CN109811380A - A kind of conducting surface treatment method before ABS plastic plating - Google Patents
A kind of conducting surface treatment method before ABS plastic plating Download PDFInfo
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- CN109811380A CN109811380A CN201910217077.7A CN201910217077A CN109811380A CN 109811380 A CN109811380 A CN 109811380A CN 201910217077 A CN201910217077 A CN 201910217077A CN 109811380 A CN109811380 A CN 109811380A
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Abstract
The invention discloses the conducting surface treatment methods before a kind of plating of ABS plastic, utilize the excellent electric conductivity of graphene microchip and film forming, by certain means in the direct coated graphite ene coatings of surface of plastic products, assign the ABS plastic surface of insulation certain electric conductivity.The ABS plastic that surface prepared by the method for the present invention is coated with graphene conductive layer can be directly electroplated, eliminate the complicated cumbersome process such as roughening, sensitization, activation, chemical plating in traditional handicraft, it is safer environmentally friendly, simple and easy to do, and process flow and cost is greatly shortened, industrialization plating is carried out suitable for the ABS plastic of different shape and size, there is important practical application value.By the method for the invention in the graphene conductive layer uniformly continuous of ABS plastic surface coating, and adhesive force is good, can be directly electroplated.
Description
Technical field
The invention belongs to graphene technology and frosting processing technology fields, and in particular to before a kind of plating of ABS plastic
Conducting surface treatment method.
Background technique
In recent years, with advances in technology and new material continues to bring out, the non-gold such as plastics, glass, ceramics, gypsum
Belong to material industrially with using more and more extensive, moulded now before many with the products that metal makes in daily life
The products such as material replace, these all considerably reduce the weight and cost of product.But plastics also have the shortcomings that certain: non-conductive,
It is not thermally conductive, not wear-resisting, easily-deformable, not anti-pollution, lack metallic luster and aesthetics etc., to limit it to a certain extent
Use scope.If plating one layer of metal in frosting, it is possible to make up its disadvantage, greatly improve its service performance.Due to
Plastics itself cannot be conductive, and available one layer of metal layer after frosting is using specific process processing has plastics not only
Have the characteristics that sole mass is light, is also equipped with the property of metal, such as electric conductivity, wearability and conductivity of heat.Thus, frosting
Metallization process has obtained extensive concern, and quickly grows, oneself is widely used in shield technology, microelectric technique, electricity
The fields such as chemical protection, plated circuit.
Currently, the most widely used five big general-purpose plastics includes: polyethylene (PE), polypropylene (PP), polystyrene
(PS), polyvinyl chloride (PVC) and ABS.Wherein, ABS engineering plastics be as acrylonitrile, butadiene, it is styrene copolymerized made of three
Membered copolymer, polybutadiene (PB) are mutually dispersed in polyacrylonitrile-styrene phase (SAN) with minor matters.Therefore, ABS resin has both
The excellent performance of three kinds of monomers, not only have good toughness, chemical stability, lower price, impact resistance, heat resistance,
Lower temperature resistance, excellent electric property are also equipped with the features such as easy processing, product size are stable, lustrous surface is good, and are easy
Coating, coloring can carry out the secondary operation such as surface metallization, plating, welding, hot pressing and bonding, be widely used in it is mechanical,
The industrial circles such as space flight and aviation, automobile, shipbuilding, electronic apparatus, instrument and meter, bathroom accessory, weaving and building are a kind of purposes
Extremely wide thermoplastic engineering plastic.
For aesthetics, electrical and thermal conductivity, wearability and the corrosion resistance etc. for improving ABS plastic, it usually needs to ABS work
Part is electroplated.ABS plastic plated item has the characteristic of both plastics and metal: its specific gravity is small, and corrosion resistance is good,
Molding is easy, and the texture with metallic luster and metal also has the characteristics such as conductive, magnetic conduction and welding.Due to the coat of metal pair
The extraneous factors such as light, atmosphere stability with higher, thus after plastic electroplating metal, ageing of plastics can be prevented, plastics are extended
The service life of part.With the rapid development of industry, plastic electroplating using increasingly extensive, become incrustation in plastic product
One of the important means of.The intensity property of itself not only can be enhanced by plating for ABS plastic, but also make it have more good
Good chemical stability and electric conductivity, have dicoration, so that its application field of further expansion, can be applied to electronics
The fields such as industry, medical instrument, instrument and meter, automobile parts, mechanical part, daily necessities and interior decoration.
Both at home and abroad extensively in ABS, polypropylene, polysulfones, polycarbonate, nylon, phenolic glass fiber reinforced plastics, polyphenyl
It is electroplated on the frostings such as ethylene.So-called " plastic electroplating " refers to the form to be electroplated and chemical plating be combined with each other, applies
The coat of metal is covered in a kind of processing method of frosting.Through this processing, it is high-efficient, inexpensive, light that plastics-production can be retained
Benefit, while the features such as be allowed to have thermally conductive anti-aging, conductive, metal appearance, so plastic electroplating technique is at present light
Chemical product, lathe button, optical instrument, electronics etc. are applied widely.Especially in the levels such as functionality, engineering
The effect embodied has had increased to a series of Related products indispensable one of " process ".However utilizing different function
When the engineering plastics of energy, be faced with an important problem: plastics are as a kind of non-conductor, it is difficult to it is directly electroplated,
Therefore it needs to form one layer of tie coat on plastic basis material before being electroplated, it is good outer to guarantee to be connected substrate and metal layer
Sight and binding force.In order to plate one layer of metal layer in frosting, it usually needs conducting pretreatment is carried out to frosting,
Common processing method can be divided into two major classes: one kind is dry method, is primarily referred to as metallising and vacuum coating, and vacuum coating is
Plasma etching is needed by sputtering or evaporation coating one layer of metal layer of Direct precipitation, binding force on plastic basis material to protect
Card, applicability is limited, can be only applied to several thermoplastics；Another kind of is wet process, including is directly led in frosting coating
Electric glue, or frosting is handled by chemistry roughening, sensitization, activation and electroless copper or nickel plating, have the plastics of insulation
Certain electric conductivity.These surface treatment methods or the high requirements on the equipment, higher cost, or pollution is big, process is tedious, and
There are certain selectivity and limitation to the plastics of processing without exception.In order to solve restriction present in roughening, activation process,
Both at home and abroad to the engineering plastics Chrome-free such as ABS, PI, PA, PET, PVC, PC roughening and no-palladium activating chemical plating pre-processing technique into
A large amount of research is gone, for different plastic basis materials, coarsening solution is broadly divided into MnO2、H2SO4, NaOH three major controls, can after roughening
No-palladium activating is directly carried out, it can also be in organic ligand such as chitosan, polyacrylic acid, poly- pyrrole of the surface graft rich in active function groups
It coughs up, metallize again after silane coupling agent etc..
Traditional metallization process program is successfully, generally to use already, this need not query.Currently, ABS plastic
The electroplating technology generally used can be briefly divided into two big steps: the first step is the pre-treatment of plastic electroplating, i.e. preplating, passing through
Be plated in ABS plastic surface and cover one layer of conductive film, substantially process are as follows: oil removing-roughening-neutralization-sensitization-activation-reduction-chemistry
Nickel；Second step is plastic electroplating, i.e., is further electroplated on the basis of chemical plating, obtains better conjugation and glossiness, greatly
Cause process are as follows: nickel preplating-bright copper-semi-bright nickel-bright nickel-nickel envelope-light chromium.The coarsening process of traditional chemical plating uses
Strong oxidizing solutions, the activation processes such as a large amount of chromic anhydride, sulfuric acid have used the heavy metals such as a large amount of stannous salt, trivalent titanium salt
Salt, and activating solution used in activation process contains the noble metals such as Au Ag Pt Pd, process is cumbersome, higher cost, and preplating
Process can generate a large amount of waste water and heavy metal ion, for example Cr (VI) is easy to cause serious injury to human body and environment.For a long time
Cr (VI) is infected in the trade union that microetch workshop or chrome-plating plant work, even will appear nose septal perforator and skin when serious
Cancer.And as many as annual ten thousand tons of engineering plastics are by carrying out surface metalation after chromic anhydride-sulfuric acid system microetch, thus caused by ring
Border pollution is also evident from.It can be seen that it is necessary to study a kind of pre-plating process of more easy environmental protection, simplification of flowsheet,
And avoid largely using heavy metallic salt and noble metal, so that the preplating process of ABS plastic is more economic and environment-friendly.In addition to this, it grinds
Study carefully the demand that exploitation Chrome-free pre-plating process is not only able to satisfy modern industry, but also is for protection mankind itself and living environment
It is very necessary and very urgent.
Based on problems existing for chemical plating process, people actively attempt to cancel the non-conductor table of chemical plating process
The direct electroplating technology in face.There is research to handle Nonconductor surface using colloid palladium, colloid Pd particle is generated on Nonconductor surface
Semiconduction film, be subsequently placed in plating solution and be electroplated.As a result, it has been found that non-conductive along what is be catalyzed from conductive surface
Property surface sprawling growth coating, electrodeposition process is relatively slow, and thickness of coating is very uneven, the interface of neighbouring conductive surface
Coating is most thick, and apart from interface farthest, coating is very thin.Obvious this technique is not applicable, but it gives people but with direct
The enlightenment of plating, taking this as an opportunity by correlative study person, has carried out about the numerous studies being directly electroplated, and make directly electroplating technology
It constantly tends to be perfect and there is operability and practicability.
Therefore it is carried out outside electroless copper or nickel plating except through above-mentioned conventional method in frosting, in recent years about plastics
Electroplating technique improvement also emerges a large amount of achievement, have correlative study person by frosting load polypyrrole, polyaniline,
The conductive polymer materials such as polythiophene, PEDOT-PSS, poly- thio phenyl apply to form one layer of conductive transition on plastic basis material
Layer.Some researches show that by using certain density KMnO4, dense H2SO4After being roughened with emulsifier to ABS plastic, with pyrrole
It coughs up as monomer, FeCl3For primary oxidizers and dopant, conductive poly- pyrrole is formed in frosting by the method for oxidation polymerization
Film is coughed up, is then directly electroplated.Some researches show that three kinds of principal modes being directly electroplated on plastic substrate: conductive
Property macromolecule be directly electroplated, i.e., surface of plastic matrix coat one layer of macromolecule conducting material after be electroplated；Pd/Sn activation is straight
Connect plating, i.e., the Futuron technique invented by Atotech company forms metal Pd layer in frosting and is directly electroplated or Pd layers
It is electroplated again after catalytic copper displacement tin, although saving step, palladium in colloidal pd activation solution required for activation process
Comparision contents are high, and cost is also relatively high；Carbon particle suspension is directly electroplated, and so-called carbon particle suspension is by carbon particle, glues
The composition such as agent, surfactant and water-soluble high-molecular compound is tied, and carbon particle includes graphite particle and carbon black particle, is passed through
Spray, dipping and coating etc. processes the carbon particle for having electric conductivity is attached on plastic basis material, then through peracid at
Reason and microetch processing can be directly electroplated.There are also studies have shown that being catalyzed using the processing of chalkogenide solution non-
Conductive surface converts it into the catalytic metal chalkogenide conversion coating (such as PdS) for electric conductivity, uses as directly plating
Conductive substrates layer.But these method higher costs, and operating condition is also more harsh, is only applicable to experiment at present and grinds
Study carefully, industrial mass production can not be suitable for.
Graphene was successfully prepared, just because its is excellent as a kind of novel conductive carbon nanotube material from 2004
Thermal conductivity (5300Wm-1K-1, thermal conductivity are ten times of copper), (carrier mobility is up to 15000m2V- to electric conductivity at room temperature
1S-1), optical property (light transmittance up to 97.7%), perfect quantum tunneling effect, the quantum hall effect of half-integer, room temperature iron
Magnetic and superpower mechanical property (tensile strength 130GPa, Young's modulus about 1TPa) and the research for causing domestic and international researcher
Upsurge.Wherein, the excellent photoelectric properties of graphene and superpower mechanical property have it in conductive coating and field of compound material
There is huge application potential.It therefore, if can be by certain process, by grapheme material successful application in plastic products table
Face can not only make plastic products complete preplating process under conditions of heavy metal free and noble metal, and can push stone
The development and practical application of black alkene technology.Compared with conducting polymer and traditional carbon particle, grapheme material has better
Electric conductivity and mechanical property can be allowed to carry out self assembly film forming in frosting, and graphene is only by being modified it
Special two dimensional crystal structure makes it easier to plastic covering surface, and adhesive force is good.Some researches show that utilize conductive black itself
Electric conductivity, filming performance and its absorption property to metal ion form conductive layer on ABS plastic surface, then carry out electricity
Copper facing.Although the process avoids the techniques such as roughing in surface, activation, reduce the use of chromic acid, hydrochloric acid etc., but it is walked
Rapid still excessively cumbersome, since conductive blacking is easily reunited, and its electric conductivity can not show a candle to grapheme material, need first to carbon black
Particle carries out oxidation processes and carried metal nano particle, which needs using price precious metal salt costly and absolutely
The dispersion moisture agent of edge, so that its cost fails preferably to be controlled, and coated conductive also will receive large effect.
Some researches show that be put into graphene to be stirred in kneading machine and mix, then squeezed by screw rod with plastic resins such as ABS, PC
Machine extruding pelletization out obtains plastic electroplating part of the surface with micropore finally by injection molding.Utilize the plastic electroplating of this method
When workpiece is electroplated, chemical pre-treatment can be cancelled, shorten plating process, reduce environmental pollution.It is contemplated that graphite
Dispersion problem of the alkene material in resin matrix, this method are only applicable to fill out using graphene oxide and its derivative as inorganic
Material, applicability are relatively narrow.And be not significantly improved by plastic workpiece electric conductivity prepared by this method, only moulding
Material workpiece surface forms many micropores, mainly eliminates roughening step in the plating process, grapheme material it is other excellent
Performance is not fully utilized during plastic electroplating.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide the conduction before a kind of ABS plastic plating
Change surface treatment method, solves the problems in above-mentioned background technique.
The technical solution adopted by the present invention to solve the technical problems is: the conduction before providing a kind of plating of ABS plastic
Change surface treatment method, includes the following steps:
(1) oil removing alkali is prepared, surface degreasing processing is carried out to ABS plastic；
(2) it prepares graphene composite conductive slurry: taking 10~20 parts of conductive filler, mixed solvent 300~550 by mass parts
Part, 10~25 parts of auxiliary agent and 10~30 parts of link stuff, ground and mixed modification obtain composite conducting slurry；
Wherein, the conductive filler include graphene, carbon nanotube, conductive black, expanded graphite, in conductive carbon fibre
It is at least one；The mixed solvent is mixed by organic solvent and water with the volume ratio of 1:1~8:1, the organic solvent packet
It is sub- to include ethyl alcohol, ethylene glycol, glycerine, isopropanol, terpinol, methanol, formic acid, cyclohexanone, toluene, DMF, NMP, acetone, diformazan
At least one of sulfone, tetrahydrofuran, chloroform；The auxiliary agent by mass parts includes 1~5 part of dispersing agent, 1~2 part of defoaming agent, wet
Moisten 10~15 parts and 1~2 part of thickener of agent；
(3) graphene composite conductive slurry is coated on ABS plastic surface and be dried.
In a preferred embodiment of the present invention, the graphene is single-layer graphene, few layer graphene, multi-layer graphene.
In a preferred embodiment of the present invention, the oil removing lye of the step (1) by sodium hydroxide, sodium phosphate, sodium carbonate,
Emulsifier and distilled water are made, and the emulsifier includes at least one of OP emulsifier, detergent, surfactant.
In a preferred embodiment of the present invention, the concentration of sodium hydroxide is 20~80g/L, sodium phosphate in the oil removing lye
Concentration be 30~45g/L, the concentration of sodium carbonate is 15~50g/L, and the concentration of emulsifier is 1~5ml/L.
In a preferred embodiment of the present invention, step (1) oil removal treatment is soaked in ABS plastic in oil removing lye
And 10~40min is handled in 35~75 DEG C of waters bath with thermostatic control, it then takes out and wash with distilled water to remove remaining oil removing alkali
Then liquid is dried, oil removing ABS plastic product is obtained.
In a preferred embodiment of the present invention, the link stuff is starch, protein, water-based acrylic resin, polyurethane
Resin, vinyl acetate resin, modified epoxy, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose, poly- second
At least one of enol.
In a preferred embodiment of the present invention, the step (2) carries out ground and mixed using grinding instrument and is modified, described to grind
Grinding instrument includes planetary ball mill, sand mill, basket-type grinder, three-roll grinder, end runner mill, colloid mill or horizontal ball
Grinding machine.
In a preferred embodiment of the present invention, 3~48h of ground and mixed time of the step (2).
In a preferred embodiment of the present invention, graphene composite conductive slurry is coated on ABS plastic table by the step (3)
The method in face includes dip coating, spin-coating method, spray coating method, drop-coating or plasma spraying process.
In a preferred embodiment of the present invention, the step (3) uses forced air drying, vacuum drying, natural air drying, drying
Device is dry or infrared lamp is dry.
The technical program compared with the background art, it has the following advantages:
Compared in first time improvement, pre-plating solution is prepared using graphene oxide, organic solvent and water as raw material, utilization is organic
The swelling and microcorrosion effect that solvent generates ABS plastic, change the microstructure and ingredient on ABS plastic surface, improve its parent
Aqueous and adhesion strength obtains surface packet so that graphene oxide microplate is attached to frosting and assembles film forming after reduction
The ABS product for having covered redox graphene conductive layer, is able to carry out subsequent plating, although enormously simplifying the pre- of ABS plastic
Plating process, but the pre- plating time is more difficult to control, ABS plastic is easy to happen scraping or damage in organic in the mixed solvent, behaviour
The process of work need to extremely pay attention to.
Present invention process uses the more excellent two-dimensional graphene material of electric conductivity as presoma, your gold is not used
Belonging to material or toxicant, cost is lower, and it is more environmentally friendly, and electric conductivity is more preferable.Two-dimensional grapheme material is as ultra-thin paper
It opens equally, good dispersion can be carried out in green solvent by the modified method of simple step ground and mixed, then existed
Under the synergistic effect of water-soluble link stuff, uniform firm stone is formed on ABS plastic surface by process means such as spraying, dip-coatings
Black alkene conductive layer, and any type of damage will not be caused to ABS plastic, operation is extremely easy, can be enterprising in industrial production line
Row automatic processing, the conductive treatment technique before capable of greatly simplifying ABS plastic plating, products obtained therefrom electric conductivity is excellent,
It can be directly electroplated.
Preparation process of the invention is simple and easy to do, efficiency is higher, safer environmental protection, eliminates " roughening-in the prior art
Neutralization-sensitization-activation-reduction-chemical nickel " etc. is a series of cumbersome and poisons environment and the step of operator's health, Er Qieyu
Traditional melt-blending process is different, and the present invention directly passes through simple slurry cladding process, forms uniform jail in surface of plastic products
Solid conductive coating, process flow and cost has been greatly shortened, be suitable for industrialized production, have important practical application valence
Value；
In the present invention for ABS plastic surface conductance processing solution formula safety and environmental protection, cost is relatively low, innovatively with
The expensive materials such as price more cheap grapheme material substitution heavy metallic salt, noble metal and conducting polymer, to have
As mixed solvent, prepared preprocessing solution property is stable, easily stores, has wide range of applications for solvent and water, repeats
It uses, and subsequent recovery is facilitated to handle；
The graphene conductive layer uniformly continuous that present invention process method is coated in ABS plastic product surface, and adhesive force is good
It is good, ABS plastic product excellent electric conductivity and glossiness are imparted, subsequent electroplating processes can be directly carried out, helps to push away
The further development of the broader applications and graphene technology of dynamic ABS plastic product.
Detailed description of the invention
Fig. 1 is the method for the present invention process flow chart；
Fig. 2 (a) is the apparent picture of ABS plastic product that graphene composite conductive coating has been coated prepared by embodiment 1；
Fig. 2 (b) is the apparent picture after the ABS plastic plating of articles for having coated graphene composite conductive coating prepared by embodiment 1；
Fig. 3 (a) is the apparent picture of ABS plastic product that graphene conductive coating has been coated prepared by embodiment 2；Fig. 3
(b) the apparent picture after the ABS plastic plating of articles to have coated graphene conductive coating prepared by embodiment 2；
Fig. 4 (a) is the apparent picture of ABS plastic product that graphene composite conductive coating has been coated prepared by embodiment 3；
Fig. 4 (b) is the apparent picture after the ABS plastic plating of articles for having coated graphene composite conductive coating prepared by embodiment 3；
Fig. 5 (a) is the apparent picture of ABS plastic product that graphene composite conductive coating has been coated prepared by embodiment 4；
Fig. 5 (b) is the apparent picture after the ABS plastic plating of articles for having coated graphene composite conductive coating prepared by embodiment 4；
Fig. 6 (a) is the apparent picture of ABS plastic product that graphene composite conductive coating has been coated prepared by embodiment 5；
Fig. 2 (b) is the apparent picture after the ABS plastic plating of articles for having coated graphene composite conductive coating prepared by embodiment 5；
Fig. 7 (a) is the apparent picture of ABS plastic product that graphene composite conductive coating has been coated prepared by embodiment 6；
Fig. 7 (b) is the apparent picture after the ABS plastic plating of articles for having coated graphene composite conductive coating prepared by embodiment 6.
Specific embodiment
Embodiment 1
Please refer to Fig. 1, the conducting surface treatment method before a kind of ABS plastic plating of the present embodiment, it is characterised in that
Include the following steps:
(1) oil removing alkali is prepared, surface degreasing processing is carried out to ABS plastic；
Original ABS plastic product is soaked in progress water bath with thermostatic control processing in oil removing lye, thermostat temperature is 70 DEG C, oil removing
The processing time is 30min, with distilled water that the caustic dip of ABS plastic product surface is clean and dry later, spare；
Oil removing lye used is the sodium hydroxide that will centainly match, sodium phosphate, sodium carbonate and emulsifier mixed dissolution in steaming
It is formulated in distilled water, wherein the concentration of sodium hydroxide is 20~80g/L, and the concentration of sodium phosphate is 30~45g/L, sodium carbonate
Concentration be 15~50g/L, the concentration of emulsifier is 1~5mL/L；The emulsifier includes OP emulsifier, detergent, surface work
Property at least one of agent, emulsifier used by the present embodiment is the most common detergent in life.
(2) graphene composite conductive slurry: 190 parts of isopropanols and 120 parts of H is prepared2O is as mixed solvent, 10 parts of graphite
Alkene powder and 2 parts of multi-walled carbon nanotubes are as conductive filler, 5 parts of dispersing agents, 1 part of defoaming agent, 10 parts of wetting agents and 2 parts of thickeners
As auxiliary agent, 10 parts of water-based acrylic resins carry out a step ground and mixed after ultrasound is pre-dispersed, graphene are made as link stuff
Composite conducting slurry；The graphene is single-layer graphene, few layer graphene, multi-layer graphene；It is ground using grinding instrument
Grind mixed and modified, the grinding instrument includes planetary ball mill, sand mill, basket-type grinder, three-roll grinder, two-roll mill
Machine, colloid mill or horizontal ball mill, ground and mixed modified time are 3~48h.
(3) graphene composite conductive slurry is coated on ABS plastic surface and be dried；
Above-mentioned graphene composite conductive slurry is sprayed at the ABS plastic product surface after oil removing by spray gun, after dry
The ABS plastic product that surface has coated graphene composite conductive coating is obtained, as shown in Fig. 2 (a).Exist by the method for the invention
The graphene composite conductive layer uniformly continuous coated on ABS plastic product, and electric conductivity and adhesive force is good.
(4) the ABS plastic product for having coated graphene composite conductive coating is electroplated, coats metal layer, gained gold
Shown in ABS workpiece such as Fig. 2 (b) of categoryization.
Embodiment 2
Embodiment 2 the difference from embodiment 1 is that:
(1) oil removing lye is prepared, original ABS plastic product is soaked in progress water bath with thermostatic control processing in oil removing lye, it is permanent
Temperature is 70 DEG C, and the oil removal treatment time is 30min, with distilled water that the caustic dip of ABS plastic product surface is clean later
And it is dry, it is spare；
(2) raw material of following mass parts: 190 parts of isopropanols and 120 parts of H is taken2O is as mixed solvent, 15 parts of Graphene powders
Body is as conductive filler, and 1 part of dispersing agent, 1 part of defoaming agent, 10 parts of wetting agents and 1 part of thickener are as auxiliary agent, 15 parts of aqueous acrylamides
Acid resin carries out a step ground and mixed after ultrasound is pre-dispersed, graphene composite conductive slurry is made as link stuff；
(3) above-mentioned graphene composite conductive slurry is sprayed at by the ABS plastic product surface after oil removing by spray gun, it is dry
The ABS plastic product that surface has coated graphene conductive coating is obtained afterwards, as shown in Fig. 3 (a).By the method for the invention in ABS
The graphene conductive layer uniformly continuous coated on plastic products, and electric conductivity and adhesive force is good；
(4) the ABS plastic product for having coated graphene conductive coating is electroplated, coats metal layer, gained metallization
ABS workpiece such as Fig. 3 (b) shown in.
Embodiment 3
Embodiment 3 the difference from embodiment 1 is that:
(1) oil removing lye is prepared, original ABS plastic product is soaked in progress water bath with thermostatic control processing in oil removing lye, it is permanent
Temperature is 70 DEG C, and the oil removal treatment time is 30min, with distilled water that the caustic dip of ABS plastic product surface is clean later
And it is dry, it is spare；
(2) raw material of following mass parts: 315 parts of ethyl alcohol and 200 parts of H is taken2O is as mixed solvent, 10 parts of graphene powders
With 2 parts of multi-walled carbon nanotubes as conductive filler, 1 part of dispersing agent, 2 parts of defoaming agents, 10 parts of wetting agents and 2 parts of thickeners are used as and help
Agent, 10 parts of water-based acrylic resins carry out a step ground and mixed after ultrasound is pre-dispersed, graphene composite guide are made as link stuff
Plasma-based material；
(3) the ABS plastic product after oil removing is soaked in above-mentioned graphene composite conductive slurry and carries out coating processing, soaked
The painting time is 30s, the ABS plastic product that surface has coated graphene composite conductive coating is obtained after dry, as shown in Fig. 4 (a).
The graphene composite conductive layer uniformly continuous coated on ABS plastic product by the method for the invention, and electric conductivity and adhesive force
Well；
(4) the ABS plastic product for having coated graphene composite conductive coating is electroplated, coats metal layer, gained gold
Shown in ABS workpiece such as Fig. 4 (b) of categoryization.
Embodiment 4
Embodiment 4 the difference from embodiment 1 is that:
(1) oil removing lye is prepared, original ABS plastic product is soaked in progress water bath with thermostatic control processing in oil removing lye, it is permanent
Temperature is 70 DEG C, and the oil removal treatment time is 30min, with distilled water that the caustic dip of ABS plastic product surface is clean later
And it is dry, it is spare；
(2) raw material of following mass parts: 315 parts of isopropanols and 200 parts of H is taken2O is as mixed solvent, 15 parts of Graphene powders
As conductive filler, 6 parts of dispersing agents, 1 part of defoaming agent, 15 parts of wetting agents and 1 part of thickener are used as and help for body and 5 parts of conductive blacks
Agent, 30 parts of water-based acrylic resins carry out a step ground and mixed after ultrasound is pre-dispersed, graphene composite guide are made as link stuff
Plasma-based material；
(3) the ABS plastic product after oil removing is soaked in above-mentioned graphene composite conductive slurry and carries out coating processing, soaked
The painting time is 90s, the ABS plastic product that surface has coated graphene composite conductive coating is obtained after dry, as shown in Fig. 5 (a).
The graphene composite conductive layer uniformly continuous coated on ABS plastic product by the method for the invention, and electric conductivity and adhesive force
Well；
(4) the ABS plastic product for having coated graphene composite conductive coating is electroplated, coats metal layer, gained gold
Shown in ABS workpiece such as Fig. 5 (b) of categoryization.
Embodiment 5
Embodiment 5 the difference from embodiment 1 is that:
(1) oil removing lye is prepared, original ABS plastic product is soaked in progress water bath with thermostatic control processing in oil removing lye, it is permanent
Temperature is 70 DEG C, and the oil removal treatment time is 30min, with distilled water that the caustic dip of ABS plastic product surface is clean later
And it is dry, it is spare；
(2) raw material of following mass parts: 155 parts of isopropanols, 155 parts of ethyl alcohol and 200 parts of H is taken2O is as mixed solvent, and 10
Part graphene powder and 2 parts of multi-walled carbon nanotubes are as conductive filler, 5 parts of dispersing agents, 2 parts of defoaming agents, 10 parts of wetting agents and 2 parts
As auxiliary agent, 10 parts of water-based acrylic resins carry out a step ground and mixed after ultrasound is pre-dispersed, are made thickener as link stuff
Graphene composite conductive slurry；
(3) above-mentioned graphene composite conductive slurry is sprayed at by the ABS plastic product surface after oil removing by spray gun, it is dry
The ABS plastic product that surface has coated graphene composite conductive coating is obtained afterwards, as shown in Fig. 6 (a).Exist by the method for the invention
The graphene composite conductive layer uniformly continuous coated on ABS plastic product, and electric conductivity and adhesive force is good；
(4) the ABS plastic product for having coated graphene composite conductive coating is electroplated, coats metal layer, gained gold
Shown in ABS workpiece such as Fig. 6 (b) of categoryization.
Embodiment 6
Embodiment 6 the difference from embodiment 1 is that:
(1) oil removing lye is prepared, original ABS plastic product is soaked in progress water bath with thermostatic control processing in oil removing lye, it is permanent
Temperature is 70 DEG C, and the oil removal treatment time is 30min, with distilled water that the caustic dip of ABS plastic product surface is clean later
And it is dry, it is spare；
(2) raw material of following mass parts: 315 parts of ethyl alcohol, 90 parts of terpinols and 100 parts of H is taken2O is as mixed solvent, and 15 parts
Graphene powder and 3 parts of multi-walled carbon nanotubes are as conductive filler, 1 part of dispersing agent, 2 parts of defoaming agents, 10 parts of wetting agents and 2 parts of increasings
Thick dose is used as auxiliary agent, and 10 parts of water-based acrylic resins carry out a step ground and mixed after ultrasound is pre-dispersed, stone is made as link stuff
Black alkene composite conducting slurry；
(3) above-mentioned graphene composite conductive slurry is sprayed at by the ABS plastic product surface after oil removing by spray gun, it is dry
The ABS plastic product that surface has coated graphene composite conductive coating is obtained afterwards, as shown in Fig. 7 (a).Exist by the method for the invention
The graphene composite conductive layer uniformly continuous coated on ABS plastic product, and electric conductivity and adhesive force is good；
(4) the ABS plastic product for having coated graphene composite conductive coating is electroplated, coats metal layer, gained gold
Shown in ABS workpiece such as Fig. 7 (b) of categoryization.
As shown in the figure a in Fig. 2-7, the graphene that 6 embodiments are coated in ABS plastic product surface in the present invention is compound
Conductive coating uniformly continuous, and it is very smooth, adhesive force is good.Graphene composite conductive coating also has certain silver grey coloured gold
Belong to gloss, while assigning the plastic products electric conductivity such as ABS, also substantially increases the brightness, wear-resisting of the plastic products such as ABS
Property and corrosion resistance.As shown in the figure b in Fig. 2-7, surface obtained by 6 embodiments has coated graphene composite guide in the present invention
The ABS plastic product of electrocoat is able to carry out subsequent plating, and the coat of metal is uniform and smooth, such as bright finish, and will not
It falls off or deforms, impart a series of excellent performances such as ABS plastic product aesthetics, wearability, thermal conductivity and stain resistance, from
And the application range of energy further expansion ABS plastic product.It can be seen that being coated by the method for the invention in surface of plastic products
After graphene conductive layer, plastic products can directly carry out subsequent plating, enormously simplify the plating front surface processing work of plastics
Skill.
Table 1 is ABS product surface resistivity, the stone that graphene conductive layer has been coated obtained by 6 specific embodiments of the present invention
Black alkene conductive layer adhesive force and its coat of metal adhesive force.
Table 1
In conclusion in conjunction with the ABS product surface resistivity, the graphene that have coated graphene composite conductive layer in table 1
The test result of composite conductive layers adhesive force and its coat of metal adhesive force, before illustrating a kind of ABS plastic plating of the invention
Conducting surface treatment method is practicable.Firstly, being changed after selecting suitable solvent and auxiliary agent by a step ground and mixed
The method of property can load dispersant molecule on the carbon nanomaterials such as graphene microchip, and the carbon such as graphene microchip is effectively prevent to receive
Rice material occurs to reunite in a solvent and settle, and forms stable graphene composite conductive slurry, the link stuff in slurry then can
Enough improve the adhesive property between carbon nanomaterial and plastic basis material.Then, pass through the techniques sides such as spraying, dip-coating, spin coating, drop coating
Graphene composite conductive slurry is adhered to the surface of plastic products by method, is formed graphene conductive layer in surface of plastic products, is made
The plastic products of insulation have good electric conductivity, so that preplating process is completed, in order to which plastic products directly carry out subsequent electricity
Plating.The method of the present invention is successfully realized the Chrome-free preplating of ABS plastic product, enormously simplifies pre-plating process.Side through the invention
The graphene conductive layer uniformly continuous that method is coated in ABS product surface, adhesive force is good, and has lower surface resistivity,
Meet the requirement of industrial production and application.Coated graphene composite conductive layer ABS plastic product can directly carry out it is subsequent
Electroplating processes, it is the application of ABS product that success, which is overplated with uniform bright and the excellent coat of metal of adhesive force in product surface,
Provide more possibility.Therefore, the technology of the present invention can be applied to industrialization large scale preparation ABS plated item.
Skilled person will appreciate that when technical parameter of the invention changes in the following range, it is contemplated that obtain
Same as the previously described embodiments or similar technical effect:
The link stuff is starch, protein, water-based acrylic resin, polyurethane resin, vinyl acetate resin, modified ring
At least one of oxygen resin, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol.
The method that graphene composite conductive slurry is coated on ABS plastic surface by the step (3) includes dip coating, spin coating
Method, spray coating method, drop-coating or plasma spraying process.
The step (3) is dry using forced air drying, vacuum drying, natural air drying, drier drying or infrared lamp.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. the conducting surface treatment method before a kind of ABS plastic plating, it is characterised in that include the following steps:
(1) oil removing alkali is prepared, surface degreasing processing is carried out to ABS plastic；
(2) prepare graphene composite conductive slurry: by mass parts take 10~20 parts of conductive filler, 300~550 parts of mixed solvent,
10~25 parts and 10~30 parts of link stuff of auxiliary agent, ground and mixed modification obtains composite conducting slurry；
Wherein, the conductive filler include graphene, carbon nanotube, conductive black, expanded graphite, in conductive carbon fibre at least
It is a kind of；The mixed solvent is mixed by organic solvent and water with the volume ratio of 1:1~8:1, and the organic solvent includes second
Alcohol, ethylene glycol, glycerine, isopropanol, terpinol, methanol, formic acid, cyclohexanone, toluene, DMF, NMP, acetone, dimethyl sulfoxide, four
At least one of hydrogen furans, chloroform；The auxiliary agent includes 1~5 part of dispersing agent, 1~2 part of defoaming agent, wetting agent by mass parts
10~15 parts and 1~2 part of thickener；
(3) graphene composite conductive slurry is coated on ABS plastic surface and be dried.
2. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
Stating graphene is single-layer graphene, few layer graphene, multi-layer graphene.
3. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
The oil removing lye for stating step (1) is made of sodium hydroxide, sodium phosphate, sodium carbonate, emulsifier and distilled water, and the emulsifier includes
At least one of OP emulsifier, detergent, surfactant.
4. the conducting surface treatment method before a kind of ABS plastic plating according to claim 3, it is characterised in that: institute
The concentration for stating sodium hydroxide in oil removing lye is 20~80g/L, and the concentration of sodium phosphate is 30~45g/L, and the concentration of sodium carbonate is
15~50g/L, the concentration of emulsifier are 1~5ml/L.
5. the conducting surface treatment method before a kind of ABS plastic plating according to claim 4, which is characterized in that institute
State step (1) oil removal treatment be ABS plastic is soaked in oil removing lye and in 35~75 DEG C of waters bath with thermostatic control processing 10~
40min, then take out and wash with distilled water to remove remaining oil removing lye, then dry, acquisition oil removing ABS plastic system
Product.
6. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
Stating link stuff is starch, protein, water-based acrylic resin, polyurethane resin, vinyl acetate resin, modified epoxy, hydroxyl
At least one of propyl methocel, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol.
7. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
It states step (2) to be modified using grinding instrument progress ground and mixed, the grinding instrument includes planetary ball mill, sand mill, basket
Formula grinder, three-roll grinder, end runner mill, colloid mill or horizontal ball mill.
8. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
State 3~48h of ground and mixed time of step (2).
9. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
State step (3) by graphene composite conductive slurry be coated on ABS plastic surface method include dip coating, spin-coating method, spray coating method,
Drop-coating or plasma spraying process.
10. the conducting surface treatment method before a kind of ABS plastic plating according to claim 1, it is characterised in that: institute
It is dry using forced air drying, vacuum drying, natural air drying, drier drying or infrared lamp to state step (3).
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