CN101343724A - Method for functional decoration film coating on engineering plastic rubber surface - Google Patents
Method for functional decoration film coating on engineering plastic rubber surface Download PDFInfo
- Publication number
- CN101343724A CN101343724A CNA2008100715954A CN200810071595A CN101343724A CN 101343724 A CN101343724 A CN 101343724A CN A2008100715954 A CNA2008100715954 A CN A2008100715954A CN 200810071595 A CN200810071595 A CN 200810071595A CN 101343724 A CN101343724 A CN 101343724A
- Authority
- CN
- China
- Prior art keywords
- engineering plastic
- layer
- vacuum chamber
- acetate
- carrying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Disclosed is a functional decoration film-coating method on the engineering plastic surface, which relates to a film-coating method, in particular to a functional decoration film-coating method on the engineering plastic surface. The coated film has the functions of corrosion resistance, wear resistance, abrasion resistance and colorful decoration. The invention provides a functional decoration film-coating method which can be used for mass and continuous production and can be directly performed on the engineering plastic surface. A porous conductive coating layer is prepared on the surface of an engineering plastic workpiece; plasma surface modification treatment is carried out on the surface of the engineering plastic workpiece prepared with the porous conductive coating layer; a layer of metallic film or metallic compound film is deposited as a base layer on the engineering plastic surface which ungergoes the plasma surface modification treatment; a functional combination layer is deposited on the base layer; a decoration layer is deposited on the functional combination layer; and a protection film is deposited on the decoration layer.
Description
Technical field
The present invention relates to a kind of film coating method, especially relate to a kind of method of carrying out functional decoration film coating on the engineering plastic surface.This plated film has erosion resistance, wear resistance, abrasion resistance and colorful function such as ornamental.
Background technology
Plating as a kind of important scale widespread use of Surface Treatment Engineering technology in industries such as automobile, household electrical appliances, bathroom for a long time, it depends on the metallization (pre-treatment) on plastic cement surface and electroplates.A large amount of heavy metal containing sewage dischargings is arranged in this two step process, both wasted precious resources, cause serious environmental to pollute again, needing a large amount of infusion of financial resourcess to administer loses more than gain.Therefore be badly in need of transforming and promoting.
Traditional plastic cement is electroplated and has been used sexavalent chrome, thereby brings serious pollution.Traditional plastic cement electroplate the material that can handle also very limited.
Along with the progressively enforcement of the objective of the struggle of building a resource-conserving and environment-friendly society and WEEE and ROHS, it is more urgent that the technology of green production becomes.Each state is all actively seeking the breakthrough of technology in this respect, and is especially technical in the improvement of the three wastes, but this is for taking stopgap measures but not effect a permanent cure.Trivalent chromium is developed in addition, but no matter this technology is in outward appearance, function, or all exists serious problem on the stability of Technology, and has problems such as the expensive and good article rate of cost is low.And for decorating plating, the chromium coating that this technology is worked it out is not accepted by people.
Publication number is that the Chinese invention patent application of CN1970830A discloses a kind of flexible conveying device and using method thereof, e Foerderanlage comprises power-driven system, guide rail and conveying belt, and described guide rail is circular arc or tubular shape in the plated film storehouse of vacuum coating film equipment; Guide rail is a kind of cavity design, and the part of conveying belt on width enters guide rail inside, and another part that conveying belt is exposed at the opening below outward is used to carry workpiece, and conveying belt keeps rigidity on width, demonstrate flexibility on thickness direction.Guide rail can be installed in the top of dissimilar vacuum coating film equipments, constitutes corresponding beat-type or continuous vacuum coating equipment.Guide rail is a cyclic shape in the plated film storehouse of vacuum coating film equipment, and conveying belt can be done a week or many week motions.When guide rail was in vacuum coating film equipment and is designed into the open and close scope of hatch door, this section guide rail was for by a movable guiding rail electronic or starter gear is operated, and when this section movable guiding rail produced displacement, door can open or close.After guide rail resetted, conveying belt can move smoothly.The e Foerderanlage of this invention can be used for vertical or horizontal, single or multiple lift, and perhaps many storehouses various combination in the revolution storehouse of two and two above difference in functionalitys or straight line storehouse forms multiple vacuum coating film equipments such as tinuous production.The e Foerderanlage of this invention can be realized the alternately conversion in vacuum coating film equipment of conveying belt and workpiece, can dispose the coating chamber of difference in functionality according to the different needs of coating process, realize the production of beat-type, serialization in batches, obtain the consistence of quality, color and luster; While production efficiency height, production cost reduces.
Summary of the invention
The present invention is directed to existing carry out in the surface treatment on the engineering plastic surface existing seriously polluted; traditional plastic cement electroplate problems such as the material that can handle is very limited; a kind of mass-producing continuous production that carries out is provided, can directly carries out the method for functional decoration film coating on the engineering plastic surface.
Technical scheme of the present invention is to utilize plasma surface modification technology and physics, chemical vapour deposition technique to replace traditional plastic cement electroplating technology, based on flexible transmission technology, be implemented in the revolution and the rotation of product in the coating process, be implemented in simultaneously and carry out the flexibility transmission between the different vacuum chambers, to obtain uniform settled layer.
The present invention includes following steps:
1) prepares one deck porous conductive coating at the engineering plastic workpiece surface;
2) handle carrying out plasma surface modification on the engineering plastic workpiece that has prepared porous conductive coating;
3) deposit metallic film or the metal compound film of one deck at the engineering plastic workpiece surface that carries out after plasma surface modification is handled as basal layer;
4) deposition function combinations layer on basal layer;
5) on the function combinations layer, deposit ornament layer;
6) on ornament layer, deposit protective membrane.
Prepare one deck porous conductive coating at the engineering plastic workpiece surface and can adopt following method:
(1) resin is added in the organic solvent, the dissolving back adds dispersion agent and non-solvent class material, adds nanometer conductive material particle and flow agent again, makes nano modification polymer (being called for short SNP) emulsion after mixing;
(2) frosting is cleaned oil removing after, with sulfuric acid and acetate, or sodium hydroxide activates, the oven dry back is standby;
(3) the nano modification macromolecule emulsion of step (1) preparation is sprayed on the frosting after step (2) oven dry, the oven dry back activates with the nitration mixture of sulfuric acid, hydrochloric acid and acetate, promptly prepares one deck porous conductive coating on frosting.
Resin can be ABS, polystyrene, polycarbonate, polyvinyl chloride, at least a in the acrylic resin etc.Organic solvent can be at least a in ethyl acetate, butylacetate, pentyl acetate, acetone, tetrahydrofuran (THF), butanone (MEK), heptanone, N-N-methyl-2-2-pyrrolidone N-, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate and the isophorone etc.Dispersion agent can be at least a in cetyl trimethylammonium bromide, fluorine octyl group sulphonyl (fluorocarbon surfactant), polyvinylpyrrolidone, the polymine etc.Non-solvent class material can be at least a in water, ethanol, propyl alcohol, the butanols etc.The nanometer conductive material particle can be at least a in nanometer silver, nanometer copper, carbon nanotube, nanometer carbon black, nanometer nickel, the ITO particles such as (nano indium tin metal oxides).Flow agent can be a kind of in silane coupling agent that polydimethylsiloxane, model are KH560, polyether modified silicon oil etc.Press mass ratio, the content of each raw material is organic solvent: non-solvent class material: portions of resin nanometer conductive material particle: dispersion agent: flow agent=1: (0.1～0.01): (0.4～0.1): (0.2～0.01): (0.01～0.001): (0.01～0.001).
In step (2), vitriolic concentration is preferably 1～6mol/L, acetate is preferably pure acetate, by volume, best sulfuric acid: acetate=4: 1, concentration sodium hydroxide is preferably 8～15mol/L, and the activatory time is preferably 1～10min, the temperature of oven dry is preferably 50 ℃, and the time of oven dry is preferably 20min.
In step (3), the temperature of oven dry is preferably 70～90 ℃, the time of oven dry is preferably 30～60min, vitriolic concentration is preferably 1mol/L, and the concentration of hydrochloric acid is preferably 1mol/L, the best pure acetate of acetate, by volume, the proportioning of sulfuric acid, hydrochloric acid and acetate is preferably sulfuric acid: hydrochloric acid: acetate=2: 1: 3, the activatory time is preferably 1～5min, is generally 5～20 μ m at the thickness of the prepared porous conductive coating of frosting.
Adopt organic solvent owing to prepare the method for one deck porous conductive coating at the engineering plastic workpiece surface, the dissolving macromolecule resin, obtain organic polymer solution, then to wherein adding dispersion agent and non-solvent class material, add the nanometer conductive material particle again, flow agent, generate one deck function film with the template construction from part, this layer film has other physicalies such as nano aperture structure and metallicity conductivity, can obtain regular nanometer micropore by preparation porous conductive coating on engineering plastic, simultaneously when follow-up plasma surface modification, can introduce active function groups easily, thereby improve the bonding force between modified layer and engineering plastic substrate surface and the subsequent deposition layer.This modified layer also possesses electroconductibility, thereby for the structural controllability of subsequent deposition layer provides assurance, has also widened the use range of engineering plastic material simultaneously.
Can adopt methods such as DC glow (DC), radio frequency aura (RF), ECR glow or bipolar pulse aura to carrying out the plasma surface modification processing on the engineering plastic workpiece that has prepared porous conductive coating, also can utilize ion source to carry out the plasma modification and handle, concrete steps are:
After vacuum tightness reaches at least 10Pa, preferably reach at least and in vacuum chamber, introduce working gas and reactant gases behind the 1Pa, utilize glow discharge electrode or ion source that workpiece surface is carried out plasma surface modification, introduce active function groups to the modified layer surface in vacuum tightness.Working gas can be argon gas or helium, and reactant gases can be N
2, CH
4, C
2H
2, O
2, H
2, H
2A kind of in O, the ammonia.These functional groups will and the base layer material of subsequent deposition between form bonding, thereby make the basal layer of subsequent deposition to obtain excellent bonding force in the mode of physics and chemistry.
Engineering plastic workpiece surface deposition one deck after carrying out the plasma surface modification processing can adopt evaporation, sputter or ion plating, preferred sputter as the metallic film or the metal compound film of basal layer.These technology are known prior arts.
The material of metallic film or metallic compound film is preferably at least a metal among stainless steel, Ti, Cr, the Al etc., the perhaps nitride of at least a metal among stainless steel, Ti, Cr, the Al etc., the perhaps oxide compound of at least a metal among stainless steel, Ti, Cr, the Al etc., the perhaps carbide of metals such as stainless steel, Ti, Cr, Al, preferred stainless steel, Cr or Ti.
The thickness of basal layer is at least 5nm, and the selection of the base layer thickness will upper limit is mainly according to the thermal expansivity of the deposition material of basal layer and engineering plastic material, modified layer.Bad matched coefficients of thermal expansion is very easy to cause the cracking of whole settled layer or even come off.For example when deposition material was selected metal Ti or Metal Cr, the thickness of basal layer will be controlled at 5～500nm, and better thickness is 50～200nm.When deposition material is selected metal Cu or metal A l, because these two kinds of material coefficient of thermal expansion coefficients and engineering plastic material and modified layer coupling are better, therefore can not be subjected to the requirement of upper thickness limit on the thickness, this mainly decides from the function of integral material cost and film.
Be to provide good bonding force as the metallic film of basal layer or the purpose of metal compound film at the engineering plastic workpiece surface deposition one deck that carries out after plasma surface modification is handled for the subsequent deposition layer.
Deposition function combinations layer can adopt evaporation, sputter or ion plating on basal layer, preferred sputter or ion plating.These technology are known prior arts.
The purpose of deposition function combinations layer provides anticorrosion, hardness on basal layer, functional performance such as resistance to wear, as the material of function combinations layer film is to design and select according to different functional requirements, as metal or metal alloys such as stainless steel, Cu, Ni, Ti, Zr, Cr, Al, the perhaps compound of above metal, this function combinations layer film can be individual layer or multilayer film, also can be gradient film, can also be laminated film.The thickness of function combinations layer is to select according to the requirement of function, and upper thickness limit and lower limit are not crucial, and it is normally determined preferred 1～10 μ m of the thickness of function combinations layer by functional requirement and other as requirements such as cost, outward appearances.
In order to obtain more secure bonding force, be preferably in the gradient film of preparation one transition between basal layer and the function combinations layer.
The deposition ornament layer can adopt evaporation, sputter or ion plating on the function combinations layer, preferred sputter or ion plating.These technology are known prior arts.
The color that can use the Metal Cr deposition to obtain decorating Cr, also can after having deposited Cr or directly, on the function combinations layer, prepare simulating golden colour, stainless steel colored, coffee-like, champagne, the coating of multiple color such as grey, these materials can be Zr, Ti, Cr, Al, at least a metal in the stainless steel etc., perhaps Zr, Ti, Cr, Al, the nitride of at least a metal in the stainless steel etc., perhaps Zr, Ti, Cr, Al, the carbide of at least a metal in the stainless steel etc., perhaps Zr, Ti, Cr, Al, the oxide compound of at least a metal in the stainless steel etc., perhaps Zr, Ti, Cr, Al, carbonitride of at least a metal in the stainless steel etc. or the like can also utilize the graphite target depositing carbon film or mix the carbon film production black coating of other metal.
The thickness of ornament layer is at least 10nm, more than the preferred 100nm.The upper thickness limit of ornament layer is not crucial, and normally factor determined by cost and outward appearance etc. for it.Sedimentary method and sedimentary film type as ornament layer are disclosed or generally acknowledged.
The deposition protective layer can adopt physical vaporous deposition or chemical Vapor deposition process on ornament layer, and these methods are known prior arts.
Protective layer is transparent protective film preferably; it can be used for the function of enhanced film, resistance to wears or corrosion resistance as raising, perhaps can be used to provide water repellent surface; reduce the hand trace influence of frequent contact component, perhaps the thickness by adjusting this layer film is to obtain more color.On a lot of industries, use to some extent at deposition protective membrane on the ornament layer, as DLC, SiO
X, TiO
2, ZrO
2, Al
2O
3With transparent protective films such as SiOCH or the like, employed method or technology have had suitable disclosing.The thickness of film is at least more than 1nm, and the upper limit of thickness mainly is that optical property and the needed function by deposit film determined.Sometimes also can utilize the different thickness of specific refractory power deposition of film to carry out the adjustment of color.
The present invention is owing to adopted engineering plastic surface modification and plasma surface modification, and technology such as deposition basis layer, function combinations layer, ornament layer and protective layer, based on flexible transmission technology coating process, transmission course and film layer structure and function are organically combined, to obtain uniform settled layer; Therefore overcome existing carry out on the engineering plastic surface existing seriously polluted and traditional plastic cement in the surface treatment electroplate problems such as the material that can handle is very limited; a kind of mass-producing continuous production that carries out is provided; can directly carry out the method for functional decoration film coating on the engineering plastic surface, the engineering plastic product that is obtained has high-quality function of surface decoration film coating.
Description of drawings
Fig. 1 is the structural representation of the engineering plastic monomer vacuum chamber film coating apparatus of the embodiment of the invention.
Fig. 2 is the structural representation of the engineering plastic continuous coating apparatus of the embodiment of the invention.
Fig. 3 is the engineering plastic continuous coating production line synoptic diagram of the embodiment of the invention.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Equipment of the present invention can be engineering plastic monomer vacuum chamber film coating apparatus, preferably adopts the engineering plastic continuous coating apparatus.
Referring to Fig. 1, engineering plastic monomer vacuum chamber film coating apparatus generally is provided with vacuum chamber, vacuum-pumping system, deposition source, gas control system, bias system, glow discharge electrode or ion source etc.Wherein, vacuum chamber 8 is fixedly installed on the board 1, and vacuum-pumping system is connected with vacuum pumping opening, is used to the vacuum chamber extracting vacuum.The pivoted frame 2 of carrying workpiece can be realized revolution and rotation, and bias system is connected with pivoted frame 2 and applies bias voltage for workpiece.Installation position 3 is used to install directed electric arc Style Columu Talget on big flange 7, can realize the installation of the directed column electric arc target of racemosus and the collocation of multiple target.When needs, big flange 7 can be removed mounting center hydatogenesis source, back.Installation position 4 can be installed glow discharge electrode as required, perhaps ion source, and perhaps sputtering target, the collocation that when sputtering target is installed racemosus sputtering target and multiple target can be installed, the sputter mode can be selected according to actual needs.Tracheae 5 is connected with gas control system, is used for charging in vacuum chamber 8 working gas or the reactant gases of needs.Cryogenic condensation coil pipe 6 is connected with cryogenic system, is used for the indoor steam of extracting vacuum.Engineering plastic monomer vacuum chamber film coating apparatus as shown in Figure 1 can be arranged in pairs or groups flexibly according to actual needs and be realized the application of multiple function, and the size of vacuum chamber and the quantity of deposition source are unrestricted.
Adopt engineering plastic monomer vacuum chamber film coating apparatus need in same vacuum chamber, use multiple different process at the engineering plastic surface coating, disturb and have influence on the stability of production and repeated and might cause between the different process, production efficiency is low simultaneously, therefore preferably adopts the engineering plastic continuous coating apparatus.The engineering plastic continuous coating apparatus generally is provided with at least 2 vacuum chambers, wherein has at least 1 vacuum chamber to be used to into part or goes out part.The pivoted frame of engineering plastic continuous coating apparatus as shown in Figure 2 and transmission system are based on flexible transmission technology; advance part vacuum chamber 15 and be used for the transition of atmospheric pressure state and high vacuum; it is realized with atmospheric isolated by valve 36; with what advance that part vacuum chamber 15 is connected is one to be used for the vacuum chamber 16 to the plasma surface modification on engineering plastic surface; be one to be used for the sedimentary vacuum chamber 17 of basal layer after vacuum chamber 16; after vacuum chamber 17 is to be used for the sedimentary vacuum chamber 18 of function combinations layer and to be used for the sedimentary vacuum chamber 19 of ornament layer; be to be used for the sedimentary vacuum chamber 20 of protective layer after vacuum chamber 19; be at last be used between high vacuum state and atmospheric pressure state transition go out part vacuum chamber 21, vacuum chamber 21 is to realize with atmospheric isolated by valve 43.Intervening vaive 37～42 is installed between the vacuum chamber 15～21, realizes completely cutting off between the vacuum chamber.The engineering plastic continuous coating apparatus is except pivoted frame 22～28 and transporting rail 29～35 are different, adopted and the identical vacuum chamber structure of monomer vacuum chamber film coating apparatus shown in Figure 1, each vacuum chamber is selected vacuum system, deposition source, gas and Controlling System, bias system, glow discharge electrode or ion source etc. that will be equipped with according to function and purposes separately.The quantity of vacuum chamber is expanded or reduced to the design of such vacuum chamber can be neatly according to factors such as the process requirements of reality, production efficiency, costs of investment.The needs quantity that pitch time that basis sets in this device and coating process decide conveying belt is used for workpiece loading and unloading outward but have at least a conveying belt to be in filming equipment, has at least a conveying belt to be in the vacuum coating film equipment.In coating process; plasma surface modification vacuum chamber 16, basal layer deposition vacuum chamber 17, function combinations layer deposition vacuum chamber 18, ornament layer deposition vacuum chamber 19 and protective layer deposition vacuum chamber 20 are in always because the high vacuum state of 0.005Pa does not expose atmosphere.Owing to be provided with isolated valve between two adjacent vacuum chambers, therefore such engineering plastic continuous coating apparatus can solve mutual interferential problem between the different depositing operations, guarantees quality product.
The needs quantity that pitch time that basis sets in the engineering plastic continuous coating apparatus and coating process decide conveying belt, be used for workpiece loading and unloading outward but have at least a conveying belt to be in filming equipment, have at least a conveying belt to be in the vacuum coating film equipment.
In order to reduce the influence of steam, in advancing part vacuum chamber 15, be equipped with the cryogenic trapping system at least and be used to catch steam coating process.Other vacuum chamber can be equipped with but be not necessary.
During work, to guarantee that at first valve 36 and valve 37 close, exit to atmospheric pressure state to advancing part vacuum chamber 15, Open valve 36, the conveying belt that workpiece is not plated in carrying on the device external track 44 is fed to into part vacuum chamber 15, valve-off 36, the vacuum unit that starts vacuum chamber 15 is vacuum chamber 15 extracting vacuum.When plasma surface modification is no conveying belt, Open valve 37 under valve 36 closing state, conveying belt will be transferred in the plasma surface modification vacuum chamber 16, valve-off 37, and workpiece will be handled in plasma surface modification vacuum chamber 16 accordingly.By that analogy, workpiece finally is transferred in the protective layer deposition vacuum chamber 20 and finishes corresponding plated film.At this moment, when guaranteeing out that part vacuum chamber 21 is in vacuum state and does not have conveying belt, open valve 42, conveying belt will be transferred to out part vacuum chamber 21, valve-off 42, be deflated to atmospheric pressure state to going out part vacuum chamber 21, Open valve 43, the conveying belt that workpiece has been plated in carrying is transferred to out on part vacuum chamber 21 external orbital 44 outward.Valve-off 43 is again for going out part vacuum chamber 21 extracting vacuum.So do action is realized beat-type continuous coating technology.
Above-mentioned engineering plastic continuous coating apparatus is for illustrative, and nonrestrictive.The technician of the industry can make up in actual applications flexibly; reduce or increase the quantity of vacuum chamber; handle the vacuum chamber merging as in the specific embodiment of back, advancing part vacuum chamber and plasma surface modification; basal layer deposition vacuum chamber and function combinations floor deposition vacuum chamber chamber are merged, with the protective membrane deposition vacuum chamber with go out the part vacuum chamber and merge.Certainly also can increase more vacuum chamber in order to improve productive temp.
Processing method discussed above can make up flexibly as required and be not to be that regulation is constant.
Though utilize the present invention can be directly at engineering plastic surface preparation functional decoration settled layer to replace traditional plastic cement electroplating technology, be not limited thereto, it also can combine with traditional electroplating technology and be used to prepare special surface.
Following specific embodiment will the present invention is further illustrated in conjunction with Fig. 3, and these embodiment are for illustrative, but not be the restriction of content of the present invention.
Referring to Fig. 3, this project plastic cement continuous coating apparatus is based on flexible transmission technology, by the vertical successive sedimentation device of 4 vacuum chamber combinations, the 1st vacuum chamber # 1 is used to into part and plasma surface modification processing in this device, can be equipped with glow discharge electrode or ion source; The 2nd vacuum chamber # 2 is used for the preparation of basal layer and function combinations layer, the 3rd vacuum chamber # 3 is used for the preparation of ornament layer, at least a in evaporation source, sputtering target, the electric arc target can be equipped with in the 2nd vacuum chamber and the 3rd vacuum chamber as required neatly, ion source and other subsystem can also be equipped with; The 4th vacuum chamber # 4 is used to prepare protective membrane and goes out part, and the 4th vacuum chamber can dispose PVD coating system or CVD system as required.In the middle of adjacent two vacuum chambers, be provided with by the valve of pneumatic or electronic control opening and closing (V1～V5).In the course of the work, the 2nd vacuum chamber # 2 and the 3rd vacuum chamber # 3 are in vacuum state always and do not expose atmospheric.The needs quantity that pitch time that basis sets in this device and coating process decide conveying belt is used for workpiece loading and unloading outward but have at least a conveying belt to be in filming equipment, has at least a conveying belt to be in the vacuum coating film equipment.
In order to reduce the influence of steam, in the 1st vacuum chamber, be equipped with the cryogenic trapping system at least and be used to catch steam coating process.Other vacuum chamber can be equipped with but be not necessary.
When needs when the 1st vacuum chamber # 1 advances part, to guarantee that at first valve V1 and V2 close, exit to atmospheric pressure state to the 1st vacuum chamber # 1, Open valve V1, the conveying belt that workpiece is not plated in the outer carrying of equipment is fed to the 1st vacuum chamber # 1, and valve-off V1 starts vacuum system.After the workpiece of the 1st vacuum chamber # 1 is handled, Open valve V2 under valve V1 closing state, conveying belt will be transferred among the 2nd vacuum chamber # 2, valve-off V2, and workpiece will carry out corresponding plated film in the 2nd vacuum chamber #2.By that analogy, workpiece finally is transferred among the 4th vacuum chamber # 4 and the corresponding plated film that is done.At this moment, guaranteeing to be deflated to atmospheric pressure state to the 4th vacuum chamber # 4 under the situation that valve V4 and V5 close, Open valve V5, the conveying belt that workpiece has been plated in carrying is transferred on the filming equipment outside track.Valve-off V5 is the 4th vacuum chamber # 4 extracting vacuum again.So do action is realized beat-type continuous coating technology.
Should be appreciated that, this scheme only is proposing with the needs of implementing for explanation, as the engineering plastic continuous coating apparatus various embodiments and improvement can be arranged, as increase independent advancing the part vacuum chamber and go out the part vacuum chamber, perhaps increase the deposition vacuum chamber of more difference in functionality etc.
Below provide several relevant specific embodiments.
The material of present car door operating handle mainly contains materials such as PC/ABS, nylon, the PC/ABS material is owing to the problem of its structural strength is easy to fracture, though nylon material has solved the problems referred to above, but the outward appearance of utilizing traditional electroplating technology to make again can not be satisfactory, and major part has adopted the way of spraying to carry out surface treatment.Utilize way of the present invention can on nylon material, prepare car door operating handle with good function and outward appearance.Present embodiment is to use engineering plastic continuous coating apparatus as shown in Figure 3 to prepare the car door operating handle of decorating the Cr look above the material at PA (ADELL BH38).Because car door operating handle is often contacted by staff, therefore preparing one deck can prevent that the protective layer of hand trace is necessary.In the present embodiment, the base vacuum of the 2nd vacuum chamber and the 3rd vacuum chamber is to be better than 0.005Pa, and does not expose atmospheric.
1) preparation of porous conductive coating, the gauge control of this layer is at 5～50 μ m.
Adopt magnetic stirrer to disperse, mix by following raw material and consumption, be mixed with the nano modification macromolecule emulsion.
Organic solvent (adopt butylacetate, heptanone and N-N-methyl-2-2-pyrrolidone N-, by volume, butylacetate: heptanone: N-N-methyl-2-2-pyrrolidone N-=10: 1: 1) be 45g;
Non-solvent class material (water) is 1g;
(ABS and acrylic resin are pressed mass ratio to resin, ABS: acrylic resin=3: 0.2) be 3g;
(nanometer silver and carbon nanotube are pressed mass ratio to conductive particle, nanometer silver: carbon nanotube=2: 1) be 3g;
Flow agent (polyether modified silicon oil) is 0.1g;
Dispersion agent (polymine) is 0.1g.
The PA workpiece is sprayed emulsion behind electrochemical deoiling, the oven dry back activates with dilute hydrochloric acid, carries out cleaning, drying again.
2) the said products is cleaned the back on the conveying belt that is mounted on the carrying workpiece.Guaranteeing to charge into atmosphere to atmospheric pressure state to the 1st vacuum chamber under the situation that valve V2 closes, open valve V1, the product transmission is entered the 1st vacuum chamber, valve-off V1.Start the vacuum unit extracting vacuum of the 1st vacuum chamber.
3) plasma surface modification: after treating that vacuum tightness reaches 0.5Pa, charge into Ar and oxygen as working gas in proportion at 2: 1 to the 1st vacuum chamber, pressure-controlling is opened the pivoted frame switch at 3Pa, open the aura power supply, voltage control-300～-500V carries out plasma surface modification 3min.Close gas, power supply and pivoted frame after finishing.
4) open valve V2 between the 1st vacuum chamber and the 2nd vacuum chamber, the conveying belt of carrying workpiece is transferred to the 2nd vacuum chamber, close the valve V2 between the 1st vacuum chamber and the 2nd vacuum chamber.
5) basal layer deposition: after treating the base vacuum recovery of the 2nd vacuum chamber, open the pivoted frame switch, the thick Ti metallic membrane of deposition 50nm deposits the thick Ti/Cu of 100nm then and carries plated film.
6) combination function layer deposition: in the 2nd vacuum chamber, continue the thick Cu metallic membrane of deposition 5 μ m, and then deposit the thick Ni-V alloy film of 3.5 μ m.
7) open valve V3 between the 2nd vacuum chamber and the 3rd vacuum chamber, the conveying belt of carrying workpiece is transferred to the 3rd vacuum chamber, close the valve V3 between the 2nd vacuum chamber and the 3rd vacuum chamber.
8) ornament layer deposition: after treating the base vacuum recovery of the 3rd vacuum chamber, open the pivoted frame switch, deposit the thick Metal Cr layer of 0.3 μ m.
9) open valve V4 between the 3rd vacuum chamber and the 4th vacuum chamber, the conveying belt of carrying workpiece is transferred to the 4th vacuum chamber, valve-off.
10) protective layer deposition: open the 4th vacuum chamber pivoted frame switch, use tetramethyl-ring tetrasiloxane (TMCTS) and Ar to utilize the method for PECVD to prepare the thick SiOCH film of 8nm.
11) exit to the 4th vacuum chamber open valve V5 to atmospheric pressure state, will carry and plate finished piece(s) and be transferred to outside the plated film line, valve-off V5 is the 4th vacuum chamber extracting vacuum again.
BMC (unsaturated polyester Bulk Molding Compound) adapts to various moulding processs again owing to have good electric property, mechanical property, thermotolerance and chemical resistance, can satisfy various products to performance demands, therefore more and more is subjected to liking of users.This embodiment is to use the functional decoration coating of engineering plastic continuous coating apparatus direct deposition simulating golden colour on the product of BMC as shown in Figure 3 to describe.Deposited one deck SiO in the present embodiment
2Film, this film is the chemical resistance of enhanced film on the one hand, further improves the yellow degree and the red degree of color simultaneously, makes its more approaching gold.The base vacuum of the 2nd vacuum chamber and the 3rd vacuum chamber is better than 0.005Pa in this process, does not expose atmosphere.
1) preparation of porous conductive coating, the gauge control of this layer is at 5～50 μ m.
Disperse, mix by following raw material and materials magnetic stirrer, be mixed with the nano modification macromolecule emulsion:
Organic solvent (adopt ethyl acetate, butanone and N-N-methyl-2-2-pyrrolidone N-, by volume, ethyl acetate: butanone: N-N-methyl-2-2-pyrrolidone N-=10: 1: 1) be 45g;
Non-solvent material (ethanol) is 5g;
(ABS and acrylic resin are pressed mass ratio to resin, ABS: acrylic resin=10: 1) be 6g;
(nanometer silver and nanometer copper are pressed mass ratio, nanometer silver: nanometer copper=1: 3) be 5g to conductive particle;
Flow agent (polyether modified silicon oil and KH560 silane coupling agent, by volume, polyether modified silicon oil: KH560 silane coupling agent=1: 1) be 0.1g;
Dispersion agent (polymine) is 0.1g;
The BMC workpiece is sprayed emulsion behind electrochemical deoiling, the oven dry back activates with dilute hydrochloric acid, carries out cleaning, drying again.
2) the workpiece cleaning oven dry back dress that will prepare porous conductive coating hangs on the conveying belt, under the situation that assurance valve V2 closes, exit to atmospheric pressure state to the 1st vacuum chamber, Open valve V1, the conveying belt of carrying workpiece is transferred in the 1st vacuum chamber, valve-off V1, and the vacuum unit extracting vacuum of opening the 1st vacuum chamber.
3) plasma surface modification: after the vacuum tightness for the treatment of the 1st vacuum chamber reaches 0.5Pa, starting the pivoted frame switch makes workpiece carry out rotation and revolution in vacuum chamber, in vacuum chamber, charge into Ar and oxygen in proportion at 2: 1 as working gas, control pressure is at 5Pa, open the aura power supply, control voltage-250～-500V carries out plasma surface modification 3min.Close the aura power supply afterwards, turn-off gas, turn-off the pivoted frame switch.
4) Open valve V2, the conveying belt of carrying workpiece is transferred in the 2nd vacuum chamber valve-off V2.
5) basal layer deposition: after treating the base vacuum recovery of the 2nd vacuum chamber, open the pivoted frame switch, the thick Ti metallic membrane of deposition 100nm.Preparing thickness then is the thick Ti/ stainless steel gradient film of 200nm.
5) function combinations layer deposition: continue in the 2nd vacuum chamber, to deposit the thick stainless steel layer of 3～5 μ m.Close shielding power supply, under meter, grid bias power supply and pivoted frame switch afterwards.
6) Open valve V3, the conveying belt of carrying workpiece is transferred in the 3rd vacuum chamber valve-off V3.
7) ornament layer deposition: after treating the base vacuum recovery of the 3rd vacuum chamber, open the pivoted frame switch, the pure Zr of deposition 1min on the function combinations layer.Deposit the thick ZrN of 0.25 μ m then, to obtain the ornament layer of imitative gold.Afterwards, close target power supply, under meter, grid bias power supply and pivoted frame switch.
8) Open valve V4, the conveying belt of carrying workpiece is transferred in the 4th vacuum chamber valve-off V4.
9) protective layer deposition: open the 4th vacuum chamber pivoted frame and open commentaries on classics, use positive tetraethyl orthosilicate (TEOS), O
3SiO with Ar deposition 10nm
2Film.
10) charge into atmosphere to atmospheric pressure state to the 4th vacuum chamber, open valve V5, the conveying belt that carrying has been plated finished piece(s) is transferred to outside the plated film line.Valve-off V5 is the 4th vacuum chamber extracting vacuum again.
Present embodiment is to use tinuous production to prepare to have the functional decoration coating of the champagne of good corrosion-resistant and friction resistant on PBT (polybutyl terapthalate) material.Employed PBT material is a GE VALOX series.In order to obtain better decorative effect, can on forming mould, prepare husky fourth lines or wire drawing lines with the electrical spark mode, carry out injection moulding then and directly form husky fourth or wire drawing outward appearance at product surface.The base vacuum of the 2nd vacuum chamber and the 3rd vacuum chamber is better than 0.005Pa in this process, does not expose atmosphere.
1) preparation of porous conductive coating, the gauge control of this layer is at 5～50 μ m.
Disperse, mix by following raw material and materials magnetic stirrer, be mixed with the nano modification macromolecule emulsion:
Organic solvent (adopt acetone, butylacetate, tetrahydrofuran (THF), by volume, acetone: butylacetate: tetrahydrofuran (THF)=5: 1: 8) be 45g;
Non-solvent class material (water) is 2g;
Resin (ABS and polycarbonate are pressed mass ratio, ABS: polycarbonate is 5: 1) is 2.5g;
Conductive particle (nanometer silver and nanometer carbon black are pressed mass ratio, nanometer silver: nanometer carbon black is 4: 1) is 2g;
Flow agent (polydimethylsiloxane) is 0.1g;
Dispersion agent (polymine) is 0.1g.
The PBT workpiece is sprayed emulsion behind electrochemical deoiling, the oven dry back activates with dilute hydrochloric acid, carries out cleaning, drying again.
2) the PBT product that will prepare porous conductive coating is mounted on the transport tape of carrying workpiece.Charge into atmosphere to the 1st vacuum chamber and open valve V1, the product transmission is entered in the 1st vacuum chamber.Valve-off V1 starts the vacuum unit extracting vacuum of the 1st vacuum chamber.
3) vacuum pressure for the treatment of the 1st vacuum chamber charges into O in proportion less than 1Pa at 1: 1: 2 in the 1st vacuum chamber
2, N
2With the voltage-controlled 5Pa that is made as of Ar, open the pivoted frame switch, open the aura power supply, voltage control-250～-500V carries out plasma surface modification 3min.Close gas, power supply and pivoted frame after finishing.
4) open valve V2 between the 1st vacuum chamber and the 2nd vacuum chamber, the conveying belt of carrying workpiece is transferred to the 2nd vacuum chamber, close the valve V2 between the 1st vacuum chamber and the 2nd vacuum chamber.
5) basal layer deposition: open the 2nd vacuum chamber pivoted frame switch, the Cr metallic membrane that deposition 200nm is thick in the 2nd vacuum chamber is as basal layer.
6) function combinations layer deposition: continue thick CrN/Cr multilayer film at the 2nd vacuum chamber deposition 2～3 μ m.
7) open valve V3 between the 2nd vacuum chamber and the 3rd vacuum chamber, the conveying belt of carrying workpiece is transferred to the 3rd vacuum chamber, close the valve V3 between the 2nd vacuum chamber and the 3rd vacuum chamber.
8) ornament layer deposition: open the 3rd vacuum chamber pivoted frame switch, the thick ZrCN metal compound film layer of deposition 0.25 μ m on the function combinations layer.
9) open valve V4 between the 3rd vacuum chamber and the 4th vacuum chamber, the conveying belt of carrying workpiece is transferred to vacuum chamber 4, valve-off.
10) transparent film deposition: open the 4th vacuum chamber pivoted frame switch, in the 4th vacuum chamber, utilize acetylene gas to prepare the DLC transparent protective film of 0.1 μ m.
11) opening valve V5 after the venting of the 4th vacuum chamber, with finishing outside workpiece transfer to the 4 vacuum chambers of plated film, close the 4th door for vacuum chamber, is the 4th vacuum chamber extracting vacuum again.
This embodiment is to use engineering plastic list vacuum chamber film coating apparatus to electroplate the anti-stainless steel colored functional decoration coating of preparation at the product of PC/ABS material in conjunction with wet method and describes.This embodiment carries out on copper electroplating layer, also can realize fully at electroless nickel layer, but a large amount of risings that tend to bring cost like that.
1) at first just the PC/ABS plastic parts utilizes traditional plastic cement plating means preparation that the thick copper layer of 15～25 μ m is arranged, and carries out wire drawing then and handles.Clean afterwards and toast on the back and hang up into vacuum chamber.Close door for vacuum chamber, start vacuum unit extracting vacuum.
2) treat that vacuum tightness reaches 0.01Pa, open the pivoted frame switch, the ion source in vacuum chamber is introduced Ar and the H2 as working gas, ratio is 1: 4, keep vacuum tightness at 0.5Pa, open the ion source power supply and carry out plasma clean 3min, voltage control is at 300～500V.Powered-down and Ar after finishing.
3) continue extracting vacuum, treat that vacuum indoor pressure is lower than 0.008Pa after, the multilayer film that deposition is formed as the Ni-V and the Cr of function combinations layer, thickness is at 2～5 μ m.Deposit the ornament layer of the thick ZrN of 0.15 μ m afterwards as artificial stainless steel colour.The ZrO for preparing 6～10nm then is as protective membrane.
4) in vacuum chamber (this embodiment is to use the preparation of monomer vacuum chamber), charge into atmosphere, treat after door for vacuum chamber is opened product to be taken out.
Although described some specific embodiments of the present invention for illustrative purposes, should be understood that in the total scope of the present invention to have various embodiments and improvement.
Claims (10)
1. method of carrying out functional decoration film coating on the engineering plastic surface is characterized in that may further comprise the steps:
1) prepares one deck porous conductive coating at the engineering plastic workpiece surface;
2) handle carrying out plasma surface modification on the engineering plastic workpiece that has prepared porous conductive coating;
3) deposit metallic film or the metal compound film of one deck at the engineering plastic workpiece surface that carries out after plasma surface modification is handled as basal layer;
4) deposition function combinations layer on basal layer;
5) on the function combinations layer, deposit ornament layer;
6) on ornament layer, deposit protective membrane.
2. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 1 is characterized in that preparing one deck porous conductive coating at the engineering plastic workpiece surface adopts following method:
1) resin is added in the organic solvent, the dissolving back adds dispersion agent and non-solvent class material, adds nanometer conductive material particle and flow agent again, makes the nano modification macromolecule emulsion after mixing;
2) frosting is cleaned oil removing after, with sulfuric acid and acetate, or sodium hydroxide activates, the oven dry back is standby;
3) the nano modification macromolecule emulsion with step 1) preparation is sprayed on step 2) on the frosting after the oven dry, the oven dry back activates with the nitration mixture of sulfuric acid, hydrochloric acid and acetate, promptly prepares one deck porous conductive coating on frosting.
3. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 2 is characterized in that resin is selected from ABS, polystyrene, polycarbonate, polyvinyl chloride, at least a in the acrylic resin; Organic solvent is selected from least a in ethyl acetate, butylacetate, pentyl acetate, acetone, tetrahydrofuran (THF), butanone, heptanone, N-N-methyl-2-2-pyrrolidone N-, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate and the isophorone; Dispersion agent is selected from least a in cetyl trimethylammonium bromide, fluorine octyl group sulphonyl, polyvinylpyrrolidone, the polymine; Non-solvent class material is selected from least a in water, ethanol, propyl alcohol, the butanols; The nanometer conductive material particle is selected from least a in nanometer silver, nanometer copper, carbon nanotube, nanometer carbon black, nanometer nickel, the nano indium tin metal oxide particle; Flow agent is selected from a kind of in silane coupling agent that polydimethylsiloxane, model are KH560, the polyether modified silicon oil.
4. as claim 2 or 3 described a kind of methods of carrying out functional decoration film coating on the engineering plastic surface, it is characterized in that by mass ratio the content of each raw material is organic solvent: non-solvent class material: portions of resin nanometer conductive material particle: dispersion agent: flow agent=1: (0.1～0.01): (0.4～0.1): (0.2～0.01): (0.01～0.001): (0.01～0.001).
5. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 2, it is characterized in that in step 2) in, vitriolic concentration is 1～6mol/L, acetate is pure acetate, by volume, and sulfuric acid: acetate=4: 1, concentration sodium hydroxide is 8～15mol/L, the activatory time is 1～10min, and the temperature of oven dry is 50 ℃, and the time of oven dry is 20min; In step 3), the temperature of oven dry is 70～90 ℃, the time of oven dry is 30～60min, vitriolic concentration is 1mol/L, the concentration of hydrochloric acid is 1mol/L, the pure acetate of acetate, by volume, the proportioning of sulfuric acid, hydrochloric acid and acetate is a sulfuric acid: hydrochloric acid: acetate=2: 1: 3, the activatory time is 1～5min.
6. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 1, it is characterized in that handling employing DC glow, radio frequency aura, ECR glow or bipolar pulse aura method, or utilize ion source to carry out the plasma modification and handle carrying out plasma surface modification on the engineering plastic workpiece that has prepared porous conductive coating.
7. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 1, it is characterized in that to carrying out the plasma surface modification processing on the engineering plastic workpiece that has prepared porous conductive coating be DC glow, radio frequency aura, ECR glow or bipolar pulse aura method, concrete steps are:
After reaching at least 10Pa, vacuum tightness in vacuum chamber, introduces working gas and reactant gases, utilize glow discharge electrode or ion source that workpiece surface is carried out plasma surface modification, introduce active function groups to the modified layer surface, working gas is argon gas or helium, and reactant gases is N
2, CH
4, C
2H
2, O
2, H
2, H
2A kind of in O, the ammonia.
8. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 1 is characterized in that depositing metallic film or metal compound film employing evaporation, sputter or the ion plating of one deck as basal layer at the engineering plastic workpiece surface that carries out after plasma surface modification is handled; The material of metallic film or metallic compound film is at least a metal among stainless steel, Ti, Cr, the Al, the perhaps nitride of at least a metal among stainless steel, Ti, Cr, the Al, the perhaps oxide compound of at least a metal among stainless steel, Ti, Cr, the Al, the perhaps carbide of stainless steel, Ti, Cr, Al metal.
9. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 1 is characterized in that deposition function combinations layer adopts evaporation, sputter or ion plating on basal layer; The deposition ornament layer adopts evaporation, sputter or ion plating on the function combinations layer.
10. a kind of method of carrying out functional decoration film coating on the engineering plastic surface as claimed in claim 1 is characterized in that the deposition protective layer adopts physical vaporous deposition or chemical Vapor deposition process on ornament layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100715954A CN101343724B (en) | 2008-08-15 | 2008-08-15 | Method for functional decoration film coating on engineering plastic rubber surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100715954A CN101343724B (en) | 2008-08-15 | 2008-08-15 | Method for functional decoration film coating on engineering plastic rubber surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101343724A true CN101343724A (en) | 2009-01-14 |
| CN101343724B CN101343724B (en) | 2011-01-19 |
Family
ID=40245836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100715954A Expired - Fee Related CN101343724B (en) | 2008-08-15 | 2008-08-15 | Method for functional decoration film coating on engineering plastic rubber surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101343724B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101868129A (en) * | 2009-04-16 | 2010-10-20 | 富准精密工业(深圳)有限公司 | Shell and manufacturing method thereof |
| CN101985738A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for depositing metal or hard ornament film on plastic substrate |
| CN101988187B (en) * | 2009-08-07 | 2012-11-07 | 沈阳科友真空技术有限公司 | Vacuum magnetron sputtering color plating equipment |
| CN103568428A (en) * | 2013-11-14 | 2014-02-12 | 厦门建霖工业有限公司 | Hard film structure applied to engineering plastics and preparation method thereof |
| CN103818047A (en) * | 2014-02-28 | 2014-05-28 | 厦门建霖工业有限公司 | Surface coating structure of engineering plastic and preparation method thereof |
| CN105026604A (en) * | 2012-10-23 | 2015-11-04 | 欧瑞康表面解决方案股份公司，特吕巴赫 | Plastic component coated with an embedded pvd layer |
| CN105482319A (en) * | 2016-01-18 | 2016-04-13 | 苏州法斯特信息科技有限公司 | Abrasion resistant anticorrosive plastic material and preparation method thereof |
| CN105603477A (en) * | 2015-12-22 | 2016-05-25 | 苏州禾川化学技术服务有限公司 | Novel process for pretreatment of chemical copper plating of ABS (acrylonitrile butadiene styrene) plastics |
| CN105671511A (en) * | 2016-03-29 | 2016-06-15 | 武汉诚盛电子有限公司 | Whole plasma vacuum plating process for car ornament |
| CN106978582A (en) * | 2015-10-29 | 2017-07-25 | 株式会社岛津制作所 | Film build method and film formation device |
| CN107304469A (en) * | 2016-04-23 | 2017-10-31 | 广东祖戈卫浴科技有限公司 | A kind of stainless steel surfaces stiffened treatment technology |
| CN109221102A (en) * | 2018-10-30 | 2019-01-18 | 广东粤迪厚创科技发展有限公司 | A kind of antibacterial new material |
| CN111004997A (en) * | 2019-12-12 | 2020-04-14 | 成都新柯力化工科技有限公司 | Barrier plastic film for liquid product packaging and preparation method thereof |
| CN111018362A (en) * | 2019-12-25 | 2020-04-17 | 浙江星星科技股份有限公司 | Coating processing method of 3D curved surface deep groove panel |
| WO2020238144A1 (en) * | 2019-05-31 | 2020-12-03 | 厦门大学 | Plastic electroplating method |
| CN112501535A (en) * | 2020-12-15 | 2021-03-16 | 安徽恒茂宜高电镀科技有限公司 | Method and device for enhancing binding force of new energy automobile plastic accessory coating |
-
2008
- 2008-08-15 CN CN2008100715954A patent/CN101343724B/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101868129A (en) * | 2009-04-16 | 2010-10-20 | 富准精密工业(深圳)有限公司 | Shell and manufacturing method thereof |
| CN101985738A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for depositing metal or hard ornament film on plastic substrate |
| CN101988187B (en) * | 2009-08-07 | 2012-11-07 | 沈阳科友真空技术有限公司 | Vacuum magnetron sputtering color plating equipment |
| CN105026604A (en) * | 2012-10-23 | 2015-11-04 | 欧瑞康表面解决方案股份公司，特吕巴赫 | Plastic component coated with an embedded pvd layer |
| CN105026604B (en) * | 2012-10-23 | 2018-05-18 | 欧瑞康表面解决方案股份公司，普费菲孔 | The plastic components coated with embedded PVD- layers |
| CN103568428A (en) * | 2013-11-14 | 2014-02-12 | 厦门建霖工业有限公司 | Hard film structure applied to engineering plastics and preparation method thereof |
| CN103818047B (en) * | 2014-02-28 | 2016-06-22 | 厦门建霖工业有限公司 | A kind of engineering plastic surface coating structure and preparation method thereof |
| CN103818047A (en) * | 2014-02-28 | 2014-05-28 | 厦门建霖工业有限公司 | Surface coating structure of engineering plastic and preparation method thereof |
| CN106978582A (en) * | 2015-10-29 | 2017-07-25 | 株式会社岛津制作所 | Film build method and film formation device |
| CN105603477A (en) * | 2015-12-22 | 2016-05-25 | 苏州禾川化学技术服务有限公司 | Novel process for pretreatment of chemical copper plating of ABS (acrylonitrile butadiene styrene) plastics |
| CN105603477B (en) * | 2015-12-22 | 2017-12-26 | 苏州禾川化学技术服务有限公司 | A kind of ABS plastic electro-coppering pretreatment process |
| CN105482319B (en) * | 2016-01-18 | 2018-05-04 | 淄博中南医药包装材料股份有限公司 | A kind of wear-and corrosion-resistant plastic material and preparation method thereof |
| CN105482319A (en) * | 2016-01-18 | 2016-04-13 | 苏州法斯特信息科技有限公司 | Abrasion resistant anticorrosive plastic material and preparation method thereof |
| CN105671511A (en) * | 2016-03-29 | 2016-06-15 | 武汉诚盛电子有限公司 | Whole plasma vacuum plating process for car ornament |
| CN107304469A (en) * | 2016-04-23 | 2017-10-31 | 广东祖戈卫浴科技有限公司 | A kind of stainless steel surfaces stiffened treatment technology |
| CN109221102A (en) * | 2018-10-30 | 2019-01-18 | 广东粤迪厚创科技发展有限公司 | A kind of antibacterial new material |
| WO2020238144A1 (en) * | 2019-05-31 | 2020-12-03 | 厦门大学 | Plastic electroplating method |
| CN111004997A (en) * | 2019-12-12 | 2020-04-14 | 成都新柯力化工科技有限公司 | Barrier plastic film for liquid product packaging and preparation method thereof |
| CN111018362A (en) * | 2019-12-25 | 2020-04-17 | 浙江星星科技股份有限公司 | Coating processing method of 3D curved surface deep groove panel |
| CN112501535A (en) * | 2020-12-15 | 2021-03-16 | 安徽恒茂宜高电镀科技有限公司 | Method and device for enhancing binding force of new energy automobile plastic accessory coating |
| CN112501535B (en) * | 2020-12-15 | 2023-01-13 | 安徽恒茂宜高电镀科技有限公司 | Method and device for enhancing binding force of new energy automobile plastic accessory coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101343724B (en) | 2011-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101343724B (en) | Method for functional decoration film coating on engineering plastic rubber surface | |
| CN102152541B (en) | Method for preparing composite interlayer coating film on surface of engineering plastics | |
| CN102127764B (en) | Method for implementing semi-dry plating on surface of plastic substrate | |
| EP1765921B1 (en) | Multilayer structure for polymers | |
| CN107151780B (en) | A kind of processing method of polymer surfaces | |
| CN107287555B (en) | A kind of self-assembled nanometer oxynitride coating and its preparation method and application | |
| CN101830092A (en) | Method for preparing corrosion-resistant colored decorative film | |
| CN101985738A (en) | Method for depositing metal or hard ornament film on plastic substrate | |
| CN102943293B (en) | A kind of manufacture craft having wire drawing lines plated item | |
| CN103122452B (en) | Surface metallization method for foamed plastic by adopting high-power pulse magnetron sputtering | |
| CN102463714B (en) | Covered element with fingerprint resistance and manufacture method thereof | |
| CN107326414B (en) | Plastic substrate chromium-free metallization method | |
| CN103818047A (en) | Surface coating structure of engineering plastic and preparation method thereof | |
| CN104384088A (en) | Electroplating-free antique metal surface treatment method | |
| CN102758176A (en) | Method for carrying out full dry method composite film plating on metal surface | |
| CN208121182U (en) | A kind of black conductive PVD film | |
| CN106011762B (en) | A kind of car trim and its preparation method of surface coating | |
| CN102877025A (en) | Surface coating method for plastics with metal drawn wire appearance | |
| CN103820792B (en) | A kind of surface treatment method of kirsite | |
| CN109735785A (en) | A kind of preparation method of the hydrophobic coating of the wear-resisting satisfactory mechanical property of novel fire resistant | |
| CN105316624A (en) | Surface plating technique for polymer material product | |
| CN102851639A (en) | Environment-friendly electroless plating drawn wire-imitating surface treatment method for engineering plastic | |
| CN102086511B (en) | Imitation plating processing method for surface of automobile exterior decoration | |
| CN111826619A (en) | Electroplating pre-plating process for plastic metallization | |
| CN101725037B (en) | Method for modifying surface of fibrous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 361000 Tianfeng Road, Jimei District, Xiamen, Fujian Province, No. 69 Patentee after: Runner (Xiamen) Corp. Address before: 361023 Dongting Road 155-159, Guankou Town, Jimei District, Xiamen City, Fujian Province Patentee before: Xiamen Runner Industrial Corp. |
|
| CP03 | Change of name, title or address | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110119 Termination date: 20210815 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |