CN102517618B - Copper drawing and electroplating method for plastic substrate - Google Patents
Copper drawing and electroplating method for plastic substrate Download PDFInfo
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- CN102517618B CN102517618B CN201110448699.4A CN201110448699A CN102517618B CN 102517618 B CN102517618 B CN 102517618B CN 201110448699 A CN201110448699 A CN 201110448699A CN 102517618 B CN102517618 B CN 102517618B
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Abstract
The invention relates to a copper drawing and electroplating method for a plastic substrate, and relates to a plastic surface wire drawing treatment method. According to the method, a plastic substrate is pretreated; the pretreated plastic substrate is subjected to physical vapor deposition metallization, and is sequentially subjected to physical vapor deposition plasma modification, metal bottom layer plating, metal transition layer plating and metal conductive layer plating; direct copper electroplating is performed; a drawing treatment is performed on the surface of the copper electroplating layer; a dry cleaning treatment is performed on the surface of the plastic substrate; nickel electroplating is performed; the resulting material is hung in a PVD furnace to carry out a plasma treatment, and then is subjected to a PVD film plating treatment, or an organic coating spray plating treatment is performed, or a chromium electroplating treatment is performed, or chromium electroplating is performed and finally a PVD film plating treatment is performed. With the present invention, the surface metallization of the plastic material can be achieved; the copper electroplating layer drawing is adopted to replace the nickel electroplating layer drawing so as to reduce the production cost, simplify the electroplating process, substantially reduce the discharge amount of the wastewater, and reduce the pollution to the environment and the human; and the method meets surface drawing function requirements of a plurality of the plastic substrates.
Description
Technical field
The present invention relates to a kind of frosting wire drawing treatment process, especially relate to a kind of plastic basis material copper wire drawing environment-friendly type and electroplate method.
Background technology
The chromic acid alligatoring and the hexavalent chromium plating chromium that in conventional plastic electroplating technique, all comprise high density, and sexavalent chrome can be discharged in electroplating wastewater conventionally, the chromium in waste water is larger to human body and environmental hazard! The hexavalent chromic anhydride of common chromium cpd, potassium bichromate, sodium dichromate 99, potassiumchromate, Sodium chromate etc.; The chromium sesquioxide of trivalent (chrome green, Cr
2o
3); The chromous oxide of divalence.The strongest with sexavalent chrome toxicity in the compound of chromium, trivalent chromium takes second place.Show according to the study, chromium is Mammals life and healthy required trace element.Lack chromium and can cause atherosclerosis.Per day for adults needs 500～700 μ g chromium, and in general messes every day 50～100 μ g only can be provided.The full cereal brown rice of brown sugar, unpurified oil, millet, Radix Dauci Sativae, pea are higher containing chromium.Chromium has hormesis to plant-growth, and trace chromium can improve plant harvest yield; But concentration is slightly high, can suppress again the nitrification of organic substance in soil.Chromic acid, dichromic acid and its esters have stimulation and calcination effect and cause wound, contact dermatitis people's sticking to mould and skin.These compounds enter human body with steam or dust mode, all can draw the pulmonary lesion of middle perforation of nasal septum, stomach illness, white cell decline, similar asthma.Skin contact chromium compounds, can cause " chrome ulcer " that healing is extremely slow, and in air, the concentration of chromic trioxide reaches 0.15～0.31mg/m
3time just can make perforation of nasal septum.Trivalent chromium or a kind of protein coacervation agent.Someone thinks, sexavalent chrome can bring out lung cancer.In addition, sexavalent chrome, particularly chromic acid have the effect of strong cultures shop to sewerage metallic conduit, and the sodium dichromate 99 that concentration is 0.31mg/L gets final product corrosion pipeline.Trivalent chromium waste water containing 34～17.3mg/L is filled with field, just can make all dunsiektes.
Chinese patent CN100552093C discloses a kind of special activating agent for plastic electroplating and electroplating technology, alligatoring in this technical process, and electrodeposited chromium adopts a large amount of chromic acid (sexavalent chrome), is not used as recycling, big for environment pollution.
Chinese patent CN101555614B discloses a kind of plastic surface galvanizing method, and it provides a plastic substrate; This matrix surface is carried out to pre-treatment, and this matrix surface forms a copper plate, in the copper plate surface of this matrix, with mountain valency chromium, electroplates the-the first chromium layer, at the first hexavalent chromium plating-the second chromium layer for chromium layer surface of this matrix.
Chinese patent 200910135647 discloses a kind of metal material surface copper imitation wire drawing process.Its technical scheme is: 1) metal material surface conventional chemical pre-treatment, makes metallic surface clean and smooth; 2) electrostatic spraying is containing the outdoor powder coating of transparent red or the pure transparent outdoor powder coating of pigment; 3) to imitate the thermographic transfer paper of the dark-grey blueness of copper background color or black straight burr, carry out hot transfer printing, obtain imitative copper wire-drawing effect.
Chinese patent 201110128133 discloses a kind for the treatment of process of product surface, and its flow process is: to aluminium alloy compression casting moulding processing, polished and cleaned is done in its surface, then pass through ultrasonic cleaning foul; Heavy zinc cleans again, after the heavy zinc of secondary cleans again, carries out nickel preplating in nickel bath, after nickel preplating min, cleans; Activation is cleaned, and in copper plating groove, carries out copper facing; Copper facing is by cleaning, and activation is cleaned and in nickel bath, carried out bright nickel plating again; Through cleaning after entering baking oven and drying, carry out wire drawing; After completing, wire drawing carries out electrostatic painting; Product after electrostatic painting enters through circular trackway in the baking chamber of constant temperature and dries, and the product after oven dry is the selected finished product that is mounted to again.
Chinese patent 201110080260 discloses a kind of method of implementing imitative metal wire-drawing plated film on engineering plastic surface, and its step comprises: in plastic mother granules, add pigment, the processing of dyeing; Plastic cement blank is carried out to dry clean and activation; Plastic cement blank is coated with to look coating; Workpiece is carried out to wire drawing, obtain the surface of wire drawing lines; Workpiece is carried out to dry clean and activation; By the Workpiece painting Lacquer finish finish paint of wire drawing lines, complete on engineering plastic surface and implement imitative metal wire-drawing plated film.
In plating production process, produce a large amount of waste water and a large amount of energy consumption of waste, a full automatic output is 20,000 m
2/ plating line monthly, the waste water of monthly getting rid of is 2500 tons.So many waste water is waste water resource not only, and the serious natural ecological environment that is polluting the mankind, therefore in the urgent need to improving or replacing existing electroplating technology.The wire drawing common process flow process of existing plastic electroplating is: removing oil-removing wax, alligatoring, activation, sensitization, then reduction, chemical nickel, the burnt copper of plating, electroplating acid copper, electronickelling carry out wire drawing, oil removing, activation, electrodeposited chromium or last PVD, produce a large amount of waste water and heavy metal contaminants, and on metal nickel dam, carry out wire drawing and waste expensive metallic nickel.
Summary of the invention
The object of the invention is to electroplate for existing plastic cement the shortcoming and deficiency existing in drawing process, a kind of surface metalation that can realize plastic material is provided, adopt copper electroplating layer wire drawing to replace existing electroless nickel layer wire drawing, reduce production costs, simplify electroplating technology flow process, significantly reduce wastewater discharge, reduce the pollution to environment and the mankind, be applicable to the plastic basis material copper wire drawing electric plating method of multiple plastic rubber substrate surface wire drawing functional requirement.
The present invention includes following steps:
1) plastic basis material is carried out to pre-treatment;
2) to through step 1) pretreated plastic rubber substrate carries out physical vapor deposition (PVD) metallization, and carry out successively physical vapor deposition plasma modification, metallizing bottom, metal be layer and metal conducting layer excessively;
3) to through step 2) plastic rubber substrate processed directly carries out electro-coppering;
4) to through step 3) the copper electroplating layer surface of the plastic rubber substrate processed carries out wire drawing processing;
5) to through step 4) the plastic rubber substrate surface of processing carries out dry cleaning processing;
6) to through step 5) plastic rubber substrate processed carry out electronickelling;
7) to through step 6) plastic rubber substrate processed turns linked to PVD stove and carries out, after Cement Composite Treated by Plasma, carrying out PVD coating film treatment, to meet various functions, color requirement; Or
To through step 5) plastic rubber substrate processed is dry carries out the processing of spraying plating organic coating; Or
To through step 5) plastic rubber substrate processed is dry carries out electrodeposited chromium processing; Or
To through step 5) the dry electrodeposited chromium that carries out of plastic rubber substrate processed, finally carries out PVD coating film treatment and meets various functions, color requirement.
In step 1) in, described pre-treatment, can adopt dry cleaning method oil removing scrubbing, the concrete grammar of described employing dry cleaning method oil removing scrubbing can adopt plasma flame to process, dry ice oil removal treatment, Electrostatic Treatment, at least one in the methods such as hydrocarbon vacuum cleaned.
In step 2) in, the processing condition of described physical vapor deposition plasma modification can be ion source electric current 0.3～0.5A, bias voltage 80～150V, dutycycle 50%～80%, argon gas flow velocity 10～100SCCM, oxygen gas flow rate 10～150SCCM, vacuum pressure 0.1～0.3Pa in stove, soak time 5～10min, to reach clean and to change the object that activates matrix surface; The processing condition of described metallizing bottom, the excessive layer of metal and metal conducting layer can be and adopt high-power medium-frequency pulse or high-power DC power supply, supply current is 50～300A, voltage is 400～800V, depositing time is 1～10min, bias voltage 20～60V, dutycycle 50%～80%, argon gas flow velocity 60～200SCCM.
In step 3) in, describedly directly carry out electro-coppering and can be selected from and electroplate cupric pyrophosphate, electroplate at least one in husky copper etc.; The method of described electro-coppering can adopt the known various electro-plating methods of person of ordinary skill in the field, owing to electroplating thickness and the quality of more easily controlling product electrolytic coating, and electroplates through multi-layer plating product quality out excellent;
The method of described electro-coppering is to using through step 2) plastic rubber substrate processed is as negative electrode, and copper coin is as anode, adopts that to electroplate the formula of husky copper as follows: copper sulfate CuSO
4200 ± 10g/L, sulfuric acid H
2sO 65 ± 15g/L, chlorion Cl
-80～120ppm, husky agent 303 8～12ml/L, the temperature of plating solution can be 25～40 ℃, is preferably 28～35 ℃, and galvanic current density can be 2～8A/dm
2, be preferably 3～6A/dm
2, electroplating time can be 5～40min; The adoptable formula of technique of described plating cupric pyrophosphate is as follows: cupric pyrophosphate 70 ± 10g/L, potassium pyrophosphate 300 ± 50g/L, ammoniacal liquor (28%) 1～3mL/L, cupric ion 25～35g/L, additive RS751 0.1～0.2ml/L, pH 8.5～9.5, and the temperature of plating solution can be 45～55 ℃, and galvanic current density can be 0.5～2A/dm
2, electroplating time can be 5～10min; The electroplating acid copper formula that the formula of the husky copper of described plating can adopt Le Si company to provide; The formula that the technical recipe of described plating cupric pyrophosphate can adopt Yong Xing chemical company to provide;
As adopted, electroplate cupric pyrophosphate and electroplate husky process for copper, washing process together with having with between the husky copper of plating at plating cupric pyrophosphate, the method for described washing and condition are conventionally known to one of skill in the art, the method adopts pure water rinsing 1～2min.
In step 3) plastic basis material is directly implemented to new-type environment-protection electroplating technique, new-type environment-protection electroplating is to carry out according to following standard: 1) to the washing bath of copper electroplating groove, adopt the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of cupric ion respectively; 2) to the washing bath of copper electroplating groove, adopt the mode of ion exchange resin or ultra-filtration membrane to recycle the water of washing use respectively.
In step 4) in, described wire drawing is processed, and can adopt automatic or artificial mode to carry out wire drawing, and the rotating speed of drawing wire machine can be 500～1000r/min; Pulling wheel can be nylon wheel, abrasive belt wheel, at least one in all-wing aircraft wheel etc.
In step 5) in, the concrete grammar that described employing dry cleaning is processed can adopt plasma flame to process, dry ice oil removal treatment, Electrostatic Treatment, at least one in the methods such as hydrocarbon vacuum cleaned.
In step 6) in, described electronickelling, electrodepositable is without at least one in leveling nickel, Bright Nickel Electroplating etc.; The method of described electronickelling can adopt the known various electro-plating methods of person of ordinary skill in the field, owing to electroplating thickness and the quality of more easily controlling product electrolytic coating, and electroplates through multi-layer plating product out more excellent.
The method of described electronickelling can the plastic rubber substrate after wire drawing is processed be negative electrode, and nickel plate is anode.Without leveling nickel plating, electroplate adoptable formula as follows: single nickel salt NiSO
4250～350g/L, nickelous chloride NiCl
230～68g/L, boric acid H
3bO
338～53g/L, pH 4.0～4.2, brightening agent BR 220 auxiliary 20～30ml/L, brightening agent BR 220 opens cylinder agent 7.5～15ml/L, SB 2000.5～1.5ml/L, NAW-A 2.5～4.0ml/L, the temperature of described plating solution can be 40～60 ℃, be preferably 50～60 ℃, galvanic current density can be 0.5～7A/dm
2, be preferably 2～5A/dm
2, electroplating time can be 5～30min; Without leveling nickel plating solution, can adopt the formula of the electronickelling that U.S. Luo Menha company provides.
The plating solution of described Bright Nickel Electroplating can adopt the formula of the plating light quantity nickel that U.S. Luo Menha company provides as follows: single nickel salt NiSO
4270～375g/L, nickelous chloride NiCl
235～45g/L, boric acid H
3bO
338～50g/L, pH 3.8～4.5, brightening agent SB200 4.0～7.5ml/L, brightening agent SB201 0.75～1.25ml/L, brightening agent NAW-A 1.0～4.0ml/L, the temperature of described plating solution can be 50～65 ℃, be preferably 58～60 ℃, galvanic current density can be 2～7 A/dm
2, be preferably 3～4A/dm
2, electroplating time can be 5～30min.
Described plating can be carried out activation treatment before flattening nickel, the method of described activation treatment and condition are conventionally known to one of skill in the art, described activating treatment process can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator V-3745g/L, soak time is 1～2min, and temperature is room temperature.
Described electronickelling can be carried out according to following standard: 1) washing bath after electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of nickel ion respectively; 2) mode that the washing bath after electronickelling groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
In step 7) in, described organic coating, is to adopt following methods to realize: 1) carry out electrophoretic painting, 2) carry out powder spraying, 3) carry out ultraviolet light polymerization (UV) spraying, 4) carry out polyurethane paint (PU) spraying.The spraying method of 4 kinds of organic coatings is method known in those skilled in the art, and the thickness of organic coating can be 10～30 μ m.
In step 7) in, the method that the method for described electrodeposited chromium and condition are known to the skilled person, the present invention adopts toxicological harmless to obtain trivalent chromium plating technology, chromic plating solution can adopt the formula of the electrodeposited chromium plating solution that U.S. Luo Menha company provides as follows: 3C opens cylinder salt 375～450g/L, 3C joins cylinder liquid 6～25ml/L, 3C stablizer 55～65ml/L, 3C wetting agent 9～15ml/L, 3C complexing agent 0.75～1.5ml/L, pH 2.6～3.1.The temperature of described plating solution comprises that the temperature of plating solution is 30～40 ℃, is preferably 32～35 ℃, and galvanic electric current is close is 5～18A/dm
2, be preferably 8～10A/dm
2, electroplating time is generally 1～5min.
Described have an activation treatment before electrodeposited chromium, the method of activation treatment and condition for and be known to the skilled person known, the method can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator ANKOR NFDS 2.6g/L, soak time is 1～2min, and temperature is room temperature.
In electrodeposited chromium Hou You tri-road washings, the method for washing and condition are conventionally known to one of skill in the art, and the method adopts pure water rinsing 1～2min.
In step 7) plastic basis material is directly implemented to new-type environment-protection electroplating technique, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath after electrodeposited chromium groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of chromium ion respectively; 2) mode that the washing bath after electrodeposited chromium groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
Compare with existing plating, the present invention has the following advantages:
1) plastic basis material is implemented to dry cleaning method oil removing scrubbing, replace existing ultrasonic wave except wet goods mode, can reduce the discharge of waste water;
2) adopt PVD (physical vapor deposition) metallization, and implement successively PVD plasma modification, metallizing bottom, metal excessively layer and metal conducting layer; The operations such as chromic acid alligatoring, neutralization, sensitization, reduction and chemical nickel that replace the high density of traditional plating, can greatly reduce discharge and the harm of these objectionable impuritiess to environment and the mankind of waste water.
3) implement new-type environment-protection electroplating technique and carry out copper facing or nickel plating, chromium plating operation; By waste water and waste liquid are adopted to ion exchange resin and ultrafiltration membrane treatment, the online recycling that reaches copper nickel chromium triangle re-uses and the recycling of water, and reduces its discharge.
4) the present invention can make traditional electroplating sewerage discharge reduce more than 90%, in whole technological process, do not use sexavalent chrome, reduce its harm to environment and the mankind, in the present invention simultaneously, electro-coppering, electronickelling and electrodeposited chromium have been carried out to recycling of online recycling use and water, to zero release, strided forward.
5) adopt copper electroplating layer wire drawing to replace existing electroless nickel layer wire drawing, reduce production costs.
Accompanying drawing explanation
Fig. 1 is the cultivation face figure of the product of the embodiment of the present invention 3 preparations, in Fig. 1, is respectively from bottom to up plastic basis material 11, vacuum vapor deposition layer (PVD Cr/CrCu/Cu) 12, and copper electroplating layer 13, electroless nickel layer 14, electroplates trivalent chromium layer 15.
Fig. 2 is the cultivation face figure of the product of the embodiment of the present invention 2 preparations, in Fig. 2, is respectively from bottom to up plastic basis material 21, vacuum vapor deposition layer (PVD Cr/CrCu/Cu) 22, copper electroplating layer 23, electroless nickel layer 23, protective organic (UV coating) 25.
Fig. 3 is the cultivation face figure of the product of the embodiment of the present invention 1 preparation, in Fig. 3, is respectively from bottom to up plastic basis material 31, vacuum vapor deposition layer (PVD Cr/CrCu/Cu) 32, copper electroplating layer 33, electroless nickel layer 34, vacuum vapor deposition chromium layer (PVDCr) 35.
Fig. 4 is the cultivation face figure of the product of the embodiment of the present invention 4 preparations, in Fig. 4, be respectively from bottom to up plastic basis material 41, vacuum vapor deposition layer (PVD Cr/CrCu/Cu) 42, copper electroplating layer 43, electroless nickel layer 44, electroplates trivalent chromium layer 45, vacuum vapor deposition zirconium nitride layer (PVD ZrN) 46.
Embodiment
Below in conjunction with accompanying drawing, a kind of plastic basis material copper wire drawing environment-friendly type electric plating method of the present invention is described further.
Embodiment 1
(1) MODIFIED PP plastic basis material is carried out to pre-treatment
MODIFIED PP plastic basis material is implemented to dry cleaning method, and employing plasma flame carries out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface after processing again;
(2) plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization
MODIFIED PP plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization, and implement successively PVD plasma modification, metallizing bottom, metal is layer and metal conducting layer excessively, plasma modification processing condition are ion source electric current 0.5A, bias voltage 80V, dutycycle 80%, argon gas flow velocity 50SCCM, oxygen gas flow rate 50SCCM, vacuum pressure 0.2Pa in stove, soak time 5min is to reach clean and to change the object that activates matrix surface, metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power medium-frequency pulse power supply, metallizing bottom electric current is 300A, voltage is 800V, depositing time is 1min, bias voltage 20V, dutycycle 50%, argon gas flow velocity 60SCCM, coated metal is chromium, metallizing excessively layer electric current is 150A, and voltage is 600V, and depositing time is 2min, bias voltage 60V, and dutycycle 70%, argon gas flow velocity 60SCCM, coated metal is chromium and copper, metallizing excessively layer electric current is 50A, and voltage is 400V, and depositing time is 2min, bias voltage 60V, dutycycle 70%, argon gas flow velocity 60SCCM, coated metal copper.
(3) implement new-type environment-protection electroplating technique and carry out copper facing operation;
Technical process is, the burnt copper of the advanced electroplating of MODIFIED PP plastic basis material, husky copper, and concrete technology is as follows:
Electroplate that cupric pyrophosphate process using Yong Xing chemical company provides formula as follows: cupric pyrophosphate 70 ± 10g/L, potassium pyrophosphate 300 ± 50g/L, ammoniacal liquor (28%) 1～3mL/L, cupric ion 25～35g/L, additive RS7510.1～0.2ml/L, pH 8.5, and the temperature of plating solution can be 55 ℃, and galvanic current density can be 0.5A/dm
2, electroplating time is 10min.
Electroplating husky copper adopts the formula of the electroplating acid copper that Le Si company provides as follows: the formula that plates husky copper is as follows: copper sulfate CuSO
4200 ± 10g/L, sulfuric acid H
2sO
465 ± 15g/L, chlorion Cl
-80～120ppm, husky agent 303 8～12ml/L, the temperature of plating solution can be 30 ℃, and galvanic current density can be 3A/dm
2,, electroplating time can be 20min; Electroplating cupric pyrophosphate, electroplate that between husky copper, to have one washing, the method for washing and condition be conventionally known to one of skill in the art, the method adopts pure water rinsing 2min.
In the new-type environment-protection electroplating technique of enforcement, carry out in copper facing operation, use following technology to reach mantoquita online recycling and the recycle to waste water: 1) to the washing bath of copper electroplating groove, to adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling utilization of cupric ion respectively; 2) to the washing bath of copper electroplating groove and activated bath, adopt the mode of ion exchange resin and ultra-filtration membrane to recycle the water of washing use respectively.
(4) wire drawing is processed
To carrying out wire drawing processing through plating the surface of the plastic rubber substrate after husky copper, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 1000r/min, pulling wheel is: nylon wheel.
(5) dry cleaning processing is carried out in the MODIFIED PP plastic rubber substrate surface after wire drawing processing;
MODIFIED PP plastic basis material is implemented to dry cleaning method, and employing plasma flame carries out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface after processing again;
(6) electronickelling
The method of electronickelling can the plastic rubber substrate after wire drawing is processed be negative electrode, and nickel plate is anode, electroplates adoptable formula as follows: single nickel salt NiSO without leveling nickel plating
4250～350g/L, nickelous chloride NiCl
230～68g/L, boric acid H
3bO
338～53g/L, pH 4.2, brightening agent BR 220 auxiliary 20～30ml/L, brightening agent BR 220 opens cylinder agent 7.5～15ml/L, SB 200 0.5～1.5ml/L, NAW-A 2.5～4.0ml/L, the temperature of described plating solution can be 50 ℃, and galvanic current density can be 2A/dm
2, electroplating time can be 30min; Without leveling nickel plating solution, can adopt the formula of the electronickelling that U.S. Luo Menha company provides.
Bright nickel plating plating solution can adopt the formula of the plating light quantity nickel that U.S. Luo Menha company provides as follows: single nickel salt NiSO
4270～375g/L, nickelous chloride NiCl
235～45g/L, boric acid H
3bO
338～50g/L, pH 4.5, brightening agent SB2004.0～7.5ml/L, brightening agent SB2010.75～1.25ml/L, brightening agent NAW-A 1.0～4.0ml/L, the temperature of described plating solution can be 60 ℃, and galvanic current density can be 3A/dm
2,, electroplating time can be 5min.
Before electroplating without leveling nickel, there is activation treatment, activating treatment process and condition are and are conventionally known to one of skill in the art, described activating treatment process can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator V-37 45g/L, and soak time is 2min, temperature is room temperature.
In step 6) plastic basis material is directly implemented to new-type environment-protection electroplating technique, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath after electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of nickel ion respectively; 2) mode that the washing bath after electronickelling groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
(7) PVD plated film
The MODIFIED PP plastic rubber substrate of processing through electronickelling is turned linked to PVD stove and carry out after Cement Composite Treated by Plasma, carry out the deposition of chromium layer, plasma treatment process condition is ion source electric current 0.5A, bias voltage 80V, dutycycle 80%, argon gas flow velocity 100SCCM,, vacuum pressure 0.2Pa in stove, soak time 5min, the technique of PVD metallizing chromium is that electric current is 50A, voltage is 400V, and depositing time is 5min, bias voltage 80V, dutycycle 50%, argon gas flow velocity 60SCCM.
Through test, original full automatic output is 20,000 m
2/ plating line monthly, the waste water of monthly getting rid of is 2500 tons, adopts after method of the present invention, same production capacity, but the wastewater discharge of every month is 80 tons.
The cultivation face figure of the product of embodiment 1 preparation is referring to Fig. 3.
Embodiment 2
(1) ABS plastic base material is carried out to pre-treatment
ABS plastic base material is implemented to dry cleaning method, adopt hydrocarbon vacuum cleaned to remove the greasy dirt of ABS plastic substrate surface;
(2) plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization
ABS plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization, and implement successively PVD plasma modification, metallizing bottom, metal is layer and metal conducting layer excessively, plasma modification processing condition are ion source electric current 0.3A, bias voltage 150V, dutycycle 80%, argon gas flow velocity 50SCCM, oxygen gas flow rate 80SCCM, vacuum pressure 0.3Pa in stove, soak time 6min is to reach clean and to change the object that activates matrix surface, metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power medium-frequency pulse power supply, metallizing bottom electric current is 300A, voltage is 800V, depositing time is 1min, bias voltage 60V, dutycycle 50%, argon gas flow velocity 200SCCM, coated metal is chromium, metallizing excessively layer electric current is 50A, and voltage is 400V, and depositing time is 5min, bias voltage 20V, and dutycycle 70%, argon gas flow velocity 200SCCM, coated metal is chromium and copper, metallizing excessively layer electric current is 100A, and voltage is 500V, and depositing time is 4min, bias voltage 20V, dutycycle 50%, argon gas flow velocity 200SCCM, coated metal copper.
(3) implement new-type environment-protection electroplating technique and carry out copper facing operation;
Technical process is, the burnt copper of the advanced electroplating of ABS plastic base material, husky copper, and concrete technology is as follows:
Electroplate that cupric pyrophosphate process using Yong Xing chemical company provides formula as follows: cupric pyrophosphate 70 ± 10g/L, potassium pyrophosphate 300 ± 50g/L, ammoniacal liquor (28%) 1～3mL/L, cupric ion 25～35g/L, additive RS751 0.1～0.2ml/L, pH 9.5.The temperature of plating solution can be 45 ℃, and galvanic current density can be 2A/dm
2, electroplating time is 5min.
Electroplating husky copper adopts the formula of the electroplating acid copper that Le Si company provides as follows: the formula that plates husky copper is as follows: copper sulfate CuS0
4200 ± 10g/L, sulfuric acid H
2sO 65 ± 15g/L, chlorion Cl
-80～120ppm, husky agent 303 8～12ml/L, the temperature of plating solution can be 35 ℃, and galvanic current density can be 6A/dm
2,, electroplating time can be 5min; Electroplating cupric pyrophosphate, electroplate that between husky copper, to have one washing, the method for washing and condition be conventionally known to one of skill in the art, the method adopts pure water rinsing 1min.
In the new-type environment-protection electroplating technique of enforcement, carry out in copper facing operation, use following technology to reach mantoquita online recycling and the recycle to waste water: 1) to the washing bath of copper electroplating groove, to adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling utilization of cupric ion respectively; 2) to the washing bath of copper electroplating groove and activated bath, adopt the mode of ion exchange resin and ultra-filtration membrane to recycle the water of washing use respectively.
(4) wire drawing is processed
To carrying out wire drawing processing through plating the surface of the plastic rubber substrate after husky copper, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 500r/min, pulling wheel is: abrasive belt wheel.
(5) dry cleaning processing is carried out in the ABS plastic rubber substrate surface after wire drawing processing;
ABS plastic base material is implemented to dry cleaning method, adopt hydrocarbon vacuum cleaned to remove the greasy dirt of ABS plastic substrate surface;
(6) electronickelling
The method of electronickelling can the plastic rubber substrate after wire drawing is processed be negative electrode, and nickel plate is anode.Without leveling nickel plating, electroplate adoptable formula as follows: single nickel salt NiSO
4250～350g/L, nickelous chloride NiCl
230～68g/L, boric acid H
3bO
338～53g/L, pH 4.0, brightening agent BR 220 auxiliary 20～30ml/L, brightening agent BR 220 opens cylinder agent 7.5～15ml/L, SB 2000.5～1.5ml/L, NAW-A2.5～4.0ml/L, the temperature of described plating solution can be 60 ℃, and galvanic current density can be 5A/dm
2, electroplating time can be 5min; Without leveling nickel plating solution, can adopt the formula of the electronickelling that U.S. Luo Menha company provides.
Bright nickel plating plating solution can adopt the formula of the plating light quantity nickel that U.S. Luo Menha company provides as follows: single nickel salt NiSO
4270～375g/L, nickelous chloride NiCl
235～45g/L, boric acid H
3bO
338～50g/L, pH 3.8, brightening agent SB200 4.0～7.5ml/L, brightening agent SB201 0.75～1.25ml/L, brightening agent NAW-A 1.0～4.0ml/L, the temperature of described plating solution can be 60 ℃, and galvanic current density can be 3A/dm
2,, electroplating time can be 30min.
Before electroplating without leveling nickel, there is activation treatment, activating treatment process and condition are and are conventionally known to one of skill in the art, described activating treatment process can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator V-37 45g/L, and soak time is 1min, temperature is room temperature.
In step 6) plastic basis material is directly implemented to new-type environment-protection electroplating technique, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath after electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of nickel ion respectively; 2) mode that the washing bath after electronickelling groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
(7) spraying plating protective organic
The ABS plastic rubber substrate of processing through electronickelling is carried out to ultraviolet light polymerization (UV) spraying, after spraying plating thick layer approximately 20 μ mUV paints, plastic rubber substrate is sent into infrared rays baker, spray paint rete levelling, oven dry, temperature is 70 ℃, time is 8min, finally the rete that sprays paint after levelling is accepted in ultraviolet photo-curing stove to irradiate curing cross-linked, time 30s.
Through test, original full automatic output is 20,000 m
2/ plating line monthly, the waste water of monthly getting rid of is 2500 tons.Adopt after method of the present invention, same production capacity, but the wastewater discharge of every month is 80 tons.
The cultivation face figure of the product of embodiment 2 preparations is referring to Fig. 2.
Embodiment 3
(1) MODIFIED PP plastic basis material is carried out to pre-treatment
MODIFIED PP plastic basis material is implemented to dry cleaning method, and employing plasma flame carries out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface after processing again;
(2) plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization
MODIFIED PP plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization, and implement successively PVD plasma modification, metallizing bottom, metal is layer and metal conducting layer excessively, plasma modification processing condition are ion source electric current 0.3A, bias voltage 150V, dutycycle 50%, argon gas flow velocity 100SCCM, oxygen gas flow rate 10SCCM, vacuum pressure 0.2Pa in stove, soak time 10min is to reach clean and to change the object that activates matrix surface, metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power DC power supply, metallizing bottom electric current is 50A, voltage is 400V, depositing time is 2min, bias voltage 20V, dutycycle 50%, argon gas flow velocity 100SCCM, coated metal is chromium, metallizing excessively layer electric current is 200A, and voltage is 600V, and depositing time is 3min, bias voltage 40V, and dutycycle 70%, argon gas flow velocity 100SCCM, coated metal is chromium and copper, metallizing excessively layer electric current is 300A, and voltage is 800V, and depositing time is 2min, bias voltage 40V, dutycycle 70%, argon gas flow velocity 100SCCM, coated metal copper.
(3) implement new-type environment-protection electroplating technique and carry out copper facing operation;
Technical process is, the burnt copper of the advanced electroplating of MODIFIED PP plastic basis material, husky copper, and concrete technology is as follows:
Electroplate that cupric pyrophosphate process using Yong Xing chemical company provides formula as follows: cupric pyrophosphate 70 ± 10g/L, potassium pyrophosphate 300 ± 50g/L, ammoniacal liquor (28%) 1～3mL/L, cupric ion 25～35g/L, additive RS751 0.1～0.2ml/L, pH 9.0, and the temperature of plating solution can be 50 ℃, and galvanic current density can be 1A/dm
2, electroplating time is 7min.
Electroplating husky copper adopts the formula of the electroplating acid copper that Le Si company provides as follows: the formula that plates husky copper is as follows: copper sulfate CuSO
4200 ± 10g/L, sulfuric acid H
2sO
465 ± 15g/L, chlorion Cl
-80～120ppm, husky agent 303 8～12ml/L, the temperature of plating solution can be 28 ℃, and galvanic current density can be 3A/dm
2,, electroplating time can be 40min;
Electroplating cupric pyrophosphate, electroplate that between husky copper, to have one washing, the method for washing and condition be conventionally known to one of skill in the art, the method adopts pure water rinsing 1.5min.
In the new-type environment-protection electroplating technique of enforcement, carry out in copper facing operation, use following technology to reach mantoquita online recycling and the recycle to waste water: 1) to the washing bath of copper electroplating groove, to adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling utilization of cupric ion respectively; 2) to the washing bath of copper electroplating groove and activated bath, adopt the mode of ion exchange resin and ultra-filtration membrane to recycle the water of washing use respectively.
(4) wire drawing is processed
To carrying out wire drawing processing through plating the surface of the plastic rubber substrate after husky copper, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 700r/min, pulling wheel is: all-wing aircraft wheel.
(5) dry cleaning processing is carried out in the MODIFIED PP plastic rubber substrate surface after wire drawing processing;
MODIFIED PP plastic basis material is implemented to dry cleaning method, and employing plasma flame carries out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface after processing again;
(6) electronickelling
The method of electronickelling can the plastic rubber substrate after wire drawing is processed be negative electrode, and nickel plate is anode, electroplates adoptable formula as follows: single nickel salt NiSO without leveling nickel plating
4250～350g/L, nickelous chloride NiCl
230～68g/L, boric acid H
3bO
338～53g/L, pH 4.2, brightening agent BR 220 auxiliary 20～30ml/L, brightening agent BR 220 opens cylinder agent 7.5～15ml/L, SB 2000.5～1.5ml/L, NAW-A2.5～4.0ml/L, the temperature of described plating solution can be 55 ℃, and galvanic current density can be 3A/dm
2, electroplating time can be 15min; Without leveling nickel plating solution, can adopt the formula of the electronickelling that U.S. Luo Menha company provides.
Bright nickel plating plating solution can adopt the formula of the plating light quantity nickel that U.S. Luo Menha company provides as follows: single nickel salt NiSO
4270～375g/L, nickelous chloride NiCl
235～45g/L, boric acid H
3bO
338～50g/L, pH 4.5, brightening agent SB200 4.0～7.5ml/L, brightening agent SB201 0.75～1.25ml/L, brightening agent NAW-A 1.0～4.0ml/L, the temperature of described plating solution can be 58 ℃, and galvanic current density can be 4A/dm
2,, electroplating time can be 20min.
Before electroplating without leveling nickel, there is activation treatment, activating treatment process and condition are and are conventionally known to one of skill in the art, described activating treatment process can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator V-37 45g/L, and soak time is 1.5min, temperature is room temperature.
In step 6) plastic basis material is directly implemented to new-type environment-protection electroplating technique, new-type environment-protection electroplating is to carry out according to following standard:
1) washing bath after electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of nickel ion respectively; 2) mode that the washing bath after electronickelling groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
(7) electroplate environmental protection trivalent chromium
The method that the method for described electrodeposited chromium and condition are known to the skilled person, the present invention adopts toxicological harmless to obtain trivalent chromium plating technology, chromic plating solution can adopt the formula of the electrodeposited chromium plating solution that U.S. Luo Menha company provides as follows: 3C opens cylinder salt 375～450g/L, 3C joins cylinder liquid 6～25ml/L, 3C stablizer 55～65ml/L, 3C wetting agent 9～15ml/L, 3C complexing agent 0.75～1.5ml/L, pH 3.1.The temperature of described plating solution comprises that the temperature of plating solution is 32 ℃, and galvanic electric current is close is 8A/dm
2, electroplating time is 5min.
Described have an activation treatment before electrodeposited chromium, the method of activation treatment and condition for and be known to the skilled person known, the method can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator ANKOR NFDS 2.6g/L, soak time is 1min, and temperature is room temperature.
In electrodeposited chromium Hou You tri-road washings, the method for washing and condition are conventionally known to one of skill in the art, and the method adopts pure water rinsing 1min.
Plastic basis material is directly implemented to new-type environment-protection electroplating technique, and new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath after electrodeposited chromium groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of chromium ion respectively; 2) mode that the washing bath after electrodeposited chromium groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
Through test, original full automatic output is 20,000 m
2/ plating line monthly, the waste water of monthly getting rid of is 2500 tons, adopts after method of the present invention, same production capacity, but the wastewater discharge of every month is 120 tons.
The cultivation face figure of the product of embodiment 3 preparations is referring to Fig. 1.
Embodiment 4
(1) ABS plastic base material is carried out to pre-treatment
ABS plastic base material is implemented to dry cleaning method, adopt dry ice oil removal treatment to remove greasy dirt and the dust on modified ABS plastic basis material surface;
(2) plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization
ABS plastic rubber substrate is carried out to PVD (physical vapor deposition) metallization, and implement successively PVD plasma modification, metallizing bottom, metal is layer and metal conducting layer excessively, plasma modification processing condition are ion source electric current 0.4A, bias voltage 100V, dutycycle 80%, argon gas flow velocity 10SCCM, oxygen gas flow rate 100SCCM, vacuum pressure 0.2Pa in stove, soak time 5min is to reach clean and to change the object that activates matrix surface, metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power DC power supply, metallizing bottom electric current is 200A, voltage is 600V, depositing time is 2min, bias voltage 20V, dutycycle 50%, argon gas flow velocity 100SCCM, coated metal is chromium, metallizing excessively layer electric current is 100A, and voltage is 500V, and depositing time is 2min, bias voltage 40V, and dutycycle 70%, argon gas flow velocity 100SCCM, coated metal is chromium and copper, metallizing excessively layer electric current is 50A, and voltage is 400V, and depositing time is 1min, bias voltage 40V, dutycycle 70%, argon gas flow velocity 100SCCM, coated metal copper.
(3) implement new-type environment-protection electroplating technique and carry out copper facing operation;
Technical process is, the burnt copper of the advanced electroplating of MODIFIED PP plastic basis material, husky copper, and concrete technology is as follows:
Electroplate that cupric pyrophosphate process using Yong Xing chemical company provides formula as follows: cupric pyrophosphate 70 ± 10g/L, potassium pyrophosphate 300 ± 50g/L, ammoniacal liquor (28%) 1～3mL/L, cupric ion 25～35g/L, additive RS7510.1～0.2ml/L, pH 9.0, and the temperature of plating solution can be 50 ℃, and galvanic current density can be 1A/dm
2, electroplating time is 20min.
Electroplating husky copper adopts the formula of the electroplating acid copper that Le Si company provides as follows: the formula that plates husky copper is as follows: copper sulfate CuSO
4200 ± 10g/L, sulfuric acid H
2sO
465 ± 15g/L, chlorion Cl
-80～120ppm, husky agent 303 8～12ml/L, the temperature of plating solution can be 32 ℃, and galvanic current density can be 4A/dm
2, electroplating time can be 10min;
Electroplating cupric pyrophosphate, electroplate that between husky copper, to have one washing, the method for washing and condition be conventionally known to one of skill in the art, the method adopts pure water rinsing 1min.
In the new-type environment-protection electroplating technique of enforcement, carry out in copper facing operation, use following technology to reach mantoquita online recycling and the recycle to waste water: 1) to the washing bath of copper electroplating groove, to adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling utilization of cupric ion respectively; 2) to the washing bath of copper electroplating groove and activated bath, adopt the mode of ion exchange resin and ultra-filtration membrane to recycle the water of washing use respectively.
(4) wire drawing is processed
To carrying out wire drawing processing through plating the surface of the plastic rubber substrate after husky copper, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 700r/min, pulling wheel is: nylon wheel.
(5) dry cleaning processing is carried out in the ABS plastic rubber substrate surface after wire drawing processing;
ABS plastic base material is implemented to dry cleaning method, after employing dry ice oil removal treatment, carry out again greasy dirt and the dust that Electrostatic Treatment removes ABS plastic substrate surface;
(6) electronickelling
The method of electronickelling can the plastic rubber substrate after wire drawing is processed be negative electrode, and nickel plate is anode, electroplates adoptable formula as follows: single nickel salt NiSO without leveling nickel plating
4250～350g/L, nickelous chloride NiCl
230～68g/L, boric acid H
3bO
338～53g/L, pH 4.2, brightening agent BR 220 auxiliary 20～30ml/L, brightening agent BR 220 opens cylinder agent 7.5～15ml/L, SB 2000.5～1.5ml/L, NAW-A2.5～4.0ml/L, the temperature of described plating solution can be 55 ℃, and galvanic current density can be 3A/dm
2, electroplating time can be 15min; Without leveling nickel plating solution, can adopt the formula of the electronickelling that U.S. Luo Menha company provides.
Bright nickel plating plating solution can adopt the formula of the plating light quantity nickel that U.S. Luo Menha company provides as follows: single nickel salt NiSO
4270～375g/L, nickelous chloride NiCl
235～45g/L, boric acid H
3bO
338～50g/L, pH 4.5, brightening agent SB200 4.0～7.5ml/L, brightening agent SB201 0.75～1.25ml/L, brightening agent NAW-A 1.0～4.0ml/L, the temperature of described plating solution can be 58 ℃, and galvanic current density can be 4A/dm
2,, electroplating time can be 20min.
Before electroplating without leveling nickel, there is activation treatment, activating treatment process and condition are and are conventionally known to one of skill in the art, described activating treatment process can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator V-37 45g/L, and soak time is 1.5min, temperature is room temperature.
In step 6) plastic basis material is directly implemented to new-type environment-protection electroplating technique, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath after electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of nickel ion respectively; 2) mode that the washing bath after electronickelling groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
(7) electroplate environmental protection trivalent chromium
The method that the method for electrodeposited chromium and condition are known to the skilled person, adopt toxicological harmless to obtain trivalent chromium plating technology, chromic plating solution can adopt the formula of the electrodeposited chromium plating solution that U.S. Luo Menha company provides as follows: 3C opens cylinder salt 375～450g/L, 3C joins cylinder liquid 6～25ml/L, 3C stablizer 55～65ml/L, 3C wetting agent 9～15ml/L, 3C complexing agent 0.75～1.5ml/L, pH 2.6.The temperature of described plating solution comprises that the temperature of plating solution is 35 ℃, and galvanic electric current is close is 10A/dm
2electroplating time is 1min.
Described have an activation treatment before electrodeposited chromium, the method of activation treatment and condition for and be known to the skilled person known, the method can adopt the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator ANKOR NFDS 2.6g/L, soak time is 1min, and temperature is room temperature.
In electrodeposited chromium Hou You tri-road washings, the method for washing and condition are conventionally known to one of skill in the art, and the method adopts pure water rinsing 1min.
Plastic basis material is directly implemented to new-type environment-protection electroplating technique, and new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath after electrodeposited chromium groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling utilization of chromium ion respectively; 2) mode that the washing bath after electrodeposited chromium groove and activated bath adopt ion exchange resin or ultra-filtration membrane respectively recycles the water of washing use.
(8) PVD plated film plated film
The ABS plastic rubber substrate of processing through plating trivalent chromium is turned linked to PVD stove to carry out after Cement Composite Treated by Plasma, carry out the deposition of zirconium nitride rete, plasma treatment process condition is ion source electric current 0.3A, bias voltage 80V, dutycycle 80%, argon gas flow velocity 100SCCM, vacuum pressure 0.2Pa in stove, soak time 5min, the technique of PVD plating zirconium nitride rete is: multi sphere electric current is 110A, voltage is 25V, and depositing time is 2min, bias voltage 80V, dutycycle 50%, argon gas flow velocity 60SCCM, stream of nitrogen gas speed 200SCCM, multi sphere target is zirconium target.
Through test, original full automatic output is 20,000 m
2/ plating line monthly, the waste water of monthly getting rid of is 2500 tons, adopts after method of the present invention, same production capacity, but the wastewater discharge of every month is 120 tons.
The cultivation face figure of the product of embodiment 4 preparations is referring to Fig. 4.
Claims (6)
1. a plastic basis material copper wire drawing electric plating method, is characterized in that comprising the following steps:
1) plastic basis material is carried out to pre-treatment;
2) to through step 1) pretreated plastic rubber substrate carries out physical vapor deposition metallization, and carries out physical vapor deposition plasma modification successively, metallizing bottom, intermediate metal and metal conducting layer; The processing condition of described physical vapor deposition plasma modification are ion source electric current 0.3～0.5A, bias voltage 80～150V, dutycycle 50%～80%, argon gas flow velocity 10～100SCCM, oxygen gas flow rate 10～150SCCM, vacuum pressure 0.1～0.3Pa in stove, soak time 5～10min; The processing condition of described metallizing bottom, intermediate metal and metal conducting layer are for adopting high-power medium-frequency pulse or high-power DC power supply, supply current is 50～300A, voltage is 400～800V, depositing time is 1～10min, bias voltage 20～60V, dutycycle 50%～80%, argon gas flow velocity 60～200SCCM;
3) to through step 2) plastic rubber substrate processed directly carries out electro-coppering; Describedly directly carry out electro-coppering and be selected from and electroplate cupric pyrophosphate, electroplate at least one in husky copper; The method of described electro-coppering is to using through step 2) plastic rubber substrate processed is as negative electrode, and copper coin is as anode, adopts that to electroplate the formula of husky copper as follows: copper sulfate CuSO
4200 ± 10g/L, sulfuric acid H
2sO
465 ± 15g/L, chlorion Cl
-80～120ppm, husky agent 3038～12ml/L, the temperature of plating solution is 28～35 ℃, galvanic current density is 3～6A/dm
2, electroplating time is 5～40min; The formula of the process using of described plating cupric pyrophosphate is as follows: cupric pyrophosphate 70 ± 10g/L, potassium pyrophosphate 300 ± 50g/L, ammoniacal liquor 1～3mL/L, cupric ion 25～35g/L, additive RS7510.1～0.2ml/L, pH8.5～9.5, the temperature of plating solution is 45～55 ℃, galvanic current density is 0.5～2A/dm
2, electroplating time is 5～10min;
4) to through step 3) the copper electroplating layer surface of the plastic rubber substrate processed carries out wire drawing processing;
5) to through step 4) the plastic rubber substrate surface of processing carries out dry cleaning processing;
6) to through step 5) plastic rubber substrate processed carry out electronickelling; Described electronickelling is at least one of electroplating in nothing leveling nickel, Bright Nickel Electroplating;
The method of described electronickelling is that the plastic rubber substrate after wire drawing is processed is negative electrode, and nickel plate is anode; Without leveling nickel plating, electroplate the formula adopting as follows: single nickel salt NiSO
4250～350g/L, nickelous chloride NiCl
230～68g/L, boric acid H
3bO
338～53g/L, pH4.0～4.2, brightening agent BR220 auxiliary 20～30ml/L, brightening agent BR220 opens cylinder agent 7.5～15ml/L, SB2000.5～1.5ml/L, NAW-A2.5～4.0ml/L, the temperature of described plating solution is 50～60 ℃, and galvanic current density is 2～5A/dm
2, electroplating time is 5～30min;
The formula of the Bright Nickel Electroplating that the plating solution employing U.S. Luo Menha company of described Bright Nickel Electroplating provides is as follows: single nickel salt NiSO
4270～375g/L, nickelous chloride NiCl
235～45g/L, boric acid H
3bO
338～50g/L, pH3.8～4.5, brightening agent SB2004.0～7.5ml/L, brightening agent SB2010.75～1.25ml/L, brightening agent NAW-A1.0～4.0ml/L, the temperature of described plating solution is 58～60 ℃, galvanic current density is 3～4A/dm
2, electroplating time is 5～30min;
Described plating is carried out activation treatment before without leveling nickel, and described activating treatment process adopts the formula of the activation plating solution that Japanese Ren Yuan company provides as follows: activator V-37 is 45g/L, and soak time is 1～2min, and temperature is room temperature;
7) to through step 6) plastic rubber substrate processed turns linked to PVD stove and carries out, after Cement Composite Treated by Plasma, carrying out PVD coating film treatment, to meet various functions, color requirement; Or
To through step 6) plastic rubber substrate processed carries out the processing of spraying plating organic coating; Or
To through step 6) plastic rubber substrate processed carries out electrodeposited chromium processing; Or
To through step 6) plastic rubber substrate processed carries out electrodeposited chromium, and finally carry out PVD coating film treatment and meet various functions, color requirement.
2. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1, it is characterized in that in step 1) in, described pre-treatment, to adopt dry cleaning method oil removing scrubbing, the concrete grammar of described employing dry cleaning method oil removing scrubbing adopts plasma flame to process, dry ice oil removal treatment, Electrostatic Treatment, at least one in hydrocarbon vacuum cleaned method.
3. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1, is characterized in that in step 3) in, the electroplating acid copper formula that the formula of the husky copper of described plating adopts Le Si company to provide; The formula that the technical recipe of described plating cupric pyrophosphate adopts Yong Xing chemical company to provide;
As adopted, electroplate cupric pyrophosphate and electroplate husky process for copper, washing process together with having with between the husky copper of plating at plating cupric pyrophosphate, the method for described washing and condition are conventionally known to one of skill in the art, the method adopts pure water rinsing 1～2min.
4. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1, is characterized in that in step 4) in, described wire drawing is processed, and is to adopt automatic or artificial mode to carry out wire drawing, and the rotating speed of drawing wire machine is 500～1000r/min; Pulling wheel is nylon wheel, abrasive belt wheel, at least one in all-wing aircraft wheel.
5. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1, it is characterized in that in step 5) in, the concrete grammar that described employing dry cleaning is processed is to adopt plasma flame to process, dry ice oil removal treatment, Electrostatic Treatment, at least one in hydrocarbon vacuum cleaned method.
6. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1, it is characterized in that in step 7) in, described in to be coated with the concrete grammar that organic coating processes be to adopt: 1) electrophoretic painting, 2) powder spraying, 3) ultraviolet light polymerization spraying and 4) polyurethane paint sprays;
In step 7) in, the method for described electrodeposited chromium is trivalent chromium plating, the formula of the plating solution of described trivalent chromium plating is as follows: 3C opens cylinder salt 375～450g/L, 3C joins cylinder liquid 6～25ml/L, 3C stablizer 55～65ml/L, 3C wetting agent 9～15ml/L, 3C complexing agent 0.75～1.5ml/L, pH2.6～3.1; The temperature of described plating solution comprises that the temperature of plating solution is 32～35 ℃, and galvanic electric current is close is 8～10A/dm
2, electroplating time is 1～5min;
Before described electrodeposited chromium, carry out activation treatment, the formula of the activation plating solution of described activation treatment is as follows: activator ANKOR NFDS2.6g/L, and soak time is 1～2min, temperature is room temperature;
After described electrodeposited chromium, carry out three road washings.
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