CN101696489B - Method for plating chromium on plastics - Google Patents
Method for plating chromium on plastics Download PDFInfo
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- CN101696489B CN101696489B CN2009101532777A CN200910153277A CN101696489B CN 101696489 B CN101696489 B CN 101696489B CN 2009101532777 A CN2009101532777 A CN 2009101532777A CN 200910153277 A CN200910153277 A CN 200910153277A CN 101696489 B CN101696489 B CN 101696489B
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 78
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Abstract
The invention relates to a method for plating chromium on plastics, and belongs to the fields of new materials and surface technology. The method comprises the following steps in turn: 1, spraying a layer of organic coating on a substrate material and performing ultraviolet radiation curing to obtain a first-stage semi-finished product; 2, plating chromium on the first-stage semi-finished product obtained in step 1 in vacuum to obtain a second-stage semi-finished product; and 3, plating a titanium oxide film on the second-stage semi-finished product obtained in step 2 with a medium frequency magnetron sputtering machine to obtain a finished product. The method has the advantages of low production cost, no toxicity, and simpleness and convenience, and solves the technical problems of heavy pollution, complicated process and high cost in the prior art.
Description
Technical field
The present invention relates to method for plating chromium on plastics, belong to novel material and sufacing field.
Background technology
Since the thirties in 20th century, plastic electroplating has obtained continuous development.It on plastic substrate by metalized at the thin metal level of surface deposition one deck, and then in the basic enterprising electroplating processing of this conductive layer.The composite material concurrent of being made up of plastics and metal plating has the advantage of plastics and metal.Electroplating plastic is widely used in fields such as automobile, motorcycle, household electrical appliance, ornament, packing; High performance electroplating plastic goods also are used for important departments such as aircraft, rocket, aerospace and radio communication.
Electrodeposited chromium is important technology in the plastic electroplating.Chromium coating has very strong inactivating performance in atmosphere, the beautiful gloss of argent is arranged, and can keep for a long time; Stable in corrosive mediums such as alkali, nitric acid, sulfide, carbonate, organic acid.Chromium coating also has higher hardness, good wear resistance and thermotolerance.But electrodeposited chromium has very big harm to environment and human body, and especially the sexavalent chrome toxicity of Sheng Chenging is very big, can make the people cause a series of diseases, or even serious disease such as skin carcinoma, gland cancer.People have done a large amount of research to electrodeposited chromium for many years, progressively use technology such as low concentration chromium plating and trivalent chromium chrome plating, alleviate the pollution to environment, but simultaneously technology such as trivalent chromium plating is perfect not enough, and outward appearance is not so good as sexavalent chrome with performance; And chromium plating goes to toward will plating thicker copper and nickel dam, consume metals resources such as a large amount of comparatively valuable copper, nickel and water.The plating pre-treatment of plastic electroplating has destressing, oil removing, alligatoring, sensitization, activation, dispergation etc., operation is many, wasteful, and need carry out electroless plating in order to give the certain conductive capability of plastics or other are handled, further increase the complicacy of plastic electroplating technology.
Summary of the invention
The purpose of this invention is to provide a kind of method for plating chromium on plastics, it has low, nontoxic, the convenient and simple advantage of cost, has solved prior art and has polluted greatly complex process, the technical problem that cost is high.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of method for plating chromium on plastics may further comprise the steps successively:
1. behind spraying one deck organic coating on the body material, carry out UV-irradiation and solidify, obtain first-stage semi-finished product;
2. will be vacuum chromium-coated through the first-stage semi-finished product that 1. step obtains, obtain the secondary work in-process;
3. will obtain finished product through the secondary work in-process that 2. step obtains medium frequency magnetron sputtering film machine plating titanium oxide film.
In the technique scheme of the present invention, behind plastics plating " organic coating layer/ion chromium coating/titanyl compound coating " composite deposite, both kept the density of plastics little, characteristics such as light weight, cost are low, the gloss of metal and conduction, heat conduction, performance such as wear-resisting are arranged again.Its coating adhesion, surface hardness, surface brightness and performances such as color and luster, resisting salt fog corrosion have reached product requirement, as widely used protection-decoration chrome plating, can replace existing plating chromium.Production process of the present invention has obtained significant simplification, and the consumption of power and water greatly reduces, and the metals resources that copper and mickel etc. are comparatively valuable saves fully, replaces poisonous chromium with nontoxic chromium simultaneously, has realized chromed cleaner production.
Before plastic vacuum coating, carry out " primary coat " with suitable organic coating earlier.It mainly acts on: contained moisture, residual solvent, softening agent, monomer, oligomerization material in the sealing plastics, in order to avoid these materials are overflowed in the vacuum plating process and are influenced coating quality and pumping speed; Reduce or eliminate the frosting roughness, improve the reflection and the mirror effect of vacuum-coating; Between vacuum-coating and plastic substrate, set up a kind of good transition layer, avoid surface imperfection that the significant difference because of the vacuum-coating and the plastic substrate coefficient of expansion causes such as excessive stress crack and peel off etc., and improve the sticking power and the mechanical property of vacuum-coating; Plastics for poor heat resistance; undercoat can play protective effect; in order to avoid plastic substrate sustains damage or thermal distortion takes place in the vacuum plating process, and, more need heat-resisting, radiation-resistant coating to carry out the primary coat protection for the plastics that will carry out magnetron sputtering, especially ion plating.The primary coat that the present invention adopts is that UV-irradiation is coating material solidified, and major cause is: solvent is few, and solvent evaporates is few in the UV-irradiation solidification process, helps protecting environment; Curing speed is fast, and at room temperature the several seconds is finished curing usually; Solidification value is low, needs the temperature of tens degree except the levelling stage in coating process, and all the other all at room temperature carry out; The solid content height, the coating volumetric shrinkage was little after curing was finished, and the floating coat of vacuum plating process afterwards can not overflowed volatile matter and be avoided damaging coating quality; Power consumption is few, be about heat curing coating when solidifying energy consumption 10%～30%; Coating equipment is comparatively simple, and production management is more or less freely, constant product quality, and be suitable for the streamlined operation.
As preferably, also have pre-treatment step in step before 1., described pre-treatment step comprises successively: remove greasy dirt and residual releasing agent; Remove the static and the dust of substrate material surface.
Because organic coating sticking power is not very good, thereby will improve sticking power and coating quality by pre-treatment.When pre-treatment, at first to thoroughly remove greasy dirt and residual releasing agent.Releasing agent such as Zinic stearas, silicone oil remaining causes defectives such as coating shrinkage cavity and sticking power is bad easily, so will dispose.Degreasing method has multiple, and what often adopt is organic solvent.In addition, plastics are poor conductors, and the surface is static electricity gathered easily, the absorption dust, thereby will the static and the dust of frosting be removed with electrostatic precipitator.ABS plastic can be considered further to improve coating quality with rarer chromic acid solution after degreasing.
As preferably, step 1. in, described organic coating is the alicyclic epoxy modification acrylate.
The alicyclic epoxy modified acrylate coating material is meant, mix the crosslinked photosensitive prepolymer that obtains to have concurrently alicyclic epoxy and acrylate performance characteristics with hydroxy acrylate by cycloaliphatic epoxy resin, recombinant light trigger, reactive thinner and other various additives and form.Cycloaliphatic epoxy resin is a branch of Resins, epoxy, because the epoxy group(ing) in its molecular structure is not from propylene oxide, but epoxy group(ing) directly is connected on the alicyclic ring, so compare, have thermally-stabilised good mutually, good heat resistance, electrical insulation capability excellence, processing performance and reach characteristics such as safety performance height well with bisphenol A type epoxy resin.Come modified acrylate coating material with it, can improve the thermotolerance and the radiation-resistant property of coating, for example its thermotolerance can reach more than 200 ℃.
As preferably, step 2. described vacuum chromium-coated be with the chromium plating of cathodic arc ion plating method with first-stage semi-finished product.
Cathodic arc ion plating is a kind of ion plating technique that adopts the cathodic arc evaporation source.Cathode arc source is the chromium target, and it is an evaporation source, is again to bombard purification source and ionization source in advance.After electric arc is ignited, low-voltage high-current power source will be kept the arc discharge between negative electrode and the coating chamber, and its electric current is generally several the peace to the hundreds of peace, and working power is 10V～25V.When cathode arc discharges, the cathode spot of some high brightness appears on chromium target surface, and they are discontinuous and random motion.Each spot is all launched the chromium plasma body of one highly ionized, and it is made up of electronics, chromium positive ion, also contains the neutral steam atom of many small fusion granules and chromium seldom.The plasma air-flow of a plurality of spot emissions just merges into plasma cloud between cathode and anode.Because neutral chromium atom steam seldom, proportion is lower than 2%, thereby what be deposited on workpiece surface mainly is chromium ion and drop.Indoor in enclosed vacuum, sedimentary chromium ion becomes neutral chromium atom again with electron recombination.
As preferably, step 2. in, be provided with and make plasma accelerated motion, improve beam-plasma flow density and directional property, the content of minimizing drop and the magnetic field of improving sedimentation rate, film quality and adhesion performance.
Magnetic field is set in equipment, makes plasma accelerated motion, improve beam-plasma flow density and directional property, reduce the content of drop, thereby improved sedimentation rate, film quality and adhesion performance.
As preferably, step 2. in during chromium plating chromium deposition speed reach 10nm/s～1 μ m/s.
In chrome-plating process, charge into a certain amount of argon gas earlier, increase the stability in arc source and the diffraction of plated film; Turn off argon gas before chromium plating begins, in the chromed process of ion bombardment, controlling chromed sedimentation rate is 10nm/s～1 μ m/s under high vacuum condition, and like this, the ABS plastic workpiece surface is the silvery white of high brightness, with the surface color basically identical of electrodeposited chromium.
As preferably, step is 3. described to be specially the titanium oxide film that the method that adopts intermediate frequency twin target magnetron sputtering is coated with at plating titanium oxide film on the secondary work in-process on the secondary work in-process.
In order to improve coating quality and to avoid problems such as " target poisonings ", the present invention adopts intermediate frequency twin target magnetron sputtering to be coated with the titanyl compound film.Twin magnetic controlling target links to each other with two output terminals of intermediate frequency power supply.At certain in a flash, one in the twin magnetic controlling target is to be in negative potential, and as sputter cathode, and another is as anode, and the electronics that this moment, negative electrode produced is accelerated to anode, is accumulated in the positive charge of this surface of insulating layer with previous half negative cycle that neutralizes.This magnetron sputtering coating method is compared with magnetically controlled DC sputtering, can avoid in the reactive sputtering process because of around negative electrode, depositing " the target poisoning " that very thick insulation layer causes, not only sedimentation rate is high but also operation steady in a long-term, the film layer structure densification, smooth surface, physicochemical property is further improved.
As preferably, described body material is ABS plastic or PC plastics or PC+ABS plastics.
The thermotolerance of plastics part is low, and for ABS, PC and PC+ABS plastics, Heating temperature can not be above 60～80 ℃ during plated film.
As preferably, described titanyl compound film is the mixture of titanium dioxide and other titanyl compounds.
In titanyl compound, titanium dioxide is a kind of important compound.As protectiveness coating, metal plating such as it and chromium have good tack, are transparent at visible light wave range, and higher hardness and wear resistance are arranged, and good chemical stability and excellent solidity to corrosion are arranged again, the therefore suitable protective coating of doing chromium thin film.
In sum, the present invention has following beneficial effect:
1, its use properties of chrome-plated plastic goods and the product indifference on the market of using the inventive method to make, but the inventive method is more simple, produce efficient, and also greatly minimizing of the consumption of power and water;
2, the present invention replaces traditional " copper/nickel/chromium " three metal plating structures with the structure of " organic coating/vacuum chromium-coated layer/inorganic coating ", replace poisonous chromium with nontoxic chromium, when realizing chromed cleaner production, comparatively valuable metals resources such as copper, nickel have been saved simultaneously;
3, the present invention adopts the alicyclic epoxy modified acrylate coating material, after spraying and UV-irradiation curing, make heat-resisting, radiotolerant undercoat at plastic workpiece surface, can bear the ion bombardment in the ion chrome-plating process within the specific limits, and it is defective such as crackle do not occur, and simultaneously good with the sticking power of matrix and chromium coating;
4, the present invention's cathodic arc ion plating chromium method, the chromium plating on alicyclic epoxy modification acrylate undercoat, thickness is about 2.5 μ m; Chrome-plating process is to carry out in that enclosed vacuum is indoor, and very fast the combination with electronics of sedimentary chromium ion form chromium atom, so be a kind of chrome-plating method of cleaning;
5, the present invention uses the medium frequency magnetron sputtering film coating method on the surface of ion chromium coating, deposits the titanyl compound of the about 3 μ m of a bed thickness, and it is the mixture of titanium dioxide and other titanyl compounds.This oxide compound and vacuum chromium-coated layer tack are strong, and be transparent at visible light wave range, excellent corrosion resistance, and good wear resistance is arranged, vacuum chromium-coated layer there is good provide protection;
6, the vacuum chromium-coated plastics of " alicyclic epoxy modified acroleic acid resin coating/ion chromium coating/titanyl compound coating " of the present invention structure as protection-decorative use, can extensively replace the electrodeposited chromium plastics.
Description of drawings
Fig. 1 is the process flow diagram of this electrodeposited chromium;
Fig. 2 is the process flow diagram of chrome-plating method of the present invention.
Embodiment
This specific embodiment only is an explanation of the invention; it is not a limitation of the present invention; those skilled in the art can make the modification that does not have creative contribution to present embodiment as required after reading this specification sheets, but as long as all are subjected to the protection of patent law in claim scope of the present invention.
Embodiment one
A kind of method for plating chromium on plastics in turn includes the following steps:
1, pre-treatment is cleaned with alcohol organic solvent earlier, removes ABS plastic workpiece surface greasy dirt and residual releasing agent.Soak with the chromic acid treatment solution then, with 65 ℃ to 70 ℃ washing 5min to 10min, carry out drying thereafter again.Carry out dust removal process with electrostatic precipitator or ion cleaning machine at last, in and the electric charge of frosting, and dust adsorbed is come off.
2, photocuring bottom-coating: alicyclic epoxy modification acrylate photo-cured coating.Alicyclic epoxy modification acrylate photo-cured coating mixes crosslinked forming by cycloaliphatic epoxy resin with hydroxy acrylate, it has the photosensitive prepolymer of alicyclic epoxy and acrylate performance characteristics concurrently, and it also includes light trigger, reactive thinner and other various additives simultaneously.Coating equipment: ultraviolet light polymerization production line.It is made up of first class purification district, secondary purification district, paint finishing, infrared rays levelling section, ultraviolet light polymerization section, extension, input and output material section, purifying air exhausting supply air system etc.Two regional total lengths of first class purification and secondary purification are 12m, wide 8m.Four sections long altogether 18m such as levelling, curing, extension, input and output material, wide 1.45m.The wide 0.95m of the company of conveying, stainless (steel) wire bandwidth 0.87m, entrance height is adjusted in 0.6m.The levelling section is settled 30 of 1KW infrared heating pipe.Photocuring section configuration 9 cover uviolizing light fixtures, wherein ceiling light is 3, and with 5.6KW, order is installed before and after the 8.0KW, 5.6KW; About divide two-layer up and down two the 5.6KW lamps of respectively installing; Two on end lamp, with 8.0KW, order is installed before and after the 5.6KW.Paint finishing is a dibit worker cascade spray booth, is equipped with the purification supply air system, and the spraying group that spray booth is 3.5m * 2.7m * 2.4m by two specifications becomes.The spraying condition: the curing energy is 2000～2500mj/c; m
2Viscosity is (rock field 2# cup) 8s/25 ℃.Spraying coating process: workpiece is introduced into the levelling stage after spraying, under 70 ℃ of conditions, and levelling 5min; Enter curing area then, the about 20s of irradiation under ultraviolet lamp specifically is cured as out 2 5.6KW of ceiling light and 8.0KW so that the alicyclic epoxy modification acrylate solidifies, left and right, each 5.6KW of end lamp.
3, ion chromium plating ABS plastic workpiece entered cathodic arc ion plating equipment in 1 hour after the photocuring primary coat.This equipment is vertical, and the vacuum chamber inner cavity size is ф 1200mm, high 1250mm.Air-bleed system is made up of holding pump, mechanical pump, lobe pump and oil diffusion pump etc.10 of electric arc ionization sources, cross-distribution be in vacuum-chamber wall, the stainless steel target stand, and each source powers separately, regulates indirect water-cooling, electromagnetism striking separately.Target cathode is of a size of ф 80mm * 40mm.Target is a chromium, joins the special-purpose arc power of 10 cover 3KW, 150A.In addition, join 30KW pulsed bias power supply one cover.Airing system is joined four tunnel gas mass flow amount controllers.Coating process: the ABS plastic workpiece is put in work rest, rotates.Distance is 300～400mm between target and the ABS plastic workpiece.Be evacuated to 4.0 * 10 earlier
-3Pa, argon filling makes vacuum tightness be reduced to 1.6 * 10 with the stability in increase arc source and the diffraction of plated film
-1Pa.The number of increasing income is 5.Open arc power, the control arc stream is 70A, and dutycycle is 85%, then chromium plating 2min; Then, the argon filling air valve is closed, be evacuated to 6.0 * 10
-3Pa, the control arc stream is 70A, the number of increasing income is 5, then ion bombardment chromium plating 1min.In the chromed process of ion bombardment, controlling chromed sedimentation rate is 10nm/s～1 μ m/s under high vacuum condition, and like this, the ABS plastic workpiece surface is the silvery white of high brightness, with the surface color basically identical of electrodeposited chromium.
4, intermediate frequency twin target magnetron sputtering titanium oxide film ABS plastic workpiece is gone into intermediate frequency twin target magnetron sputtering film device through ion chromium plating is laggard.Settle a pair of twin plane titanium target in the vacuum chamber of intermediate frequency twin target magnetron sputtering film device.Be of a size of long 750mm * wide 150mm * thick 10mm, join a cover 30KVA, 40KHz intermediate frequency shielding power supply.Airing system is joined four tunnel gas mass flow amount controllers.Other has the heated baking device, and this heated baking device is made up of the stainless steel heating tube, also is provided with to revise baffle plate and quartz crystal vibration thickness monitor.Coating process: the ABS plastic workpiece is put in work rest, rotates, and distance is 100mm～200mm between target and the workpiece.Be evacuated to 6.0 * 10 earlier
-3Pa, applying argon gas and oxygen then, the ratio of making it is 1: 6, makes vacuum tightness drop to 4.8 * 10 again
-1Pa opens intermediate frequency power supply, and control voltage is 644V, and electric current is 30A, and dutycycle is 80%, and frequency is 39.912KHz, carries out plated film 1.5min, closes the argon filling air valve again, keep fill oxygen to air pressure be 3.5 * 10
-1Pa, control voltage is 690V, and electric current is 30A, and dutycycle is 80%, and frequency is 39.303KHz, again plated film 1.5min.
So just made the plated film plastics with " organic coating/vacuum chromium-coated layer/inorganic coating " structure, it can be widely used in protection-decorative use, alternative existing plating chromium plastics.
Embodiment two
Only be with embodiment one difference: described body material is the PC plastics part.
Embodiment three
Only be with embodiment one difference: described body material is a PC+ABS composite plastic workpiece.
Goods are detected surface color, coating adhesion, coating hardness and cass salt-fog test life-span, and test result is as follows:
(1) (tissue 10 people are expert statement group to color and luster: Bai Liang, are contrast with traditional electrodeposited chromium goods, and the chrome-plated plastic of the embodiment of the invention one is identified, rate is divided into Bai Liang, general white bright, bright, generally bright, dark; Through 10 people comparison, there are 9 people to represent that the chrome-plated plastic of the embodiment of the invention is bright equally in vain with traditional electrodeposited chromium combinations color and lustre, 1 people represents that the chrome-plated plastic grade of the embodiment of the invention is for generally white bright)
(2) pencil hardness: 1～2H
(3) sticking power (hundred lattice): 100%
(4) cass test: 〉=72h
As can be seen, this product coating performance is good.
Claims (7)
1. method for plating chromium on plastics may further comprise the steps successively:
1. behind spraying one deck organic coating on the body material, carry out UV-irradiation and solidify, obtain first-stage semi-finished product;
2. will be vacuum chromium-coated through the first-stage semi-finished product that 1. step obtains, obtain the secondary work in-process;
3. will obtain finished product through the secondary work in-process that 2. step obtains medium frequency magnetron sputtering film machine plating titanium oxide film;
1. also have pre-treatment step in step before, described pre-treatment step comprises successively: remove greasy dirt and residual releasing agent; Remove the static and the dust of substrate material surface;
Step 1. in, described organic coating is the alicyclic epoxy modification acrylate.
2. a kind of method for plating chromium on plastics according to claim 1 is characterized in that: step 2. described vacuum chromium-coated be with cathodic arc ion plating method plating chromium with first-stage semi-finished product.
3. a kind of method for plating chromium on plastics according to claim 1 is characterized in that: 3. step is specially the titanium oxide film that the method that adopts intermediate frequency twin target magnetron sputtering is coated with at plating titanium oxide film on the secondary work in-process on the secondary work in-process.
4. a kind of method for plating chromium on plastics according to claim 1 is characterized in that: described body material is ABS plastic or PC plastics or PC+ABS plastics.
5. a kind of method for plating chromium on plastics according to claim 1, it is characterized in that: step 2. in, be provided with magnetic field, can make plasma accelerated motion, improve beam-plasma flow density and directional property, reduce the content of drop and improve sedimentation rate, film quality and adhesion performance.
6. a kind of method for plating chromium on plastics according to claim 2 is characterized in that: described titanium oxide film is the mixture of titanium dioxide and other titanyl compounds.
7. a kind of method for plating chromium on plastics according to claim 1, it is characterized in that: chromium deposition speed reaches 10nm/s～1 μ m/s during chromium plating, in chrome-plating process, charge into the argon gas that increases arc source stability and plated film diffraction earlier, the argon gas ion bombardment was closed in the chromium plating end in last minute.
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| CN102086511B (en) * | 2011-01-06 | 2013-01-09 | 嘉兴敏惠汽车零部件有限公司 | Imitation plating processing method for surface of automobile exterior decoration |
| CN102390134A (en) * | 2011-09-23 | 2012-03-28 | 湖州金泰科技股份有限公司 | Polycarbonate product |
| CN103484827A (en) * | 2012-06-07 | 2014-01-01 | 富优技研股份有限公司 | Manufacture method for plastic part with sputtered film |
| CN103046003B (en) * | 2012-12-31 | 2014-11-05 | 厦门建霖工业有限公司 | Plastic substrate surface processing method for obtaining self cleaning function |
| CN105710081B (en) * | 2015-12-29 | 2018-03-09 | 苏州金研光电科技有限公司 | A kind of process of surface treatment of automobile plastic ornament |
| CN106398095A (en) * | 2016-08-31 | 2017-02-15 | 宁波威丰新材料有限公司 | Magnetron sputtering plastic target film |
| CN106835128A (en) * | 2016-12-22 | 2017-06-13 | 马鞍山市鑫程纳米新材料科技有限公司 | A kind of preparation method of nontoxic chrome-plated plastic |
| CN110699634B (en) * | 2019-09-11 | 2021-07-20 | 神通科技集团股份有限公司 | Plastic part surface treatment method |
| CN111040473B (en) * | 2019-11-26 | 2021-02-23 | 广东盈骅新材料科技有限公司 | Titanium suboxide black pigment and preparation method thereof |
| CN114164429B (en) * | 2021-11-02 | 2023-11-24 | 襄阳光瑞汽车零部件有限公司 | Parting surface titanizing process of injection mold of automobile skylight framework |
| CN115305447A (en) * | 2022-07-21 | 2022-11-08 | 厦门建霖健康家居股份有限公司 | Method for plating bright chromium on plastic base material |
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