CN101985738A - Method for depositing metal or hard ornament film on plastic substrate - Google Patents
Method for depositing metal or hard ornament film on plastic substrate Download PDFInfo
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- CN101985738A CN101985738A CN2009101122734A CN200910112273A CN101985738A CN 101985738 A CN101985738 A CN 101985738A CN 2009101122734 A CN2009101122734 A CN 2009101122734A CN 200910112273 A CN200910112273 A CN 200910112273A CN 101985738 A CN101985738 A CN 101985738A
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Abstract
The invention relates to a method for depositing a metal or hard ornament film on a plastic substrate. In the method, the metal or hard ornament film is prepared on the surface of a plastic substrate material by using a radio frequency magnetron sputtering technology, and good binding force exists between the prepared ornament film and the substrate. The plastic substrate material comprises ABS plastic (terpolymer of acrylonitrile-butadiene-styrene), PMMA (polymethyl methacrylate) organic glass, PE (poly ethylene) plastics, PP (polypropylene) plastics and the like. The metal ornament film comprises chromium, nickel, titanium, aluminum, aurum, silver, iridium or alloys and the like, and the hard ornament film comprises metal nitrides, carbon compounds, oxides, diamonds and the like. The method has the advantages of simple operation, no pollution and low cost, and the prepared film is good in adhesive force.
Description
Technical field
The preparation method who the present invention relates to belongs to decorative materials technology.
Background technology
Plastics be a kind of cheap, chemical stability good, corrosion resistance and good, rigidity and the good light material of workability.Based on above advantage, metallic substance is substituted by plastics gradually in a lot of fields.But, compare frosting with metallic substance and generally do not have metalluster, make that the decorate properties of plastics is not too fully up to expectations.In order to improve this limitation of plastics, people have done many work frosting have been carried out modification.By cover the surface abrasion resistance that layer of metal film or hard films both can improve plastics in surface of plastic products, can improve the outward appearance of plastics again, improve its ornamental performance.Methods such as general at present employing acid treatment or monomer processing make frosting present concavo-convex situation, simultaneously at the surface attachment polar group, make frosting have electroconductibility, thereby can adopt the wet method electric plating method at the frosting depositing metallic films.This method must be carried out modification to frosting, and technology is complicated, energy consumption is high, also have very strong contaminative simultaneously.In addition, doing plating method (sputtering method, vapor phase process etc.) also is a kind of comparatively simple method at the frosting depositing metallic films that grows up at present.Do the plating method and do not require that frosting must conduct electricity, and can not produce the pollution Litter, film thickness is controlled easily.But do the plating method some shortcomings are arranged also, for example adhesive force and wear resistance are not fine.Do some problems that the plating method exists in order to solve, people have been incorporated into dried plating method with the method for frosting modification.China publication CN 1504499A discloses a kind of employing arene compounds, grease, alcohols and oxygenant and has carried out surface modification, handle through the 1000V electrical spark then, applied coating through acroleic acid polyurethane again, after do the method that the plating legal system is equipped with metallic membrane.This method has improved the sticking power of metallic membrane, but operation or more complicated are unfavorable for industrial production.United States Patent (USP) 3801368 discloses a kind of at first sputter plastic material surface mixing materials such as gold, platinum, and then the method for electroplating metal film.Chinese patent CN 1481448A discloses a kind of at first using plasma and has handled frosting, then uses organic solution to soak plastics, adopts palladium (Pd) to make catalyzer then and carries out electroless plating and prepare the metallic membrane method.And hard films such as nitride, carbon compound, oxide compound and diamond can not adopt the wet method electric plating method to prepare, and can only adopt and do the preparation of plating method.
The present invention has proposed to use the method for radiofrequency magnetron sputtering technology at frosting metal refining or hard decorative film from improving the angle of plastics taste.This method at first uses nitrogen, argon, oxygen, helium a kind of or several plasma bodys wherein that frosting is bombarded pre-treatment in advance, metal refining or hard decorative film then, two steps can be carried out continuously, simplified depositing operation, significantly improved production efficiency, prepared metallic membrane sticking power is good.Be intended to simplify existing metal film deposition technology, propose method simultaneously in frosting deposition hard films.
Summary of the invention
The present invention levies the current technology for preparing metallic membrane at frosting complicated, propose to adopt nitrogen, argon, oxygen, helium a kind of or several plasma bodys wherein that frosting is bombarded pre-treatment in advance, used the method for radiofrequency magnetron sputtering technology metal refining or hard decorative film then.
The present invention at the plastic material comprise ABS plastic (terpolymer of acrylonitrile-butadiene-styrene (ABS)), PMMA synthetic glass (polymethylmethacrylate), PE plastics (polyethylene) and PP plastics (polypropylene) etc.; At decorative metal film comprise precious metals such as chromium, nickel, titanium, tungsten, aluminium, stainless steel, Wimet and gold and silver, iridium, platinum, rhodium; The hard decorative film comprises titanium nitride, nitrogen aluminium titanium, tungsten nitride, tungsten nitride titanium, wolfram varbide, titanium carbide, titanium carbonitride, silicon carbide, quasi-diamond, tungsten quasi-diamond, aluminium nitride, silicon nitride, aluminum oxide, titanium monoxide, titanium dioxide etc., and EMI film, antistatic film, the anti-width of cloth are penetrated film etc.
At decorative metal film be the bright metal look, the hard decorative film is golden yellow, black, blueness, silver gray, grey black etc.
Metal targets relative densities such as chromium used in the present invention, nickel and titanium are higher than 90%, and ceramic target relative densities such as the titanium nitride that is adopted, titanium carbide, titanium carbonitride are higher than 90%, and target purity all is not less than 95%.
The present invention at first adopts ultrasonic cleaning plastic such as deionized water, dehydrated alcohol, and nitrogen, argon, oxygen, helium a kind of or several plasma bodys wherein bombard pre-treatment in advance to frosting, to improve the sticking power of metal and hard decorative film; Plasma process conditions is: working gas is nitrogen, argon gas, oxygen, helium or its mixed gas, and flow is 0.1～200sccm (a standard milliliter per minute), and operating pressure is 0.1～100Pa, 0.1～20 minute treatment time.
Plastic is directly delivered to sputtering chamber metal refining or hard decorative film among the present invention after plasma bombardment is handled; Substrate after the processing does not expose atmosphere, can improve adhesion of thin film.
Among the present invention in the rf magnetron sputtering process working gas be argon gas, nitrogen, helium, acetylene, methane or two or more mixed gas wherein, gas flow is 0.1～200sccm (a standard milliliter per minute), operating pressure is 0.1～10Pa, and underlayer temperature is low temperature or room temperature or is lower than 80 ℃.
In the film preparation process, process applies the bias voltage of varying strength respectively according to thicknesses of layers and before and after being coated with, and improving the bonding force of metal and hard decorative film and plastics, thereby prevents demoulding.
Description of drawings
Accompanying drawing is Cement Composite Treated by Plasma and magnetic control sputtering system synoptic diagram, wherein 1, the sample transfer device; 2, sample library; 3, plasma processing chambers body; 4, high vacuum push-pull valve; 5, sample; 6, baffle plate; 7, sputtering chamber; 8, magnetic controlling target rifle; 9, plasma processor.
Embodiment
Embodiment 1: plastic is cleaned and method of plasma processing
Plastic such as ABS, PMMA, PE and PP are put into deionized water or dehydrated alcohol carries out ultrasonic cleaning, plastic after the cleaning is put on the intravital sample library of plasma processing chambers after drying, is higher than 6 * 10 with being evacuated to vacuum tightness in the cavity then
-3Pa, plastic on the sample library is transmitted the bar taking-up with magnetic force to be positioned on the plasma processor, be high-purity argon gas, nitrogen or its mixed gas of 20～100sccm then toward the interior feeding of cavity flow, regulating the interior pressure of cavity is 3～10Pa, and applying power to plasma generator is 10W/cm
2Radio-frequency power supply, the treatment time is controlled to be 3～10 minutes.Plastic after the processing directly is sent to the deposition that sputtering chamber carries out metal or hard films by the sample transfer device.
Rf magnetron sputtering prepares decorative metal film on the embodiment 2:PMMA plastic
Sputter is 99% with chromium, nickel or titanium metal target purity, and relative density is～0.98, and chromium, nickel or titanium target correctly are installed in the target rifle, is evacuated to sputtering chamber base vacuum degree and is higher than 2.0 * 10
-4Pa is a substrate with the PMMA plastics after handling through embodiment 1, and substrate does not heat (being controlled at room temperature with water-cooled), feeds a certain amount of argon gas in sputtering chamber, and pressure is 0.2～5Pa in the adjusting sputtering chamber, and the radio-frequency sputtering power regulation is 20W/cm
2, depositing time is controlled to be 10～60 minutes, and prepared metallic membrane is silver lustre white metal gloss.
Rf magnetron sputtering prepares the hard decorative film on the embodiment 3:ABS plastic
Sputter is 99% with titanium, titanium nitride, titanium carbide or titanium carbonitride target purity, and relative density is～0.96, in correct installation of target and target rifle, is evacuated to sputtering chamber base vacuum degree and is higher than 2.0 * 10
-4Pa, with the ABS plastic substrate after handling through embodiment 1 is substrate, substrate does not heat (being controlled at room temperature with water-cooled), in sputtering chamber, feed a certain amount of argon gas, helium, nitrogen, acetylene, methane or its mixed gas, regulating the interior pressure of sputtering chamber is 0.5～8Pa, and the radio-frequency sputtering power regulation is 15W/cm
2, depositing time is controlled to be 5～80 minutes, and prepared hard films is golden yellow, black, blueness or silver gray.
Claims (10)
1. the method for metal refining or hard decorative film on a plastic, it is characterized in that: this method adopts radio frequency or medium-high frequency magnetron sputtering technique to prepare decorating film.
Claim 1 described on plastic the method for metal refining or hard decorative film, it is characterized in that: the right plastic material of levying comprises: ABS plastic (terpolymer of acrylonitrile-butadiene-styrene (ABS)), PMMA synthetic glass (polymethylmethacrylate), PE plastics (polyethylene) and PP plastics (polypropylene) etc.
Claim 1 described on plastic the method for metal refining or hard decorative film, it is characterized in that: at decorative metal film comprise precious metals such as chromium, nickel, titanium, tungsten, aluminium, stainless steel, Wimet and gold and silver, iridium, platinum, rhodium; The hard decorative film comprises titanium nitride, nitrogen aluminium titanium, tungsten nitride, tungsten nitride titanium, wolfram varbide, titanium carbide, titanium carbonitride, silicon carbide, quasi-diamond, tungsten quasi-diamond, aluminium nitride, silicon nitride, aluminum oxide, titanium monoxide, titanium dioxide etc., and EMI film, antistatic film, the anti-width of cloth are penetrated film etc.
Claim 1 or 2 or 3 described on plastic the method for metal refining or hard decorative film, it is characterized in that: prepared decorative metal film is the bright metal look, the hard decorative film is golden yellow, black, blueness, silver gray, grey black etc.
Claim 1 described on plastic the method for metal refining or hard decorative film, it is characterized in that: metal targets relative densities such as the chromium that is adopted, nickel and titanium are higher than 90%, ceramic target relative densities such as the titanium nitride that is adopted, titanium carbide, titanium carbonitride are higher than 90%, and target purity all is not less than 95%.
Claim 1 or 2 described on plastic the method for metal refining or hard decorative film, it is characterized in that: the plastic before the plated film is carried out the soak cleaning pre-treatment, to remove surperficial grease, dust.
Claim 1 or 2 described on plastic the method for metal refining or hard decorative film, it is characterized in that: with nitrogen, argon, oxygen, helium a kind of or several plasma bodys wherein frosting is bombarded pre-treatment in advance in the preparation process, to improve the sticking power of metal and hard decorative film; Plasma process conditions is: working gas is nitrogen, argon gas, oxygen, helium or its mixed gas, and flow is 0.1～200sccm (a standard milliliter per minute), and operating pressure is 0.1～100Pa, 0.1～20 minute treatment time.
Claim 1 or 2 described on plastic the method for metal refining or hard decorative film, it is characterized in that: with nitrogen, argon, oxygen, helium a kind of or several high energy ion beams wherein frosting is bombarded pre-treatment in advance in the preparation process, to improve the sticking power of metal and hard decorative film.
9. the described preparation method of claim 1, it is characterized in that: working gas is argon gas, nitrogen, helium, acetylene, methane or two or more mixed gas wherein in the magnetron sputtering process, gas flow is 0.1～200sccm (a standard milliliter per minute), operating pressure is 0.1～10Pa, and underlayer temperature is low temperature or room temperature or is lower than 80 ℃.
10. claim 1 or 2 described preparation methods is characterized in that: in the film preparation process, process applies the bias voltage of varying strength respectively according to thicknesses of layers and before and after being coated with, and improving the bonding force of metal and hard decorative film and plastics, thereby prevents demoulding.
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| CN2009101122734A CN101985738A (en) | 2009-07-29 | 2009-07-29 | Method for depositing metal or hard ornament film on plastic substrate |
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| CN2009101122734A CN101985738A (en) | 2009-07-29 | 2009-07-29 | Method for depositing metal or hard ornament film on plastic substrate |
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| CN102206800A (en) * | 2011-04-28 | 2011-10-05 | 中南大学 | Ion beam sputtering method for preparing golden yellow decorative film, and film |
| CN102328477A (en) * | 2011-05-31 | 2012-01-25 | 厦门建霖工业有限公司 | Method for compounding double-layer plating films on plastic surface by fully dry method |
| CN102363383A (en) * | 2011-08-30 | 2012-02-29 | 常熟市江顺塑料制品有限公司 | Composite plastic element |
| CN102392344A (en) * | 2011-07-08 | 2012-03-28 | 中国科学院理化技术研究所 | Method for preparing medical high molecular material by magnetron sputtering technology |
| CN102424950A (en) * | 2012-01-13 | 2012-04-25 | 广东志成冠军集团有限公司 | Method for plating aluminum film on plastic substrate |
| CN102534531A (en) * | 2012-01-10 | 2012-07-04 | 清华大学 | Preparation method of titanium dioxide/titanium nitride composite film with adjustable band gaps |
| CN102747322A (en) * | 2011-04-22 | 2012-10-24 | 鸿富锦精密工业（深圳）有限公司 | Preparation method of plated film member and plated film member prepared by method thereof |
| 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 |
| CN102810347A (en) * | 2012-03-30 | 2012-12-05 | 梧州三和新材料科技有限公司 | Preparation method for carbon-metal embedded and seeped type conducting film applied to non-metal material |
| US20130071680A1 (en) * | 2011-09-21 | 2013-03-21 | Fih (Hong Kong) Limited | Coated article and method for making same |
| CN103935075A (en) * | 2013-01-23 | 2014-07-23 | 深圳富泰宏精密工业有限公司 | Shell and manufacturing method thereof |
| CN104099568A (en) * | 2013-04-12 | 2014-10-15 | 昆山艾诺美航天材料有限公司 | Aerial organic glass multilayer coating technology |
| CN105229195A (en) * | 2013-05-31 | 2016-01-06 | 三星电子株式会社 | Manufacture the method for multilayer film and comprise parts and the electronic product of this film |
| CN105350050A (en) * | 2015-11-19 | 2016-02-24 | 东莞金稞电子科技有限公司 | Surface treatment technology for plastic product |
| CN106350843A (en) * | 2016-10-11 | 2017-01-25 | 上海瑞尔实业有限公司 | Pre-treatment method for electroplating plastic |
| CN106398095A (en) * | 2016-08-31 | 2017-02-15 | 宁波威丰新材料有限公司 | Magnetron sputtering plastic target film |
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| CN102206800A (en) * | 2011-04-28 | 2011-10-05 | 中南大学 | Ion beam sputtering method for preparing golden yellow decorative film, and film |
| CN102328477A (en) * | 2011-05-31 | 2012-01-25 | 厦门建霖工业有限公司 | Method for compounding double-layer plating films on plastic surface by fully dry method |
| CN102328477B (en) * | 2011-05-31 | 2014-01-08 | 厦门建霖工业有限公司 | Method for compounding double-layer plating films on plastic surface by fully dry method |
| CN102392344A (en) * | 2011-07-08 | 2012-03-28 | 中国科学院理化技术研究所 | Method for preparing medical high molecular material by magnetron sputtering technology |
| CN102392344B (en) * | 2011-07-08 | 2015-08-12 | 中国科学院理化技术研究所 | Magnetron sputtering technique is adopted to prepare the method for medical macromolecular materials |
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Application publication date: 20110316 |