CN103525154A - Ion metallic paint for electroless copper plating pretreatment of plastic matrix and process - Google Patents
Ion metallic paint for electroless copper plating pretreatment of plastic matrix and process Download PDFInfo
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- CN103525154A CN103525154A CN201310454344.5A CN201310454344A CN103525154A CN 103525154 A CN103525154 A CN 103525154A CN 201310454344 A CN201310454344 A CN 201310454344A CN 103525154 A CN103525154 A CN 103525154A
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Abstract
The invention discloses ion metallic paint for electroless copper plating pretreatment of a plastic matrix and a process. The invention relates to paint for surface treatment of the plastic matrix and a method for carrying out surface treatment by utilizing the paint. The invention aims to solve the technical problems of difficulty in flash plating of electroless copper plating, low binding force between a copper layer and a paint layer and poor uniformity of the paint layer of an existing method of enabling the surface of a plastic workpiece to have catalytic activity by adopting a paint coating method. The paint is prepared by mixing biological binder solution, metal salt, a metal chelating agent, a wetting agent and deionized water and then regulating pH of the solution to the range of 6 to 9 by a pH modifier. The pretreatment process comprises the following steps: after carrying out chemical degreasing processing on the surface of the plastic matrix, coating the surface of the plastic matrix with the ion metallic paint; and then carrying out low temperature drying to obtain a coating with a dry film thickness of 0.1 to 1 micron, and completing electroless copper plating pretreatment of the plastic matrix. The method has a high flash plating speed, obtains the uniform coating and can be used in the field of chemical plating.
Description
Technical field
The present invention relates to a kind of surface of plastic matrix and process coating used and utilize it to carry out surface-treated method, relate in particular 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 plastic-metal concurrently.At present plastic-metal mainly contains 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 plating.Plastics copper facing mainly comprises Physical and chemical method, and Physical is such as the equipment costs such as ion sputtering are expensive, and bonding force has problem, to processing workpiece, has dimensional requirement.And chemical method is not affected by these, chemical method mainly comprises plastics Direct Electroplating and electroless plating.Electroless plating is also electroless plating, is a kind of chemical reaction process of autocatalysis, and it does not need additional power source, is a kind of process of utilizing reductive agent in plating solution to carry out reducing metal ion.The matrix of electroless plating need to have catalytic activity, and namely workpiece surface must have the metal inducement material of energy redox agent.Will realize thus plastics part electroless copper key is in pre-treatment, to make plastic workpiece surface having have catalytic activity.Wherein adopting coating cladding process to make plastic workpiece surface having have the method for catalytic activity is that coating is coated in to plastic workpiece surface after treatment, make workpiece surface there is catalytic activity, the disclosed method of Chinese patent that for example application number is 201210287898.6 is that ionic palladium is mixed with urethane resin and makes coating activation solution, be coated in plastic workpiece surface, the temperature of 150～200 ℃, toast again, then electroless copper.But the problem that this method exists is exactly this coating oven dry, rear surface presents hydrophobicity, and chemical copper plating solution is the aqueous solution, due to the existence of interfacial tension, must affect the plating of opening of electroless copper; The introducing of certain thickness resin glue simultaneously, because this resin glue has the thermal expansivity different from matrix, can make the bonding force of copper layer and dope layer reduce, for printed board or optical material etc., thermal expansivity or the strict material of stability requirement are not suitable for adopting this method.Application number is to propose at organic non-conductive matrix surface coated with conductive coating in 201110314195.3 Chinese patent, baking-curing afterwards, then take mechanical polishing to destroy hydrophobicity and expose active site, then electroless copper.The method that in the method, mechanical polishing exposes active site is for throwing the very difficult control of uniformity of light, especially for irregular workpiece.
Summary of the invention
The present invention will solve existing employing coating cladding process to make plastic workpiece surface having have the technical problem of the lack of homogeneity of the low and dope layer of the bonding force that opens plating difficulty, copper layer and dope layer of electroless copper of method of catalytic activity, and a kind of ionic metal coating and technique for the pre-treatment of plastic substrate chemical plating copper is provided.
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 by 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 the deionized water of 75～95 parts, to be made by ratio of weight and the number of copies;
Wherein biological binding agent monomer is a kind of in dopamine hydrochloride, noradrenalin, 5-hydroxydopamine, Droxidopa, alpha-methyldopa amine, dextrorotation DOPA, levodopa, alpha-methyldopa and nitro Dopamine HCL or wherein several combination;
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, take by ratio of weight and the number of copies 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 the deionized water of 65～90 parts;
Two, 2/3 deionized water is poured in container, added metal chelating agent to be stirred to dissolving;
Three, under whipped state, metal-salt is joined in container, to be dissolved after, add biological binder solution;
Four, under whipped state, wetting agent is joined in container, after stirring, remaining deionized water is poured in container, then stirred;
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.
The technique of utilizing the above-mentioned ionic metal coating for the pre-treatment of plastic substrate chemical plating copper to carry out the pre-treatment of plastic substrate chemical plating copper, specifically carry out according to the following steps:
One, surface of plastic matrix is carried out to electrochemical deoiling processing;
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;
Electrochemical deoiling is processed in the electrochemical deoiling liquid that specifically surface of plastic matrix is immersed in to 60～80 ℃ and is soaked 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 to the solution obtaining;
Two, the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper is coated in to the plastic basis material surface of processing through step 1, then under being the condition of 25～65 ℃, temperature dries 0.5～5min, on plastic basis material surface, obtain build and be the coating of 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 forces.In coating described in this technique, adopted the biological binding agent that contains catechol structure, the binding agent of this catechol structure derives from biological mussel mucus, can adhere to almost any plastic substrate.Process and to compare with conventional ion metal activation, the coating of this art breading and the reactive force between matrix are chemical bond but not grappling effect, therefore resulting electroless copper binding force of cladding material is very high.
2, technique is simple.
1) compare with applying catalytic coatings technique, coating dry film thickness, at Nano grade, without high temperature sintering, only needs low-temperature short-time to dry;
2) compare with applying catalytic coatings technique, dry rear surface and still present wetting ability, therefore expose catalytic activity point without 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) compare with traditional activation solution technique, without chemical roughen step, avoided using environmentally harmful coarsening solution, environmentally friendly;
4) without chemical reduction step.Compare with conventional ion metal activation method, saved with reductive agent reduction and obtained the step of electroless plating catalysed particulate, 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.
Compare with the catalytic solution that applies Coating Method employing with conventional plastic absorption method, metal ion exists with ionic condition in coating, and metal can with biological binding agent in catechol structure 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 high temperature sintering, and the catalytic performance and coating rear surface total hydrophilic, not the Presence of an interface strain problem that only need low-temperature short-time oven dry just to have; Not limited 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; Directly utilize self reductive agent of chemical plating solution to reduce, without increase reduction step as ionic metal activation solution in the past.By the method, can the technique by cheap and simple environmental protection obtain the electroless copper metal plating that bonding force is good, outward appearance is good at surface of plastic matrix.
Accompanying drawing explanation
Fig. 1 is 400 times of optical microscope photographs of the copper layer on embodiment 1PI plastics test piece surface;
Fig. 2 is 400 times of optical microscope photographs of copper layer on the epoxy resin glass-fiber-plate FR-4 surface of embodiment 2;
Fig. 3 is 400 times of optical microscope photographs of copper layer on the ABS plastic plate surface of embodiment 3;
Fig. 4 is 400 times of optical microscope photographs of copper layer of the PET plastic sheet 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 by 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 the deionized water of 75～95 parts, to be made by ratio of weight and the number of copies; Wherein biological binding agent monomer is a kind of in dopamine hydrochloride, noradrenalin, 5-hydroxydopamine, Droxidopa, alpha-methyldopa amine, dextrorotation DOPA, levodopa, alpha-methyldopa and nitro Dopamine HCL or wherein several combination.
The biological binding agent monomer of present embodiment all has catechol structure.
Embodiment two: present embodiment is different from embodiment one is that oxygenant in biological binder solution is a kind of in clorox, potassium permanganate, oxygen, ammonium persulphate and sodium peroxide or wherein several combination; Other is identical with embodiment one.
When oxygenant is composition, each oxygenant is by any combination.
Embodiment three: present embodiment is different from embodiment one or two is that pH buffer reagent in biological binder solution is borax, sodium-acetate, tris hydrochloride or SODIUM PHOSPHATE, MONOBASIC; Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that in biological binder solution, silane coupling agent is a kind of in KH550, KH792, KH560 and KH602 or wherein several combination; 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 improving with matrix.
Embodiment five: present embodiment is different from one of embodiment one to four is that the preparation method of biological binder solution is as follows:
A, take 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 the deionized water of 75～95 parts by ratio of weight and the number of copies;
B, 2/3 deionized water is poured in encloses container, added pH buffer reagent to be stirred to dissolving, and then add biological binding agent monomer, be stirred to monomer and all dissolve;
C, under agitation, joins oxygenant in encloses container, then temperature is warming up to 45～50 ℃ and keep reaction 20～24h by normal temperature;
D, silane coupling agent is joined in encloses container, continue at 45～50 ℃ and keep reaction 20～24h;
E, remaining deionized water is poured in encloses container, stirred, obtain biological binder solution.
Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that described metal-salt is palladium salt, silver salt, nickel salt or mantoquita; Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from embodiment six is that described palladium salt is a kind of in Palladous chloride, palladous sulfate and palladium or wherein several combination; 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 is different from embodiment six is that described silver salt is a kind of in Silver Nitrate, silver fluoride and silver perchlorate or wherein several combination; Other is identical with embodiment six.
When in present embodiment, silver salt is composition, various silver salt are by any combination.
Embodiment nine: present embodiment is different from embodiment six is that described nickel salt is a kind of in nickelous chloride, nickel sulfamic acid, single nickel salt, nickel acetate and basic nickel carbonate or wherein several combination; Other is identical with embodiment six.
When in present embodiment, nickel salt is composition, various nickel salts are by any combination.
Embodiment ten: present embodiment is different from embodiment six is that described mantoquita is a kind of in copper sulfate, cupric nitrate and cupric chloride or wherein several combination; Other is identical with embodiment six.
When in present embodiment, mantoquita is composition, various mantoquitas are by any combination.
Embodiment 11: what present embodiment was different from one of embodiment one to ten is that metal chelating agent is thanomin, quadrol, sodium ethylene diamine tetracetate and N, N, a kind of in N'N'-tetra-(2-hydroxypropyl) quadrol or wherein several combination; 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: present embodiment is different from one of embodiment one to 11 is that wetting agent is a kind of in sodium lauryl sulphate, sodium laurylsulfonate and sodium cetanesulfonate or wherein several combination; Other is identical with one of embodiment one to 11.
When in present embodiment, wetting agent is composition, each wetting agent is by any combination.
Embodiment 13: what present embodiment was different from one of embodiment one to 12 is that pH adjusting agent is ammoniacal liquor, hydrochloric acid or sulfuric acid; Other is identical with one of embodiment one to 12.
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, take by ratio of weight and the number of copies 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 the deionized water of 65～90 parts;
Two, 2/3 deionized water is poured in container, added metal chelating agent to be stirred to dissolving;
Three, under whipped state, metal-salt is joined in container, to be dissolved after, add biological binder solution;
Four, under whipped state, wetting agent is joined in container, after stirring, remaining deionized water is poured in container, then stirred;
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: the technique of utilizing the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in embodiment one to carry out the pre-treatment of plastic substrate chemical plating copper, specifically carry out according to the following steps:
One, surface of plastic matrix is carried out to electrochemical deoiling processing;
Two, the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper is coated in to the plastic basis material surface of processing through step 1, then under being the condition of 25～65 ℃, temperature dries 0.5～5min, on plastic basis material surface, obtain build and be the coating of 0.1～1 micron, complete the pre-treatment of plastic substrate chemical plating copper.
Embodiment 16: what present embodiment was different from embodiment 15 is that described plastic substrate is general engineering plastics or pcb substrate.Other are identical with embodiment 15.
Embodiment 17: what present embodiment was different from embodiment 15 or 16 is that 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.Other are identical with embodiment 15 or 16.
Embodiment 18: present embodiment is different from embodiment 15 or 16 is that electrochemical deoiling is processed in the electrochemical deoiling liquid that specifically surface of plastic matrix is immersed in to 60～80 ℃ and soaked 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 to the solution obtaining.Other are identical with embodiment 15 or 16.
With case verification beneficial effect of the present invention 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 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 the deionized water of 90 parts by ratio of weight and the number of copies;
B, 2/3 deionized water is poured in encloses container, added tris hydrochloride to be stirred to dissolving, and then add dopamine hydrochloride, be stirred to dopamine hydrochloride and all dissolve;
C, under agitation, joins ammonium persulphate in encloses container, then temperature is warming up to 50 ℃ and keep reaction 24h by normal temperature;
D, Silane coupling agent KH550 is joined in encloses container, continue at 50 ℃ and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stirred, obtain the biological binder solution of Dopamine HCL.
Two, utilize the biological binder solution of the synthetic Dopamine HCL of step 1 for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, concrete preparation method is as follows:
F, take 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 the deionized water of 84 parts by ratio of weight and the number of copies;
G, 2/3 deionized water is poured in container, added metal chelating agent sodium ethylene diamine tetracetate to be stirred to dissolving;
H, under whipped state, Palladous chloride is joined in container, to be dissolved after, add the biological binder solution of Dopamine HCL;
I, under whipped state, sodium lauryl sulphate is joined in container, after stirring, remaining deionized water is poured in container, then is stirred;
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, with the synthetic palladium ion metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2, carry out the pre-treatment of the special-purpose PI plastic substrate chemical plating of flexible printed circuit copper, its concrete technology step is as follows:
K, by the special-purpose PI plastics of flexible printed circuit, be cut into 2 * 2cm
2, 0.1 centimetre of thickness test piece, put into electrochemical deoiling liquid, in temperature, be, under the condition of 65 ℃, to soak 4min; After taking out, distilled water cleans, and dries up; Wherein electrochemical deoiling liquid is to obtain after the sodium carbonate of 40g/L sodium hydroxide and 25g/L is added to the water;
L, the palladium ion metallic paint that the PI plastics of processing through step 1 are immersed in for the pre-treatment of plastic substrate chemical plating copper soak 2min, then sample is taken out, at 50 ℃, dry 2min, obtain build and be the PI plastics test piece with ionic palladium dope layer of 0.5 micron; (can be by x-ray fluorescence spectrometry, selected palladium is internal standard element, sets up thickness-palladium content standard curve)
Four, in the PI plastics test piece of preparing in step 3, carry out electroless copper, specific as follows:
M, the concentration that is 0.04mol/L, Seignette salt by the concentration of copper sulfate are that the concentration of 0.2mol/L, sodium hydroxide is that the concentration of 0.25mol/L, 37% formaldehyde is that the concentration of 10mL/L, MBT is that 0.2mg/L adds copper sulfate, Seignette salt, sodium hydroxide, 37wt% formaldehyde and MBT in deionized water, stir, obtain chemical copper plating solution;
N, the test piece of PI plastics is put into the chemical copper plating solution of 40 ℃, plating 1h, obtains copper layer on PI plastics test piece surface, completes electroless copper.
In step 3, build utilizes x-ray fluorescence spectrometry, and selected palladium is internal standard element, sets up thickness-palladium content standard 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 μ m/h.
Coating deposition rate is at 1-3 μ m/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 levodopa of 5 parts, the clorox of 2 parts, the borax of 2 parts, the silane coupling agent KH560 of 1 part and the deionized water of 90 parts by ratio of weight and the number of copies;
B, 2/3 deionized water is poured in encloses container, added borax to be stirred to dissolving, and then add levodopa, be stirred to levodopa and all dissolve;
C, under agitation, joins clorox in encloses container, after clorox dissolves, temperature is warming up to 50 ℃ and keep reaction 24h by normal temperature;
D, silane coupling agent KH560 is joined in encloses container, continue at 50 ℃ and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stirred, obtain the biological binder solution of levodopa.
Two, utilize the biological binder solution of the synthetic levodopa of step 1 for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, concrete preparation method is as follows:
F, take 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 the deionized water of 78 parts by ratio of weight and the number of copies;
G, 2/3 deionized water is poured in container, added metal chelating agent quadrol to be stirred to dissolving;
H, under whipped state, Silver Nitrate is joined in container, to be dissolved after, add the biological binder solution of levodopa;
I, under whipped state, sodium lauryl sulphate is joined in container, after stirring, remaining deionized water is poured in container, then is stirred;
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, with the synthetic silver ions metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2, carry out the pre-treatment of rigid printed board base material epoxy resin glass-fiber-plate FR-4 basal body chemical plating copper, 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, 0.1 centimetre of thickness test piece, put into electrochemical deoiling liquid, in temperature, be, under the condition of 60 ℃, to soak 3min; After taking out, distilled water cleans, and dries up; Wherein electrochemical deoiling liquid is to obtain after the sodium carbonate of 30g/L sodium hydroxide and 25g/L is added to the water;
L, the silver ions metallic paint that the epoxy resin glass-fiber-plate of processing through step 1 is immersed in for the pre-treatment of plastic substrate chemical plating copper soak 2min, then sample is taken out, at 50 ℃, dry 2min, obtain build and be the epoxy resin glass-fiber-plate with ionic silver dope layer of 0.5 micron;
Four, on the epoxy resin glass-fiber-plate of preparing in step 3, carry out electroless copper, specific as follows:
M, the concentration that is 0.04mol/L, Seignette salt by the concentration of copper sulfate are that the concentration of 0.2mol/L, sodium hydroxide is that the concentration of 0.25mol/L, 37% formaldehyde is that the concentration of 10mL/L, MBT is that 0.2mg/L adds copper sulfate, Seignette salt, sodium hydroxide, 37wt% formaldehyde and MBT in deionized water, stir, obtain chemical copper plating solution;
N, the test piece of epoxy resin glass-fiber-plate is put into the chemical copper plating solution of 40 ℃, plating 1h, obtains copper layer 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 μ m/h.
The process of the test of example 3 the present embodiment 3 is as follows:
One, the biological binder solution of preparation 5-hydroxydopamine, its preparation method is as follows:
A, take the 5-hydroxydopamine of 5 parts, the potassium permanganate of 3 parts, the sodium-acetate of 2 parts, the silane coupling agent KH792 of 1 part and the deionized water of 84 parts by ratio of weight and the number of copies;
B, 2/3 deionized water is poured in encloses container, added sodium-acetate to be stirred to dissolving, and then add 5-hydroxydopamine, be stirred to 5-hydroxydopamine and all dissolve;
C, under agitation, joins potassium permanganate in encloses container, after potassium permanganate dissolves, temperature is warming up to 50 ℃ and keep reaction 24h by normal temperature;
D, silane coupling agent KH792 is joined in encloses container, continue at 50 ℃ and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stirred, obtain the biological binder solution of 5-hydroxydopamine.
Two, utilize the biological binder solution of the synthetic 5-hydroxydopamine of step 1 for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, concrete preparation method is as follows:
F, take 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 the deionized water of 78 parts by ratio of weight and the number of copies;
G, 2/3 deionized water is poured in container, added metal chelating agent sodium ethylene diamine tetracetate to be stirred to dissolving;
H, under whipped state, single nickel salt is joined in container, to be dissolved after, add the biological bonding of 5-hydroxydopamine
Agent solution;
I, under whipped state, sodium cetanesulfonate is joined in container, after stirring, remaining deionized water is poured in container, then is stirred;
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, with the synthetic nickel ion metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2, carry out the pre-treatment of ABS plastic basal body chemical plating copper, its concrete technology step is as follows:
K, by ABS plastic, be cut into 2 * 2cm
2, 0.125 centimetre of thickness test piece, put into electrochemical deoiling liquid, in temperature, be, under the condition of 65 ℃, to soak 3min; After taking out, distilled water cleans, and dries up; Wherein electrochemical deoiling liquid is to obtain after the sodium carbonate of 30g/L sodium hydroxide and 25g/L is added to the water;
L, the nickel ion metallic paint that the ABS plastic plate of processing through step 1 is immersed in for the pre-treatment of plastic substrate chemical plating copper soak 2min, then sample are taken out, and at 50 ℃, dry 2min, obtain build and be the ABS plastic plate of 0.8 micron;
Four, on the ABS plastic plate of preparing in step 3, carry out electroless copper, specific as follows:
M, press copper sulfate 0.04mol/L, glycine 0.2mol/L, sodium hydroxide 0.25mol/L, sodium hypophosphite 0.09mol/L, MBT 0.2mg/L adds copper sulfate, glycine, sodium hydroxide, sodium hypophosphite and MBT in deionized water, stir, obtain chemical copper plating solution;
N, the test piece of ABS plastic plate is put into the chemical copper plating solution of 75 ℃, plating 1h, obtains copper layer 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 μ m/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 Droxidopa of 10 parts, the ammonium persulphate of 3 parts, the SODIUM PHOSPHATE, MONOBASIC of 2 parts, the silane coupling agent KH602 of 1 part and the deionized water of 84 parts by ratio of weight and the number of copies;
B, 2/3 deionized water is poured in encloses container, added SODIUM PHOSPHATE, MONOBASIC to be stirred to dissolving, and then add Droxidopa, be stirred to Droxidopa and all dissolve;
C, under agitation, joins ammonium persulphate in encloses container, after ammonium persulphate dissolves, temperature is warming up to 50 ℃ and keep reaction 24h by normal temperature;
D, silane coupling agent KH602 is joined in encloses container, continue at 50 ℃ and keep reaction 24h;
E, remaining deionized water is poured in encloses container, stirred, obtain the biological binder solution of Droxidopa.
Two, utilize the biological binder solution of the synthetic Droxidopa of step 1 for the preparation of the ionic metal coating of plastic substrate chemical plating copper pre-treatment, 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) quadrol, the sodium cetanesulfonate of 1 part and the deionized water of 78 parts by ratio of weight and the number of copies;
G, 2/3 deionized water is poured in container, added metal chelating agent N, N, N'N'-tetra-(2-hydroxypropyl) quadrol is stirred to dissolving;
H, under whipped state, copper sulfate is joined in container, to be dissolved after, add the biological binder solution of Droxidopa;
I, under whipped state, sodium cetanesulfonate is joined in container, after stirring, remaining deionized water is poured in container, then is stirred;
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, with the synthetic cupric ion metallic paint for the pre-treatment of plastic substrate chemical plating copper of step 2, carry out the pre-treatment of PET plastic substrate chemical plating copper, its concrete technology step is as follows:
K, by PET plastics, be cut into 2 * 2cm
2, 0.1 centimetre of thickness test piece, put into electrochemical deoiling liquid, in temperature, be, under the condition of 60 ℃, to soak 3min; After taking out, distilled water cleans, and dries up; Wherein electrochemical deoiling liquid is to obtain after the sodium carbonate of 30g/L sodium hydroxide and 25g/L is added to the water;
L, the cupric ion metallic paint that the PET plastic plate of processing through step 1 is immersed in for the pre-treatment of plastic substrate chemical plating copper soak 2min, then sample are taken out, and at 50 ℃, dry 2min, obtain build and be the PET plastic plate of 0.8 micron;
Four, on the PET plastic plate of preparing in step 3, carry out electroless copper, specific as follows:
M, the concentration that is 0.04mol/L, Seignette salt by the concentration of copper sulfate are that the concentration of 0.2mol/L, sodium hydroxide is that the concentration of 0.25mol/L, 37% formaldehyde is that the concentration of 10mL/L, MBT is that 0.2mg/L adds copper sulfate, Seignette salt, sodium hydroxide, 37wt% formaldehyde and MBT in deionized water, stir, obtain chemical copper plating solution;
N, the test piece of PET plastic plate is put into the chemical copper plating solution of 40 ℃, plating 1h, obtains copper layer at PET plastic 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 μ m/h.
Coating deposition rate is at 2-3 μ m/h.
The chemical plating copper layer that above-mentioned 4 embodiment are obtained carries out the sign of outward appearance, bonding force, electroconductibility.The stability of ionic metal coating is carried out to centrifugal test and catalytic performance observation experiment simultaneously.
Outward appearance is observed with 400 times of opticmicroscopes, observes homogeneity and surface imperfection.Fig. 1 is 400 times of optical microscope photographs of the copper layer on embodiment 1PI plastics test piece surface; Fig. 2 is 400 times of optical microscope photographs of copper layer on the epoxy resin glass-fiber-plate FR-4 surface of embodiment 2; Fig. 3 is 400 times of optical microscope photographs of copper layer on the ABS plastic plate surface of embodiment 3; Fig. 4 is 400 times of optical microscope photographs of copper layer of the PET plastic sheet surface of embodiment 4.From Fig. 1～4, can find out, all copper layers that obtain are even zero defect all.
Bonding force adopts thermal shock test.Through 100 ℃ (25min), 0 ℃ of (frozen water 5min) thermal shock test 10 times, observes coating and has or not foaming, crackle and obscission.The bonding force situation of judgement copper coating.
The measurement of electroconductibility adopts universal meter, chooses the one side that exists together, at a distance of 2 points of 1cm on the face of test piece, surveys its resistance value, and the result obtaining 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 was weighed by the plating time of opening to 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.
In table, find out by ionic metal coating for electroless copper pre-treatment resulting successful.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 by 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 the deionized water of 75～95 parts, to be made by ratio of weight and the number of copies; Wherein biological binding agent monomer is a kind of in dopamine hydrochloride, noradrenalin, 5-hydroxydopamine, Droxidopa, alpha-methyldopa amine, dextrorotation DOPA, levodopa, alpha-methyldopa and nitro Dopamine HCL or wherein several combination.
2. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, is characterized in that oxygenant in biological binder solution is a kind of in clorox, potassium permanganate, oxygen, ammonium persulphate and sodium peroxide or wherein several combination.
3. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, is characterized in that pH buffer reagent in biological binder solution is a kind of in borax, sodium-acetate, tris hydrochloride or SODIUM PHOSPHATE, MONOBASIC or wherein several combination.
4. a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper according to claim 1, is characterized in that silane coupling agent in biological binder solution is a kind of in KH550, KH792, KH560 and KH602 or wherein several combination.
5. according to a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in claim 1,2,3 or 4, it is characterized in that the preparation method of biological binder solution is as follows:
A, take 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 the deionized water of 75～95 parts by ratio of weight and the number of copies;
B, 2/3 deionized water is poured in encloses container, added pH buffer reagent to be stirred to dissolving, and then add biological binding agent monomer, be stirred to monomer and all dissolve;
C, under agitation, joins oxygenant in encloses container, then temperature is warming up to 45～50 ℃ and keep reaction 20～24h by normal temperature;
D, silane coupling agent is joined in encloses container, continue at 45～50 ℃ and keep reaction 20～24h;
E, remaining deionized water is poured in encloses container, stirred, 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 in Palladous chloride, palladous sulfate and palladium or wherein several combination; Salt is a kind of in Silver Nitrate, silver fluoride and silver perchlorate or wherein several combination; Nickel salt is a kind of in nickelous chloride, nickel sulfamic acid, single nickel salt, nickel acetate and basic nickel carbonate or wherein several combination; Mantoquita is a kind of in copper sulfate, cupric nitrate and cupric chloride or wherein several combination.
7. according to a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in claim 1 or 6, it is characterized in that metal chelating agent is thanomin, quadrol, sodium ethylene diamine tetracetate and N, N, a kind of in N'N'-tetra-(2-hydroxypropyl) quadrol or wherein several combination.
8. according to a kind of ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in claim 1 or 6, it is characterized in that wetting agent is a kind of in sodium lauryl sulphate, sodium laurylsulfonate and sodium cetanesulfonate or wherein several combination.
9. the technique of utilizing the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper described in claim 1 to carry out the pre-treatment of plastic substrate chemical plating copper, is characterized in that this technique carries out according to the following steps:
One, surface of plastic matrix is carried out to electrochemical deoiling processing;
Two, the ionic metal coating for the pre-treatment of plastic substrate chemical plating copper is coated in to the plastic basis material surface of processing through step 1, then under being the condition of 25～65 ℃, temperature dries 0.5～5min, on plastic basis material surface, obtain build and be the coating of 0.1～1 micron, complete the pre-treatment of plastic substrate chemical plating copper.
10. the technique that utilization according to claim 9 is carried out the pre-treatment of plastic substrate chemical plating copper for the ionic metal coating of plastic substrate chemical plating copper pre-treatment, is characterized in that described plastic substrate is general engineering plastics or pcb substrate.
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