 3 is as follows:
One, prepare the biological binder solution of 5-hydroxydopamine, its preparation method is as follows:
A, take the deionized water of the 5-hydroxydopamine of 5 parts, the potassium permanganate of 3 parts, the sodium-acetate of 2 parts, 1 part silane coupling agent KH792 and 84 part by ratio of weight and the number of copies;
B, the deionized water of 2/3 is poured in encloses container, add sodium-acetate and be stirred to dissolving, and then add 5-hydroxydopamine, be stirred to 5-hydroxydopamine and all dissolve;
C, under agitation, potassium permanganate to be joined in encloses container, after potassium permanganate dissolves, temperature is warming up to 50 DEG C by normal temperature and keeps reaction 24h;
D, silane coupling agent KH792 is joined in encloses container, continue at 50 DEG C and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stir, obtain the biological binder solution of 5-hydroxydopamine.
Two, the biological binder solution of the 5-hydroxydopamine utilizing step one to synthesize is for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, and concrete preparation method is as follows:
F, take the deionized water of the biological binder solution of 5-hydroxydopamine of 15 parts, the single nickel salt of 0.1 part, the sodium ethylene diamine tetracetate of 5 parts, the sodium cetanesulfonate of 1 part and 78 parts by ratio of weight and the number of copies;
G, the deionized water of 2/3 is poured in container, add metal chelating agent sodium ethylene diamine tetracetate and be stirred to dissolving;
H, under whipped state, single nickel salt to be joined in container, after to be dissolved, add 5-hydroxydopamine biology bonding
Agent solution;
I, under whipped state, sodium cetanesulfonate to be joined in container, after stirring, remaining deionized water is poured in container, then stir;
J, under whipped state, add ammoniacal liquor, regulate pH to 7.5, continue to stir 12h, obtain the nickel ion metallic paint for the pre-treatment of plastic substrate chemical plating copper.
Three, carry out the pre-treatment of ABS plastic basal body chemical plating copper with the nickel ion metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2 synthesis, its concrete technology step is as follows:
K, by ABS plastic, be cut into 2 × 2cm
2, thickness 0.125 centimetre test piece, putting into electrochemical deoiling liquid, is under the condition of 65 DEG C in temperature, soak 3min; After taking out, distilled water cleaning, dries up; Wherein electrochemical deoiling liquid obtains after being added to the water by the sodium carbonate of 30g/L sodium hydroxide and 25g/L;
L, be immersed in the ABS plastic plate processed through step one for the pre-treatment of plastic substrate chemical plating copper nickel ion metallic paint in soak 2min, then sample is taken out, at 50 DEG C, dries 2min, obtain the ABS plastic plate that build is 0.8 micron;
Four, the ABS plastic plate prepared in step 3 carries out electroless copper, specific as follows:
M, by copper sulfate 0.04mol/L, glycine 0.2mol/L, sodium hydroxide 0.25mol/L, sodium hypophosphite 0.09mol/L, copper sulfate, glycine, sodium hydroxide, sodium hypophosphite and MBT add in deionized water by MBT 0.2mg/L, stir, obtain chemical copper plating solution;
N, the test piece of ABS plastic plate put into the chemical copper plating solution of 75 DEG C, plating 1h, obtains layers of copper on ABS plastic plate surface, completes electroless copper.
In step 3, build utilizes x-ray fluorescence spectrometry, and selected nickel is internal standard element, sets up thickness-nickel content standard curve, then according to the nickel content of dry film, calculates build.
In step 4, the sedimentation velocity of electroless copper is at 3-8 μm/h.
The process of the test of example 4 the present embodiment 4 is as follows:
One, prepare the biological binder solution of Droxidopa, its preparation method is as follows:
A, take the deionized water of the Droxidopa of 10 parts, the ammonium persulphate of 3 parts, the SODIUM PHOSPHATE, MONOBASIC of 2 parts, 1 part silane coupling agent KH602 and 84 part by ratio of weight and the number of copies;
B, the deionized water of 2/3 is poured in encloses container, add SODIUM PHOSPHATE, MONOBASIC and be stirred to dissolving, and then add Droxidopa, be stirred to Droxidopa and all dissolve;
C, under agitation, ammonium persulphate to be joined in encloses container, after ammonium persulphate dissolves, temperature is warming up to 50 DEG C by normal temperature and keeps reaction 24h;
D, silane coupling agent KH602 is joined in encloses container, continue at 50 DEG C and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stir, obtain the biological binder solution of Droxidopa.
Two, the biological binder solution of the Droxidopa utilizing step one to synthesize is for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, and concrete preparation method is as follows:
F, take the biological binder solution of Droxidopa of 16 parts, the copper sulfate of 1 part, 3 parts of N, N, N'N'-tetra-(2-hydroxypropyl) quadrols, the sodium cetanesulfonate of 1 part and deionized waters of 78 parts by ratio of weight and the number of copies;
G, pour in container by the deionized water of 2/3, add metal chelating agent N, N, N'N'-tetra-(2-hydroxypropyl) quadrol is stirred to dissolving;
H, under whipped state, copper sulfate to be joined in container, after to be dissolved, add the biological binder solution of Droxidopa;
I, under whipped state, sodium cetanesulfonate to be joined in container, after stirring, remaining deionized water is poured in container, then stir;
J, under whipped state, add sulfuric acid, regulate pH to 7, continue to stir 12h, obtain the cupric ion metallic paint for the pre-treatment of plastic substrate chemical plating copper.
Three, carry out the pre-treatment of PET basal body chemical plating copper with the cupric ion metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2 synthesis, its concrete technology step is as follows:
K, by PET, be cut into 2 × 2cm
2, thickness 0.1 centimetre test piece, putting into electrochemical deoiling liquid, is under the condition of 60 DEG C in temperature, soak 3min; After taking out, distilled water cleaning, dries up; Wherein electrochemical deoiling liquid obtains after being added to the water by the sodium carbonate of 30g/L sodium hydroxide and 25g/L;
L, be immersed in the PET plate processed through step one for the pre-treatment of plastic substrate chemical plating copper cupric ion metallic paint in soak 2min, then sample is taken out, at 50 DEG C, dries 2min, obtain the PET plate that build is 0.8 micron;
Four, the PET plate prepared in step 3 carries out electroless copper, specific as follows:
M, by the concentration of copper sulfate be 0.04mol/L, the concentration of Seignette salt is 0.2mol/L, the concentration of sodium hydroxide is 0.25mol/L, the concentration of 37% formaldehyde is 10mL/L, the concentration of MBT is that copper sulfate, Seignette salt, sodium hydroxide, 37wt% formaldehyde and MBT add in deionized water by 0.2mg/L, stir, obtain chemical copper plating solution;
N, the test piece of PET plate put into the chemical copper plating solution of 40 DEG C, plating 1h, obtains layers of copper at PET plate upper surface, completes electroless copper.
In step 3, build utilizes x-ray fluorescence spectrometry, and selected copper is internal standard element, sets up thickness-copper content standard curve, then according to the copper content of dry film, calculates build.
In step 4, the sedimentation velocity of electroless copper is at 3-8 μm/h.
Coating deposition rate is at 2-3 μm/h.
The chemical plating copper layer obtained above-mentioned 4 embodiments carries out the sign of outward appearance, bonding force, electroconductibility.Centrifugal test and catalytic performance observation experiment are carried out to the stability of ionic metal coating simultaneously.
Outward appearance 400 times of opticmicroscopes are observed, and observe homogeneity and surface imperfection.Fig. 1 is 400 times of optical microscope photographs of the layers of copper of embodiment 1PI plastics strip; Fig. 2 is 400 times of optical microscope photographs of the layers of copper on the epoxy resin glass-fiber-plate FR-4 surface of embodiment 2; Fig. 3 is 400 times of optical microscope photographs of the layers of copper on the ABS plastic plate surface of embodiment 3; Fig. 4 is 400 times of optical microscope photographs of the layers of copper on the PET plate surface of embodiment 4.As can be seen from Fig. 1 ~ 4, all layers of copper obtained are zero defect all evenly.
Bonding force adopts thermal shock test.Through 100 DEG C (25min), 0 DEG C of (frozen water 5min) thermal shock test 10 times, observes coating with or without foaming, crackle and obscission.Judge the bonding force situation of copper coating.
The measurement of electroconductibility adopts universal meter, and the face of test piece is chosen 2 points of the one side that exists together, apart 1cm, and survey its resistance value, the result obtained is as shown in table 1.
The stability of ionic metal coating adopts whizzer under 5000 revs/min of rotating speeds centrifugal 30 minutes, then observes coating and whether occurs layering or sedimentation.
The catalytic performance of ionic metal coating is weighed by the plating time of opening of electroless copper, and by manual time-keeping, the time is shorter, and catalytic performance is stronger.
The measuring result of embodiment 1 ~ 4 is as shown in table 1.
By finding out in table, ionic metal coating is used in electroless copper pre-treatment, the successful obtained.Deposit appearance bonding force and electroconductibility are all good, and paint stability and catalytic are also all good.
Claims (10)
1. the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper, after it is characterized in that this coating is mixed by the deionized water of the biological binder solution of 5 ~ 20 parts, the metal-salt of 0.01 ~ 5 part, the metal chelating agent of 1 ~ 10 part, the wetting agent of 0.1 ~ 1 part and 65 ~ 90 parts by ratio of weight and the number of copies, then with obtaining behind pH adjusting agent regulator solution pH to 6 ~ 9; Wherein biological binder solution is made up of the deionized water of the biological binding agent monomer of 0.5 ~ 15 part, the oxygenant of 0.1 ~ 5 part, the pH buffer reagent of 0.5 ~ 5 part, the silane coupling agent of 0.1 ~ 1 part and 75 ~ 95 parts by ratio of weight and the number of copies; Wherein biological binding agent monomer is a kind of or wherein several combination in dopamine hydrochloride, noradrenalin, 5-hydroxydopamine, Droxidopa, alpha-methyldopa amine, dextrorotation DOPA, levodopa, alpha-methyldopa and nitro Dopamine HCL.
2. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, the oxygenant that it is characterized in that in biological binder solution is a kind of or wherein several combination in clorox, potassium permanganate, oxygen, ammonium persulphate and sodium peroxide.
3. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, the pH buffer reagent that it is characterized in that in biological binder solution is a kind of or wherein several combination in borax, sodium-acetate, tris hydrochloride or SODIUM PHOSPHATE, MONOBASIC.
4. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, the silane coupling agent that it is characterized in that in biological binder solution is a kind of or wherein several combination in KH550, KH792, KH560 and KH602.
5. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1,2,3 or 4, is characterized in that the preparation method of biological binder solution is as follows:
A, take the deionized water of the biological binding agent monomer of 0.5 ~ 15 part, the oxygenant of 0.1 ~ 5 part, the pH buffer reagent of 0.5 ~ 5 part, the silane coupling agent of 0.1 ~ 1 part and 75 ~ 95 parts by ratio of weight and the number of copies;
B, the deionized water of 2/3 is poured in encloses container, add pH buffer reagent and be stirred to dissolving, and then add biological binding agent monomer, be stirred to monomer and all dissolve;
C, under agitation, oxygenant to be joined in encloses container, then temperature be warming up to 45 ~ 50 DEG C by normal temperature and keep reaction 20 ~ 24h;
D, silane coupling agent is joined in encloses container, continue at 45 ~ 50 DEG C and keep reaction 20 ~ 24h;
E, remaining deionized water is poured in encloses container, stir, obtain biological binder solution.
6. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, is characterized in that metal-salt is palladium salt, silver salt, nickel salt or mantoquita; Wherein palladium salt is a kind of or wherein several combination in Palladous chloride, palladous sulfate and palladium; Silver salt is a kind of or wherein several combination in Silver Nitrate, silver fluoride and silver perchlorate; Nickel salt is a kind of or wherein several combination in nickelous chloride, nickel sulfamic acid, single nickel salt, nickel acetate and basic nickel carbonate; Mantoquita is a kind of or wherein several combination in copper sulfate, cupric nitrate and cupric chloride.
7. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1 or 6, it is characterized in that metal chelating agent is thanomin, quadrol, sodium ethylene diamine tetracetate and N, a kind of or wherein several combination in N, N'N'-tetra-(2-hydroxypropyl) quadrol.
8. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1 or 6, is characterized in that wetting agent is a kind of or wherein several combination in sodium lauryl sulphate, sodium laurylsulfonate and sodium cetanesulfonate.
9. utilize the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in claim 1 to carry out the technique of plastic substrate chemical plating copper pre-treatment, it is characterized in that this technique is carried out according to the following steps:
One, electrochemical deoiling process is carried out to surface of plastic matrix;
Two, the ionic metal coating being used for the pre-treatment of plastic substrate chemical plating copper is coated in the plastic basis material surface processed through step one, then be dry 0.5 ~ 5min under the condition of 25 ~ 65 DEG C in temperature, obtain on plastic basis material surface the coating that build is 0.1 ~ 1 micron, complete the pre-treatment of plastic substrate chemical plating copper.
10. utilization according to claim 9 is used for the technique that the ionic metal coating of plastic substrate chemical plating copper pre-treatment carries out the pre-treatment of plastic substrate chemical plating copper, it is characterized in that described plastic substrate is general engineering plastics or pcb substrate.
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