CN102517618A - Copper drawing and electroplating method for plastic substrate - Google Patents

Copper drawing and electroplating method for plastic substrate Download PDF

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Publication number
CN102517618A
CN102517618A CN2011104486994A CN201110448699A CN102517618A CN 102517618 A CN102517618 A CN 102517618A CN 2011104486994 A CN2011104486994 A CN 2011104486994A CN 201110448699 A CN201110448699 A CN 201110448699A CN 102517618 A CN102517618 A CN 102517618A
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plating
electroplating
copper
treatment
plastic
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CN102517618B (en
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余水
柯学标
乔永亮
李明仁
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Runner Xiamen Corp
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Xiamen Runner Industrial Corp
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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

A kind of plastic basis material copper wire drawing electric plating method
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 sexavalent chrome electrodeposited chromium that all comprise high density in the conventional plastic electroplating technology, and sexavalent chrome can be discharged in the electroplating wastewater usually, the chromium in the waste water is bigger to human body and environmental hazard! The hexavalent chromic anhydride of common chromium cpd, SRM 935a, sodium dichromate 99, potassiumchromate, Sodium chromate-51Cr etc.; Tervalent chromium sesquioxide (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 that according to the study chromium is mammal 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, that pea contains chromium is higher.Chromium has hormesis to plant-growth, and trace chromium can improve plant Yield; But concentration is high slightly, can suppress the nitrification of organic substance in the soil again.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 get into 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.The skin exposure chromium compounds can cause " chrome ulcer " that healing is extremely slow, and the concentration of chromic trioxide reaches 0.15~0.31mg/m in air 3The time just can make perforation of nasal septum.Trivalent chromium still is a kind of protein coacervation agent.Someone thinks that sexavalent chrome can bring out lung cancer.In addition, sexavalent chrome, particularly chromic acid have the effect of strong cultures shop to the sewerage metallic conduit, and concentration is that the sodium dichromate 99 of 0.31mg/L gets final product corrosion pipeline.The trivalent chromium waste water that contains 34~17.3mg/L is irritated the 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, and is 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 pre-treatment, and this matrix surface forms a copper plate, electroplates-the first chromium layer in the copper plate surface of this matrix with mountain valency chromium, electroplates-the second chromium layer at the first chromium laminar surface of this matrix with sexavalent chrome.
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 cleaning and smooth; 2) electrostatic spraying contains the outdoor powder coating of transparent red or the pure transparent outdoor powder coating of pigment; 3) the thermographic transfer paper with imitative dark-grey blueness of copper background color or black straight burr carries out hot transfer printing, obtains imitative copper wire drawing effect.
Chinese patent 201110128133 discloses a kind of treatment process of product surface, and its flow process is: to aluminium alloy compression casting moulding and processing, polished and cleaned is done on its surface, passed through the ultrasonic cleaning foul again; Heavy zinc cleans again, and the heavy zinc of secondary cleans the back again and in nickel bath, carries out nickel preplating, cleans behind the nickel preplating min; Activation is cleaned, and in copper plating groove, carries out copper facing; Copper facing is after clean, and activation is cleaned and in nickel bath, carried out bright nickel plating again; After drying, baking oven carries out wire drawing through cleaning to get into; Wire drawing is carried out electrostatic painting after accomplishing; Product behind the electrostatic painting gets in the homothermic baking chamber through circular trackway and dries the selected again finished product that is mounted to of the product after the oven dry.
Chinese patent 201110080260 discloses a kind of method of implementing imitative metal wire-drawing plated film on the engineering plastic surface, and its step comprises: in plastic mother granules, add pigment, the processing of dyeing; The plastic cement blank is carried out dry clean and activation; The plastic cement blank is coated with the look coating; Workpiece is carried out wire drawing, obtain the surface of wire drawing lines; Workpiece is carried out dry clean and activation; With the Workpiece painting Lacquer finish finish paint of wire drawing lines, promptly accomplish on the engineering plastic surface and implement imitative metal wire-drawing plated film.
Produce a large amount of waste water energy consumption a large amount of with waste in the plating production process, a full automatic output is 20,000 m 2/ every month plating line, the waste water of getting rid of in every month is 2500 tons.So many waste water is waste water resource not only, and serious is polluting human natural ecological environment, therefore presses for to improve or replace existing plating technology.The wire drawing common process flow process of existing plastic electroplating is: removing oil-removing wax; Alligatoring, activation, sensitization; Wire drawing is carried out in reduction, chemical nickel, the burnt copper of plating, electroplating acid copper, electronickelling then; Oil removing, activation, electrodeposited chromium or last PVD produce a large amount of waste water and heavy metal contaminants, and at the expensive metallic nickel of the enterprising capable wire drawing waste of metal nickel dam.
Summary of the invention
The objective of the invention is to electroplate the shortcoming and deficiency that exists in the drawing process to existing plastic cement; A kind of surface metalation that can realize plastic material is provided, adopts the copper electroplating layer wire drawing to replace the wire drawing of existing plating nickel dam, reduce production costs; Simplify the electroplating technology flow process; Reduce wastewater discharge significantly, reduce, be fit to the plastic basis material copper wire drawing electric plating method of multiple plastic rubber substrate surface wire drawing functional requirement environment and human pollution.
The present invention includes following steps:
1) plastic basis material is carried out pre-treatment;
2) metallize to carrying out physical vapor deposition (PVD) through the pretreated plastic rubber substrate of step 1), and carry out the physical vapor deposition plasma modification successively, metallizing bottom, metal be layer and metal conducting layer excessively;
3) to through step 2) plastic rubber substrate handled directly carries out electro-coppering;
4) wire drawing being carried out on the copper electroplating layer surface of the plastic rubber substrate handled through step 3) handles;
5) dry cleaning being carried out on the plastic rubber substrate surface of handling through step 4) handles;
6) to the electronickelling of carrying out of the plastic rubber substrate handled through step 5);
7) plastic rubber substrate of handling through step 6) is turned linked to after the PVD stove carries out plasma treatment, carry out the PVD coating film treatment, to satisfy various functions, color requirement; Or
The dried spraying plating organic coating that carries out of plastic rubber substrate to handling through step 5) is handled; Or
The dried electrodeposited chromium that carries out of plastic rubber substrate to handling through step 5) is handled; Or
The dried electrodeposited chromium that carries out of plastic rubber substrate to handling through step 5) carries out the PVD coating film treatment at last and satisfies various functions, color requirement.
In step 1), said pre-treatment can be adopted dry cleaning method oil removing scrubbing, and the concrete grammar of said employing dry cleaning method oil removing scrubbing can adopt plasma flame to handle, dry ice oil removal treatment, Electrostatic Treatment, at least a in the methods such as hydrocarbon vacuum cleaned.
In step 2) in, the processing condition of said 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, vacuum pressure 0.1~0.3Pa in the oxygen gas flow rate 10~150SCCM, stove; Soak time 5~10min is to reach the purpose of cleaning and change activation matrix surface; The processing condition of said 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, and depositing time is 1~10min, bias voltage 20~60V; Dutycycle 50%~80%, argon gas flow velocity 60~200SCCM.
In step 3), saidly directly carry out electro-coppering and can be selected from and electroplate cupric pyrophosphate, electroplate at least a in the husky copper etc.; The method of said electro-coppering can adopt the known various electro-plating methods of person of ordinary skill in the field, controls product thickness of plating layer and quality more easily owing to electroplate, and electroplates the product quality excellence that the process multi-layer plating comes out;
The method of said electro-coppering is with through step 2) plastic rubber substrate handled is as negative electrode, and copper coin adopts the prescription of electroplating husky copper following: copper sulfate CuSO as anode 4200 ± 10g/L, sulfuric acid H 2SO 65 ± 15g/L, cl ions Cl -80~120ppm, husky agent 303 8~12ml/L, the temperature of plating bath 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 prescription of the technology of said plating cupric pyrophosphate is following: 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 bath 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 prescription that the prescription of the husky copper of said plating can adopt Le Si company to provide; The prescription that the technical recipe of said plating cupric pyrophosphate can adopt star chemical company forever to provide;
As adopt and electroplate cupric pyrophosphate and electroplate husky process for copper, then with electroplating between the husky copper washing process being arranged at the plating cupric pyrophosphate, the method for said washing and condition are conventionally known to one of skill in the art, this method adopts pure water rinsing 1~2min.
In step 3) plastic basis material is directly implemented new-type environment-protection electroplating technology, new-type environment-protection electroplating is to carry out according to following standard: 1) adopt the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of cupric ion to the washing bath of electro-coppering groove respectively; 2) mode that respectively washing bath of electro-coppering groove is adopted ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness.
In step 4), said wire drawing is handled, and can adopt automatic perhaps 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 a in the all-wing aircraft wheel etc.
In step 5), the concrete grammar that said employing dry cleaning is handled can adopt plasma flame to handle, dry ice oil removal treatment, Electrostatic Treatment, at least a in the methods such as hydrocarbon vacuum cleaned.
In step 6), said electronickelling, electrodepositable does not have at least a in leveling nickel, the electroplating bright nickel etc.; The method of said electronickelling can adopt the known various electro-plating methods of person of ordinary skill in the field, controls product thickness of plating layer and quality more easily owing to electroplate, and it is more excellent to electroplate the product that comes out through multi-layer plating.
The method of said electronickelling can be a negative electrode through the plastic rubber substrate after wire drawing is handled, and the nickel plate is an anode.It is following that adoptable prescription is electroplated in nothing leveling nickel plating: 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 auxiliarys 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 said plating bath 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; There is not the prescription that the leveling nickel plating solution can adopt the electronickelling that U.S. Luo Menha company provides.
The plating bath of said electroplating bright nickel can adopt the prescription of the plating light quantity nickel that U.S. Luo Menha company provides following: 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 said plating bath 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.
Said plating can not carried out activation treatment before having leveling nickel; The method of said activation treatment and condition are conventionally known to one of skill in the art; Said activating treatment process can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator V-3745g/L; Soak time is 1~2min, and temperature is a room temperature.
Said electronickelling can be carried out according to following standard: 1) washing bath behind the electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of nickel ion respectively; 2) washing bath behind the electronickelling groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
In step 7), said organic coating is to adopt following method 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 a method known in those skilled in the art, and the thickness of organic coating can be 10~30 μ m.
In step 7), the method for said electrodeposited chromium and condition are for well known to a person skilled in the art method, and the present invention adopts toxicological harmless to get the trivalent chromium plating technology; Chromic plating bath can adopt the prescription of the electrodeposited chromium plating bath that U.S. Luo Menha company provides following: 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 said plating bath comprises that the temperature of plating bath is 30~40 ℃, is preferably 32~35 ℃, and galvanic electric current is close to be 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 are and are known for well known to a person skilled in the art; This method can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator ANKOR NFDS 2.6g/L; Soak time is 1~2min, and temperature is a room temperature.
The washing of three roads is arranged behind electrodeposited chromium, and the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 1~2min.
In step 7) plastic basis material is directly implemented new-type environment-protection electroplating technology, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath behind the electrodeposited chromium groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of chromium ion respectively; 2) washing bath behind the electrodeposited chromium groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
Compare with existing plating, the present invention has the following advantages:
1) plastic basis material is implemented dry cleaning method oil removing scrubbing, replace existing UW and remove the wet goods mode, can reduce the discharging of waste water;
2) adopt PVD (physical vapor deposition) metallization, and implement PVD plasma modification, metallizing bottom, metal excessively layer and metal conducting layer successively; The operations such as chromic acid alligatoring, neutralization, sensitization, reduction and chemical nickel that replace traditional galvanized high density, discharging and these objectionable impuritiess that can significantly reduce waste water are to environment and human harm.
3) implement new-type environment-protection electroplating technology and carry out copper facing or nickel plating, chromium plating operation; Through waste water and waste liquid are adopted ion exchange resin and ultrafiltration membrane treatment, the online recovery that reaches the copper nickel chromium triangle re-uses and the recycling of water, and reduces its discharging.
4) the present invention can make traditional electroplating sewerage discharging reduce more than 90%; Do not use sexavalent chrome in the whole technological process; Reduce it to environment and human harm; Among the present invention simultaneously electro-coppering, electronickelling and electrodeposited chromium have been carried out recycling of online recovery use and water, strided forward to zero release.
5) adopt the copper electroplating layer wire drawing to replace the wire drawing of existing plating nickel dam, reduce production costs.
Description of drawings
Fig. 1 in Fig. 1, is respectively plastic basis material 11 for the face of the planting figure of the product of the embodiment of the invention 3 preparations from bottom to up, vacuum vapor deposition layer (PVD Cr/CrCu/Cu) 12, and copper electroplating layer 13, electroless nickel layer 14 is electroplated trivalent chromium layer 15.
Fig. 2 in Fig. 2, is respectively 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 from bottom to up for the face of the planting figure of the product of the embodiment of the invention 2 preparations.
Fig. 3 in Fig. 3, is respectively 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 from bottom to up for the face of the planting figure of the product of the embodiment of the invention 1 preparation.
Fig. 4 in Fig. 4, is respectively plastic basis material 41 for the face of the planting figure of the product of the embodiment of the invention 4 preparations from bottom to up; Vacuum vapor deposition layer (PVD Cr/CrCu/Cu) 42, copper electroplating layer 43, electroless nickel layer 44; Electroplate 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) the MODIFIED PP plastic basis material is carried out pre-treatment
The MODIFIED PP plastic basis material is implemented the dry cleaning method, carry out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface again after the employing plasma flame is handled;
(2) plastic rubber substrate is carried out PVD (physical vapor deposition) metallization
The MODIFIED PP plastic rubber substrate is carried out PVD (physical vapor deposition) metallization, and implement PVD plasma modification, metallizing bottom, metal excessively layer and metal conducting layer successively, plasma modified technique condition is ion source electric current 0.5A; Bias voltage 80V, dutycycle 80%, argon gas flow velocity 50SCCM; Vacuum pressure 0.2Pa in the oxygen gas flow rate 50SCCM, stove, soak time 5min is to reach the purpose of cleaning and change activation matrix surface; Metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power medium-frequency pulse power supply, and metallizing bottom electric current is 300A, and voltage is 800V; Depositing time is 1min, bias voltage 20V, dutycycle 50%; Argon gas flow velocity 60SCCM, coated metal are 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 are 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 technology and carry out the copper facing operation;
Technical process does, the burnt copper of the advanced electroplating of MODIFIED PP plastic basis material, husky copper, and concrete technology is following:
Electroplate the cupric pyrophosphate process using forever star chemical company provide prescription following: 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 bath can be 55 ℃, and galvanic current density can be 0.5A/dm 2, electroplating time is 10min.
Electroplating husky copper adopts the prescription of the electroplating acid copper that Le Si company provides following: the prescription that plates husky copper is following: copper sulfate CuSO 4200 ± 10g/L, sulfuric acid H 2SO 465 ± 15g/L, cl ions Cl -80~120ppm, husky agent 303 8~12ml/L, the temperature of plating bath can be 30 ℃, and galvanic current density can be 3A/dm 2,, electroplating time can be 20min; Between plating cupric pyrophosphate, the husky copper of plating, one washing arranged, the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 2min.
Carry out in the copper facing operation implementing new-type environment-protection electroplating technology, use following technology to reach: 1) adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling of cupric ion to the washing bath of electro-coppering groove respectively to the online recovery of mantoquita and to the recycle of waste water; 2) mode that respectively washing bath and the activated bath of electro-coppering groove is adopted ion exchange resin and ultra-filtration membrane recycles the water of washing usefulness.
(4) wire drawing is handled
Handle carrying out wire drawing through the surface of the plastic rubber substrate behind the husky copper of plating, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 1000r/min, and pulling wheel is: nylon wheel.
(5) dry cleaning being carried out on the MODIFIED PP plastic rubber substrate surface after the wire drawing processing handles;
The MODIFIED PP plastic basis material is implemented the dry cleaning method, carry out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface again after the employing plasma flame is handled;
(6) electronickelling
The method of electronickelling can be a negative electrode through the plastic rubber substrate after wire drawing is handled, and the nickel plate is an anode, and it is following that adoptable prescription is electroplated in nothing leveling nickel plating: single nickel salt NiSO 4250~350g/L, nickelous chloride NiCl 230~68g/L, boric acid H 3BO 338~53g/L, pH 4.2, brightening agent BR 220 auxiliarys 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 said plating bath can be 50 ℃, and galvanic current density can be 2A/dm 2, electroplating time can be 30min; There is not the prescription that the leveling nickel plating solution can adopt the electronickelling that U.S. Luo Menha company provides.
The bright nickel plating plating bath can adopt the prescription of the plating light quantity nickel that U.S. Luo Menha company provides following: 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 said plating bath can be 60 ℃, and galvanic current density can be 3A/dm 2,, electroplating time can be 5min.
Before electroplating nothing leveling nickel, activation treatment is arranged; Activating treatment process and condition are and are conventionally known to one of skill in the art; Said activating treatment process can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator V-37 45g/L, soak time are 2min, and temperature is a room temperature.
In step 6) plastic basis material is directly implemented new-type environment-protection electroplating technology, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath behind the electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of nickel ion respectively; 2) washing bath behind the electronickelling groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
(7) PVD plated film
To pass through MODIFIED PP plastic rubber substrate that electronickelling handles and turn linked to after the PVD stove carries out plasma treatment, and carry out the deposition of chromium layer, the 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 the stove; Soak time 5min, the technology of PVD metallizing chromium is that electric current is 50A, and 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/ every month plating line, the waste water of getting rid of in every month is 2500 tons, adopt method of the present invention after, same production capacity, but the wastewater discharge of every month is 80 tons.
The face of the planting figure of the product of embodiment 1 preparation is referring to Fig. 3.
Embodiment 2
(1) the ABS plastic base material is carried out pre-treatment
The ABS plastic base material is implemented the dry cleaning method, adopt hydrocarbon vacuum cleaned to remove the greasy dirt of ABS plastic substrate surface;
(2) plastic rubber substrate is carried out PVD (physical vapor deposition) metallization
The ABS plastic rubber substrate is carried out PVD (physical vapor deposition) metallization, and implement PVD plasma modification, metallizing bottom, metal excessively layer and metal conducting layer successively, plasma modified technique condition is ion source electric current 0.3A; Bias voltage 150V, dutycycle 80%, argon gas flow velocity 50SCCM; Vacuum pressure 0.3Pa in the oxygen gas flow rate 80SCCM, stove, soak time 6min is to reach the purpose of cleaning and change activation matrix surface; Metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power medium-frequency pulse power supply, and metallizing bottom electric current is 300A, and voltage is 800V; Depositing time is 1min, bias voltage 60V, dutycycle 50%; Argon gas flow velocity 200SCCM, coated metal are 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 are 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 technology and carry out the copper facing operation;
Technical process does, the burnt copper of the advanced electroplating of ABS plastic base material, husky copper, and concrete technology is following:
Electroplate the cupric pyrophosphate process using forever star chemical company provide prescription following: 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 bath can be 45 ℃, and galvanic current density can be 2A/dm 2, electroplating time is 5min.
Electroplating husky copper adopts the prescription of the electroplating acid copper that Le Si company provides following: the prescription that plates husky copper is following: copper sulfate CuS0 4200 ± 10g/L, sulfuric acid H 2SO 65 ± 15g/L, cl ions Cl -80~120ppm, husky agent 303 8~12ml/L, the temperature of plating bath can be 35 ℃, and galvanic current density can be 6A/dm 2,, electroplating time can be 5min; Between plating cupric pyrophosphate, the husky copper of plating, one washing arranged, the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 1min.
Carry out in the copper facing operation implementing new-type environment-protection electroplating technology, use following technology to reach: 1) adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling of cupric ion to the washing bath of electro-coppering groove respectively to the online recovery of mantoquita and to the recycle of waste water; 2) mode that respectively washing bath and the activated bath of electro-coppering groove is adopted ion exchange resin and ultra-filtration membrane recycles the water of washing usefulness.
(4) wire drawing is handled
Handle carrying out wire drawing through the surface of the plastic rubber substrate behind the husky copper of plating, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 500r/min, and pulling wheel is: abrasive belt wheel.
(5) dry cleaning being carried out on the ABS plastic rubber substrate surface after the wire drawing processing handles;
The ABS plastic base material is implemented the dry cleaning method, adopt hydrocarbon vacuum cleaned to remove the greasy dirt of ABS plastic substrate surface;
(6) electronickelling
The method of electronickelling can be a negative electrode through the plastic rubber substrate after wire drawing is handled, and the nickel plate is an anode.It is following that adoptable prescription is electroplated in nothing leveling nickel plating: 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 auxiliarys 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 said plating bath can be 60 ℃, and galvanic current density can be 5A/dm 2, electroplating time can be 5min; There is not the prescription that the leveling nickel plating solution can adopt the electronickelling that U.S. Luo Menha company provides.
The bright nickel plating plating bath can adopt the prescription of the plating light quantity nickel that U.S. Luo Menha company provides following: 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 said plating bath can be 60 ℃, and galvanic current density can be 3A/dm 2,, electroplating time can be 30min.
Before electroplating nothing leveling nickel, activation treatment is arranged; Activating treatment process and condition are and are conventionally known to one of skill in the art; Said activating treatment process can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator V-37 45g/L, soak time are 1min, and temperature is a room temperature.
In step 6) plastic basis material is directly implemented new-type environment-protection electroplating technology, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath behind the electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of nickel ion respectively; 2) washing bath behind the electronickelling groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
(7) spraying plating protective organic
The ABS plastic rubber substrate that will pass through the electronickelling processing carries out ultraviolet light polymerization (UV) spraying; Behind the about 20 μ mUV lacquer of spraying plating one bed thickness, plastic rubber substrate is sent into the infrared rays baker, spray paint rete levelling, oven dry; Temperature is 70 ℃; Time is 8min, at last the rete that sprays paint behind the levelling is accepted irradiation curing cross-linked, time 30s in the ultraviolet photo-curing stove.
Through test, original full automatic output is 20,000 m 2/ every month plating line, the waste water of getting rid of in every month is 2500 tons.After adopting method of the present invention, same production capacity, but the wastewater discharge of every month is 80 tons.
The face of the planting figure of the product of embodiment 2 preparations is referring to Fig. 2.
Embodiment 3
(1) the MODIFIED PP plastic basis material is carried out pre-treatment
The MODIFIED PP plastic basis material is implemented the dry cleaning method, carry out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface again after the employing plasma flame is handled;
(2) plastic rubber substrate is carried out PVD (physical vapor deposition) metallization
The MODIFIED PP plastic rubber substrate is carried out PVD (physical vapor deposition) metallization, and implement PVD plasma modification, metallizing bottom, metal excessively layer and metal conducting layer successively, plasma modified technique condition is ion source electric current 0.3A; Bias voltage 150V, dutycycle 50%, argon gas flow velocity 100SCCM; Vacuum pressure 0.2Pa in the oxygen gas flow rate 10SCCM, stove, soak time 10min is to reach the purpose of cleaning and change activation matrix surface; Metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power DC power supply, and metallizing bottom electric current is 50A, and voltage is 400V; Depositing time is 2min, bias voltage 20V, dutycycle 50%; Argon gas flow velocity 100SCCM, coated metal are 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 are 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 technology and carry out the copper facing operation;
Technical process does, the burnt copper of the advanced electroplating of MODIFIED PP plastic basis material, husky copper, and concrete technology is following:
Electroplate the cupric pyrophosphate process using forever star chemical company provide prescription following: 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 bath can be 50 ℃, and galvanic current density can be 1A/dm 2, electroplating time is 7min.
Electroplating husky copper adopts the prescription of the electroplating acid copper that Le Si company provides following: the prescription that plates husky copper is following: copper sulfate CuSO 4200 ± 10g/L, sulfuric acid H 2SO 465 ± 15g/L, cl ions Cl -80~120ppm, husky agent 303 8~12ml/L, the temperature of plating bath can be 28 ℃, and galvanic current density can be 3A/dm 2,, electroplating time can be 40min;
Between plating cupric pyrophosphate, the husky copper of plating, one washing arranged, the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 1.5min.
Carry out in the copper facing operation implementing new-type environment-protection electroplating technology, use following technology to reach: 1) adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling of cupric ion to the washing bath of electro-coppering groove respectively to the online recovery of mantoquita and to the recycle of waste water; 2) mode that respectively washing bath and the activated bath of electro-coppering groove is adopted ion exchange resin and ultra-filtration membrane recycles the water of washing usefulness.
(4) wire drawing is handled
Handle carrying out wire drawing through the surface of the plastic rubber substrate behind the husky copper of plating, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 700r/min, and pulling wheel is: the all-wing aircraft wheel.
(5) dry cleaning being carried out on the MODIFIED PP plastic rubber substrate surface after the wire drawing processing handles;
The MODIFIED PP plastic basis material is implemented the dry cleaning method, carry out greasy dirt and the dust that Electrostatic Treatment removes MODIFIED PP plastic basis material surface again after the employing plasma flame is handled;
(6) electronickelling
The method of electronickelling can be a negative electrode through the plastic rubber substrate after wire drawing is handled, and the nickel plate is an anode, and it is following that adoptable prescription is electroplated in nothing leveling nickel plating: single nickel salt NiSO 4250~350g/L, nickelous chloride NiCl 230~68g/L, boric acid H 3BO 338~53g/L, pH 4.2, brightening agent BR 220 auxiliarys 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 said plating bath can be 55 ℃, and galvanic current density can be 3A/dm 2, electroplating time can be 15min; There is not the prescription that the leveling nickel plating solution can adopt the electronickelling that U.S. Luo Menha company provides.
The bright nickel plating plating bath can adopt the prescription of the plating light quantity nickel that U.S. Luo Menha company provides following: 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 said plating bath can be 58 ℃, and galvanic current density can be 4A/dm 2,, electroplating time can be 20min.
Before electroplating nothing leveling nickel, activation treatment is arranged; Activating treatment process and condition are and are conventionally known to one of skill in the art; Said activating treatment process can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator V-37 45g/L, soak time are 1.5min, and temperature is a room temperature.
In step 6) plastic basis material is directly implemented new-type environment-protection electroplating technology, new-type environment-protection electroplating is to carry out according to following standard:
1) washing bath behind the electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of nickel ion respectively; 2) washing bath behind the electronickelling groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
(7) electroplate the environmental protection trivalent chromium
The method of said electrodeposited chromium and condition are for well known to a person skilled in the art method; The present invention adopts toxicological harmless to get the trivalent chromium plating technology, and chromic plating bath can adopt the prescription of the electrodeposited chromium plating bath that U.S. Luo Menha company provides following: 3C opens cylinder salt 375~450g/L, and 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 said plating bath comprises that the temperature of plating bath is 32 ℃, and galvanic electric current is close to be 8A/dm 2, electroplating time is 5min.
Described have an activation treatment before electrodeposited chromium; The method of activation treatment and condition are and are known for well known to a person skilled in the art; This method can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator ANKOR NFDS 2.6g/L; Soak time is 1min, and temperature is a room temperature.
The washing of three roads is arranged behind electrodeposited chromium, and the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 1min.
Plastic basis material is directly implemented new-type environment-protection electroplating technology, and new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath behind the electrodeposited chromium groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of chromium ion respectively; 2) washing bath behind the electrodeposited chromium groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
Through test, original full automatic output is 20,000 m 2/ every month plating line, the waste water of getting rid of in every month is 2500 tons, adopt method of the present invention after, same production capacity, but the wastewater discharge of every month is 120 tons.
The face of the planting figure of the product of embodiment 3 preparations is referring to Fig. 1.
Embodiment 4
(1) the ABS plastic base material is carried out pre-treatment
The ABS plastic base material is implemented the dry cleaning method, adopt the dry ice oil removal treatment to remove the greasy dirt and the dust on modified ABS plastic basis material surface;
(2) plastic rubber substrate is carried out PVD (physical vapor deposition) metallization
The ABS plastic rubber substrate is carried out PVD (physical vapor deposition) metallization, and implement PVD plasma modification, metallizing bottom, metal excessively layer and metal conducting layer successively, plasma modified technique condition is ion source electric current 0.4A; Bias voltage 100V, dutycycle 80%, argon gas flow velocity 10SCCM; Vacuum pressure 0.2Pa in the oxygen gas flow rate 100SCCM, stove, soak time 5min is to reach the purpose of cleaning and change activation matrix surface; Metallizing bottom, the excessive layer of metal and metal conducting layer are to adopt high-power DC power supply, and metallizing bottom electric current is 200A, and voltage is 600V; Depositing time is 2min, bias voltage 20V, dutycycle 50%; Argon gas flow velocity 100SCCM, coated metal are 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 are 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 technology and carry out the copper facing operation;
Technical process does, the burnt copper of the advanced electroplating of MODIFIED PP plastic basis material, husky copper, and concrete technology is following:
Electroplate the cupric pyrophosphate process using forever star chemical company provide prescription following: 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 bath can be 50 ℃, and galvanic current density can be 1A/dm 2, electroplating time is 20min.
Electroplating husky copper adopts the prescription of the electroplating acid copper that Le Si company provides following: the prescription that plates husky copper is following: copper sulfate CuSO 4200 ± 10g/L, sulfuric acid H 2SO 465 ± 15g/L, cl ions Cl -80~120ppm, husky agent 303 8~12ml/L, the temperature of plating bath can be 32 ℃, and galvanic current density can be 4A/dm 2, electroplating time can be 10min;
Between plating cupric pyrophosphate, the husky copper of plating, one washing arranged, the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 1min.
Carry out in the copper facing operation implementing new-type environment-protection electroplating technology, use following technology to reach: 1) adopt the mode of ion exchange resin and ultra-filtration membrane to carry out the online recycling of cupric ion to the washing bath of electro-coppering groove respectively to the online recovery of mantoquita and to the recycle of waste water; 2) mode that respectively washing bath and the activated bath of electro-coppering groove is adopted ion exchange resin and ultra-filtration membrane recycles the water of washing usefulness.
(4) wire drawing is handled
Handle carrying out wire drawing through the surface of the plastic rubber substrate behind the husky copper of plating, adopt automatic mode to carry out wire drawing, the rotating speed of drawing wire machine is 700r/min, and pulling wheel is: nylon wheel.
(5) dry cleaning being carried out on the ABS plastic rubber substrate surface after the wire drawing processing handles;
The ABS plastic base material is implemented the dry cleaning method, carry out greasy dirt and the dust that Electrostatic Treatment removes the ABS plastic substrate surface again after the employing dry ice oil removal treatment;
(6) electronickelling
The method of electronickelling can be a negative electrode through the plastic rubber substrate after wire drawing is handled, and the nickel plate is an anode, and it is following that adoptable prescription is electroplated in nothing leveling nickel plating: single nickel salt NiSO 4250~350g/L, nickelous chloride NiCl 230~68g/L, boric acid H 3BO 338~53g/L, pH 4.2, brightening agent BR 220 auxiliarys 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 said plating bath can be 55 ℃, and galvanic current density can be 3A/dm 2, electroplating time can be 15min; There is not the prescription that the leveling nickel plating solution can adopt the electronickelling that U.S. Luo Menha company provides.
The bright nickel plating plating bath can adopt the prescription of the plating light quantity nickel that U.S. Luo Menha company provides following: 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 said plating bath can be 58 ℃, and galvanic current density can be 4A/dm 2,, electroplating time can be 20min.
Before electroplating nothing leveling nickel, activation treatment is arranged; Activating treatment process and condition are and are conventionally known to one of skill in the art; Said activating treatment process can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator V-37 45g/L, soak time are 1.5min, and temperature is a room temperature.
In step 6) plastic basis material is directly implemented new-type environment-protection electroplating technology, new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath behind the electronickelling groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of nickel ion respectively; 2) washing bath behind the electronickelling groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
(7) electroplate the environmental protection trivalent chromium
The method of electrodeposited chromium and condition are for well known to a person skilled in the art method; Adopt toxicological harmless to get the trivalent chromium plating technology, chromic plating bath can adopt the prescription of the electrodeposited chromium plating bath that U.S. Luo Menha company provides following: 3C opens cylinder salt 375~450g/L, and 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 said plating bath comprises that the temperature of plating bath is 35 ℃, and galvanic electric current is close to be 10A/dm 2Electroplating time is 1min.
Described have an activation treatment before electrodeposited chromium; The method of activation treatment and condition are and are known for well known to a person skilled in the art; This method can adopt the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator ANKOR NFDS 2.6g/L; Soak time is 1min, and temperature is a room temperature.
The washing of three roads is arranged behind electrodeposited chromium, and the method for washing and condition are conventionally known to one of skill in the art, and this method adopts pure water rinsing 1min.
Plastic basis material is directly implemented new-type environment-protection electroplating technology, and new-type environment-protection electroplating is to carry out according to following standard: 1) washing bath behind the electrodeposited chromium groove adopts the mode of ion exchange resin or ultra-filtration membrane to carry out the online recycling of chromium ion respectively; 2) washing bath behind the electrodeposited chromium groove and the activated bath mode that adopts ion exchange resin or ultra-filtration membrane recycles the water of washing usefulness respectively.
(8) PVD plated film plated film
To pass through and electroplate ABS plastic rubber substrate that trivalent chromium handles and turn linked to after the PVD stove carries out plasma treatment, and carry out the deposition of zirconium nitride rete, the plasma treatment process condition is ion source electric current 0.3A, bias voltage 80V; Dutycycle 80%, vacuum pressure 0.2Pa in the argon gas flow velocity 100SCCM, stove; Soak time 5min, the technology of PVD plating zirconium nitride rete is: the multi sphere electric current is 110A, and voltage is 25V; Depositing time is 2min, bias voltage 80V, dutycycle 50%; Argon gas flow velocity 60SCCM, stream of nitrogen gas speed 200SCCM, the multi sphere target is the zirconium target.
Through test, original full automatic output is 20,000 m 2/ every month plating line, the waste water of getting rid of in every month is 2500 tons, adopt method of the present invention after, same production capacity, but the wastewater discharge of every month is 120 tons.
The face of the planting figure of the product of embodiment 4 preparations is referring to Fig. 4.

Claims (10)

1. plastic basis material copper wire drawing electric plating method is characterized in that may further comprise the steps:
1) plastic basis material is carried out pre-treatment;
2) metallize to carrying out physical vapor deposition through the pretreated plastic rubber substrate of step 1), and carry out the physical vapor deposition plasma modification successively, metallizing bottom, metal be layer and metal conducting layer excessively;
3) to through step 2) plastic rubber substrate handled directly carries out electro-coppering;
4) wire drawing being carried out on the copper electroplating layer surface of the plastic rubber substrate handled through step 3) handles;
5) dry cleaning being carried out on the plastic rubber substrate surface of handling through step 4) handles;
6) to the electronickelling of carrying out of the plastic rubber substrate handled through step 5);
7) plastic rubber substrate of handling through step 6) is turned linked to after the PVD stove carries out plasma treatment, carry out the PVD coating film treatment, to satisfy various functions, color requirement; Or
The dried spraying plating organic coating that carries out of plastic rubber substrate to handling through step 5) is handled; Or
The dried electrodeposited chromium that carries out of plastic rubber substrate to handling through step 5) is handled; Or
The dried electrodeposited chromium that carries out of plastic rubber substrate to handling through step 5) carries out the PVD coating film treatment at last and satisfies 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) said pre-treatment is to adopt dry cleaning method oil removing scrubbing; The concrete grammar of said employing dry cleaning method oil removing scrubbing adopts plasma flame to handle; The dry ice oil removal treatment, Electrostatic Treatment, at least a in the 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 2) in, the processing condition of said 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 the stove, soak time 5~10min; The processing condition of said 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, and depositing time is 1~10min, bias voltage 20~60V; Dutycycle 50%~80%, argon gas flow velocity 60~200SCCM.
4. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1 is characterized in that in step 3), saidly directly carries out electro-coppering and is selected from and electroplates cupric pyrophosphate, electroplate at least a in the husky copper;
The method of said electro-coppering is with through step 2) plastic rubber substrate handled is as negative electrode, and copper coin adopts the prescription of electroplating husky copper following: copper sulfate CuSO as anode 4200 ± 10g/L, sulfuric acid H 2SO 65 ± 15g/L, cl ions Cl -80~120ppm, husky agent 303 8~12ml/L, the temperature of plating bath is 25~40 ℃, is preferably 28~35 ℃, galvanic current density is 2~8A/dm 2, be preferably 3~6A/dm 2, electroplating time is 5~40min.
5. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1 is characterized in that in step 3) the prescription of the process using of said plating cupric pyrophosphate is following: 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 8.5~9.5, and the temperature of plating bath is 45~55 ℃, and galvanic current density is 0.5~2A/dm 2, electroplating time is 5~10min.
6. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1 is characterized in that in step 3), the electroplating acid copper prescription that the prescription of the husky copper of said plating adopts Le Si company to provide; The prescription that the technical recipe of said plating cupric pyrophosphate adopts star chemical company forever to provide;
As adopt and electroplate cupric pyrophosphate and electroplate husky process for copper, then with electroplating between the husky copper washing process being arranged at the plating cupric pyrophosphate, the method for said washing and condition are conventionally known to one of skill in the art, this method adopts pure water rinsing 1~2min.
7. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1 is characterized in that in step 4), and said wire drawing is handled, and is to adopt automatic perhaps artificial mode to carry out wire drawing, and the rotating speed of drawing wire machine is 500~1000r/min; Pulling wheel is a nylon wheel, at least a in the abrasive belt wheel, all-wing aircraft wheel.
8. 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) the concrete grammar that said employing dry cleaning is handled is to adopt plasma flame to handle the dry ice oil removal treatment; Electrostatic Treatment, at least a in the hydrocarbon vacuum cleaned method.
9. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1 is characterized in that in step 6), and said electronickelling is electroplate not have at least a in leveling nickel, the electroplating bright nickel;
The method of said electronickelling can be a negative electrode through the plastic rubber substrate after wire drawing is handled, and the nickel plate is an anode; The prescription that does not have leveling nickel plating plating employing is following: 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 auxiliarys 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 said plating bath is 40~60 ℃; Be preferably 50~60 ℃, galvanic current density is 0.5~7A/dm 2, preferred 2~5A/dm 2, electroplating time is 5~30min;
The plating bath of said electroplating bright nickel can adopt the prescription of the plating light quantity nickel that U.S. Luo Menha company provides following: 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 said plating bath is 50~65 ℃; Be preferably 58~60 ℃, galvanic current density is 2~7A/dm 2, be preferably 3~4A/dm 2, electroplating time can be 5~30min;
Said plating has leveling can not carry out activation treatment before the nickel, and said activating treatment process adopts the prescription of the activation plating bath that Japanese Ren Yuan company provides following: acvator V-3745g/L, soak time are 1~2min, and temperature is a room temperature.
10. a kind of plastic basis material copper wire drawing electric plating method as claimed in claim 1 is characterized in that in step 7) said organic coating; Be to adopt following method to realize: 1) carry out electrophoretic painting; 2) carry out powder spraying, 3) carry out ultraviolet light polymerization spraying, 4) carry out the polyurethane paint spraying;
In step 7), the method for said electrodeposited chromium is a trivalent chromium plating, and the prescription of the plating bath of said trivalent chromium plating is following: 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 said plating bath comprises that the temperature of plating bath is 30~40 ℃, is preferably 32~35 ℃, and galvanic electric current is close to be 5~18A/dm 2, be preferably 8~10A/dm 2, electroplating time is 1~5min;
Can carry out activation treatment before the said electrodeposited chromium, the prescription of the activation plating bath of said activation treatment is following: acvator ANKORNFDS 2.6g/L, soak time are 1~2min, and temperature is a room temperature;
Can carry out the washing of three roads after the said electrodeposited chromium.
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CN102851639A (en) * 2012-09-27 2013-01-02 厦门建霖工业有限公司 Environment-friendly electroless plating drawn wire-imitating surface treatment method for engineering plastic
CN102851715A (en) * 2012-09-27 2013-01-02 厦门建霖工业有限公司 Method for directly plating plastic with drawn wire appearance
CN102877025A (en) * 2012-09-27 2013-01-16 厦门建霖工业有限公司 Surface coating method for plastics with metal drawn wire appearance
CN103590082A (en) * 2013-12-03 2014-02-19 厦门建霖工业有限公司 Phosphor-less hexavalent chromium-less environmentally-friendly plastic electroplating method
CN104144571A (en) * 2014-06-18 2014-11-12 四川深北电路科技有限公司 High-density interconnection integrated circuit board manufacturing method
WO2015062161A1 (en) * 2013-10-31 2015-05-07 丁佐军 Barrier and explosion-proof composite material and manufacturing process therefor
CN105200669A (en) * 2015-10-27 2015-12-30 上海锦湖日丽塑料有限公司 Electroplating pretreatment method for plastic parts for electroplating
CN105780078A (en) * 2016-03-29 2016-07-20 武汉诚盛电子有限公司 Local laser grain machining process for car trim
CN107227474A (en) * 2017-06-27 2017-10-03 东莞市纳百川电子科技有限公司 A kind of metal surface treatment process
CN108611667A (en) * 2018-07-13 2018-10-02 九牧厨卫股份有限公司 Environmentally friendly composite deposite and preparation method thereof on a kind of copper alloy substrate
CN109097772A (en) * 2017-12-15 2018-12-28 深圳科诺桥科技股份有限公司 The preparation method of flexibility coat copper plate

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CN102758178A (en) * 2012-07-31 2012-10-31 厦门建霖工业有限公司 Method for high-power vacuum plating and wire drawing of plastic substrate
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CN102851639A (en) * 2012-09-27 2013-01-02 厦门建霖工业有限公司 Environment-friendly electroless plating drawn wire-imitating surface treatment method for engineering plastic
CN102851715A (en) * 2012-09-27 2013-01-02 厦门建霖工业有限公司 Method for directly plating plastic with drawn wire appearance
CN102877025A (en) * 2012-09-27 2013-01-16 厦门建霖工业有限公司 Surface coating method for plastics with metal drawn wire appearance
CN102851715B (en) * 2012-09-27 2014-12-31 厦门建霖工业有限公司 Method for directly plating plastic with drawn wire appearance
CN102851639B (en) * 2012-09-27 2014-12-31 厦门建霖工业有限公司 Environment-friendly electroless plating drawn wire-imitating surface treatment method for engineering plastic
WO2015062161A1 (en) * 2013-10-31 2015-05-07 丁佐军 Barrier and explosion-proof composite material and manufacturing process therefor
CN103590082A (en) * 2013-12-03 2014-02-19 厦门建霖工业有限公司 Phosphor-less hexavalent chromium-less environmentally-friendly plastic electroplating method
CN103590082B (en) * 2013-12-03 2016-03-02 厦门建霖工业有限公司 A kind of without phosphorus, non-hexavalent chromium environment friendly shape glue electro-plating method
CN104144571A (en) * 2014-06-18 2014-11-12 四川深北电路科技有限公司 High-density interconnection integrated circuit board manufacturing method
CN105200669A (en) * 2015-10-27 2015-12-30 上海锦湖日丽塑料有限公司 Electroplating pretreatment method for plastic parts for electroplating
CN105200669B (en) * 2015-10-27 2017-11-24 上海锦湖日丽塑料有限公司 Plastic part electro-plating pre-treatment method is used in one kind plating
CN105780078A (en) * 2016-03-29 2016-07-20 武汉诚盛电子有限公司 Local laser grain machining process for car trim
CN107227474A (en) * 2017-06-27 2017-10-03 东莞市纳百川电子科技有限公司 A kind of metal surface treatment process
CN109097772A (en) * 2017-12-15 2018-12-28 深圳科诺桥科技股份有限公司 The preparation method of flexibility coat copper plate
CN108611667A (en) * 2018-07-13 2018-10-02 九牧厨卫股份有限公司 Environmentally friendly composite deposite and preparation method thereof on a kind of copper alloy substrate

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