WO2018133234A1 - Procédé de préparation d'un revêtement étanche aux liquides ayant une structure à gradient croissant - Google Patents

Procédé de préparation d'un revêtement étanche aux liquides ayant une structure à gradient croissant Download PDF

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Publication number
WO2018133234A1
WO2018133234A1 PCT/CN2017/081786 CN2017081786W WO2018133234A1 WO 2018133234 A1 WO2018133234 A1 WO 2018133234A1 CN 2017081786 W CN2017081786 W CN 2017081786W WO 2018133234 A1 WO2018133234 A1 WO 2018133234A1
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monomer
plasma
discharge
reaction chamber
flow rate
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PCT/CN2017/081786
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English (en)
Chinese (zh)
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宗坚
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江苏菲沃泰纳米科技有限公司
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Publication of WO2018133234A1 publication Critical patent/WO2018133234A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges

Definitions

  • the invention belongs to the technical field of plasma chemical vapor deposition, and particularly relates to a preparation method of a liquid proof coating.
  • Plasma chemical vapor deposition is a technique in which a reactive gas is activated by a plasma to promote a chemical reaction on a surface of the substrate or in a near surface space to form a solid film.
  • Plasma coating technology has the following advantages over other coating preparation methods: 1) Dry process, the resulting film is uniform without pinholes; (2) The coating preparation temperature is low, and can be carried out under normal temperature conditions, effectively avoiding damage to temperature sensitive devices; (3) The plasma process can not only prepare coatings with a thickness of micron and can prepare ultra-thin nano-scale coatings; (4) The plasma polymerized film is stable in chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, and abrasion resistance; (5) the adhesion between the plasma polymerization film and the substrate is good.
  • Fluorocarbon resin with a strong C-F The bond is a skeleton, and its heat resistance, chemical resistance, cold resistance, low temperature flexibility, weather resistance and electrical properties are better than other resins, and it also has non-adhesiveness and non-wetting property. Therefore, the fluorocarbon resin coating is particularly suitable for the protection of the surface of the material, not only can give the material good physical and chemical durability, but also can give the material excellent waterproof and oil proof functions. In recent years, the preparation of fluorocarbon protective coatings by plasma technology has been studied and applied in microelectronics, optics, medical, precision equipment and high-end clothing.
  • thick coatings or ultra-thick coatings with dense structures and coatings having a multi-layer structure have significant advantages over thin coatings in terms of liquid, corrosion and liquid penetration resistance.
  • thick coatings and ultra-thick coatings mostly have residual stresses, which are prone to stress cracking under conditions of temperature change and deformation, and poor compatibility between interfaces of multilayer structure coatings is also prone to peeling and cracking, and loss of barrier properties.
  • uniform coatings usually have a single performance, and it is difficult to ensure that the coating has excellent bonding strength, mechanical properties, hydrophobic properties, and the like.
  • the present invention provides a method for preparing a gradient-incremental structure liquid-repellent coating, which is prepared by a multi-channel control method using a plasma chemical vapor deposition technique to prepare a liquid-repellent coating having a structural and composition gradient change.
  • the feeding mode of different monomer materials is controlled, and different process conditions are set at the same time to obtain a liquid-repellent coating with structural and composition gradient changes to achieve hydrophobicity, water repellency and long-term surface of the material. Effective regulation of resistance to underwater electricity.
  • a method for preparing a gradient-increasing structure liquid-repellent coating comprising: the following steps:
  • the first monomer vapor is: a monofunctional unsaturated fluorocarbon resin
  • the second monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative
  • the third monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative
  • the flow rate of the first monomer vapor is 10-1000 ⁇ L/min;
  • the initial flow rate of the second monomer vapor is 0 ⁇ L/min; the second monomer steam is increased in flow rate, and the increasing rate is 1-10 ⁇ L/min, the maximum flow rate is 500 ⁇ L/min;
  • the initial flow rate of the third monomer vapor is 0 ⁇ L/min; the third monomer steam inlet flow is increased, and the increasing rate is 1-10 ⁇ L/min, the maximum flow rate is 500 ⁇ L/min;
  • the plasma power source is turned off, and the first monomer vapor, the second monomer vapor, and the third monomer vapor are stopped.
  • the vacuum of the reaction chamber at 10-200 mTorr for 1-5 min, then pass into the atmosphere to an atmospheric pressure, and then remove the substrate.
  • the substrate in the step (1) is a solid material including an electronic component, an electrical component, a fabric or a garment.
  • the volume of the plasma chamber in the step (1) is 50 to 1000 liters, and the temperature of the plasma chamber is controlled at 30 to 60. °C; the flow rate of the inert gas or nitrogen gas is 5 to 300 sccm, and the inert gas is one of argon gas or helium gas, or a mixture of argon gas and helium gas.
  • the first monomer steam is introduced into the reaction chamber by atomization and volatilization through a feed pump, and is introduced into the reaction chamber from a low pressure of 10 to 200 mTorr;
  • the second monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and introducing the reaction chamber from a low pressure of 10 to 200 mTorr;
  • the third monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and introducing the reaction chamber from a low pressure of 10 to 200 mTorr.
  • the monofunctional unsaturated fluorocarbon resin includes:
  • the polyfunctional unsaturated hydrocarbon derivative includes:
  • the power of the ion discharge is set to 2 to 500 W before the introduction of the monomer vapor in the step (2), and the continuous discharge time is 300 ⁇ 600s, carry out bombardment pretreatment of the substrate by glow discharge, clean the surface impurities of the substrate and activate the surface of the substrate.
  • the power of the plasma discharge in the step (2) is 2 ⁇ 500W, and the continuous discharge time is 300 ⁇ 600s.
  • the plasma discharge mode is radio frequency discharge, microwave discharge, intermediate frequency discharge or electric spark discharge.
  • the plasma during radio frequency discharge The energy output mode of the control plasma RF is pulse or continuous output.
  • the pulse width is 2 ⁇ s-1ms, and the repetition frequency is 20Hz-10kHz.
  • a pulsed voltage is applied to increase the uniformity of film formation and to reduce free radicals remaining in the coating.
  • the present invention produces a nano-polymer graded coating having a gradient in structure and composition, which is introduced at the same rate by simultaneously introducing monomer vapor and controlling the flow rate of monomer vapor.
  • the toughness hardness of the prepared coating structure is gradient change, which can reduce stress cracking and deformation, and has better barrier protection performance.
  • the bottom layer of the coating is a loose layer structure with good toughness and strong adhesion to the substrate. From the surface of the substrate, the cross-linking effect of the monomer is gradually enhanced, and the compactness of the coating is relatively enhanced, so that the coating has a continuous function of blocking the contact of water vapor with the surface of the material.
  • the active groups with higher energy in the monomer component are broken to form active sites, and the additional active sites introduced are cross-linked in a plasma environment to form a network structure, a network structure. It has better compactness and can effectively improve the protective performance of the film.
  • plasma polymerization uses a monofunctional monomer to obtain a loose coating structure.
  • the crosslinked structure is formed by a plurality of active sites formed by random interruption of the monomer during plasma glow discharge to form a crosslinked structure.
  • the present invention introduces an additional cross-linking point by introducing other monomer components having a polyfunctional cross-linking structure to form a cross-linked structure, and the introduction of a cross-linking structure of the polyfunctional group, so that the coating forms a dense network structure, and the introduction is much
  • the functional monomer accounts for the mass percentage of the monomer. 10-80%. Not only can the material be given good physical and chemical durability, but it can also impart excellent water and oil repellency to the material.
  • the surface is activated to obtain a plurality of active sites, and the active sites are combined with the active sites of the monomers with strong chemical bonds, so that the film obtained by the coating has superior bonding force and mechanical strength. .
  • a method for preparing a gradient-increasing structure liquid-repellent coating comprising: the following steps:
  • the plasma chamber volume is 50 liters, the plasma chamber temperature is controlled at 30 °C, and the nitrogen gas flow rate is 5 sccm.
  • the first monomer vapor is: a monofunctional unsaturated fluorocarbon resin, and the monofunctional unsaturated fluorocarbon resin is 2-perfluorooctyl acrylate.
  • the first monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the first monomer vapor is 10 ⁇ L/min;
  • the second monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; the polyfunctional unsaturated hydrocarbon derivative is diethylene glycol divinyl ether,
  • the second monomer vapor is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the second monomer vapor is 0 ⁇ L/min.
  • the second monomer steam inlet flow rate is increased, the increasing rate is 1 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the third monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; the polyfunctional unsaturated hydrocarbon derivative is ethylene glycol diacrylate,
  • the third monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the third monomer vapor is 0 ⁇ L/min.
  • the third monomer steam inlet flow rate is increased, the increasing rate is 8 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the glow discharge is performed on the substrate by bombardment pretreatment to clean the surface impurities of the substrate and activate the surface of the substrate.
  • the plasma discharge has a power of 2 W and a sustained discharge time of 600 s, and the plasma discharge mode is radio frequency.
  • the plasma during radio frequency discharge The energy output mode of the control plasma RF is pulse or continuous output.
  • the pulse width is 2 ⁇ s and the repetition frequency is 20Hz.
  • a pulsed voltage is applied to increase the uniformity of film formation and to reduce free radicals remaining in the coating.
  • the plasma power supply is turned off, the monomer vapor is stopped, and the vacuum is continuously applied to maintain the vacuum of the reaction chamber at 10 mTorr. After 1 min, it is introduced into the atmosphere to an atmospheric pressure, and then the substrate is taken out.
  • the substrate in step (1) is a solid material, and the solid material is an electrical component, and the vacuum in the reaction chamber is drawn to 200.
  • the mTorr was introduced with an inert gas; the plasma chamber volume was 1000 liters, the plasma chamber temperature was controlled at 60 ° C; the inert gas flow rate was 300 sccm, and the inert gas was argon gas.
  • step (2) 1.
  • the first monomer vapor is: a monofunctional unsaturated fluorocarbon resin, and the monofunctional unsaturated fluorocarbon resin is 2-(perfluorodecyl) Ethyl methacrylate, the first monomer vapor is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the first monomer vapor is 1000. ⁇ L/min ;
  • the second monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; the polyfunctional unsaturated hydrocarbon derivative is ethylene glycol diacrylate,
  • the second monomer vapor is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the second monomer vapor is 0 ⁇ L/min.
  • the second monomer steam inlet flow rate is increased, the increasing rate is 10 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the third monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; and the polyfunctional unsaturated hydrocarbon derivative is neopentyl glycol diacrylate.
  • the third monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the third monomer vapor is 0 ⁇ L/min.
  • the third monomer steam inlet flow rate is increased, the increasing rate is 6 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the glow discharge is performed on the substrate by bombardment pretreatment to clean the surface impurities of the substrate and activate the surface of the substrate.
  • the power of the plasma discharge in step (2) is 500W, and the continuous discharge time is 300s.
  • the plasma discharge mode is microwave discharge.
  • step (3) keep the vacuum of the reaction chamber at 200 mTorr for 5 min and then pass to the atmosphere to an atmospheric pressure.
  • the substrate in step (1) is a solid material, the solid material is a fabric, and the vacuum in the reaction chamber is drawn to 50.
  • the mTorr was introduced with an inert gas; the plasma chamber volume was 200 liters, the plasma chamber temperature was controlled at 40 ° C; the inert gas flow rate was 100 sccm, and the inert gas was helium gas.
  • step (2) 1.
  • the first monomer vapor is: a monofunctional unsaturated fluorocarbon resin, and the monofunctional unsaturated fluorocarbon resin is 1-ethynyl-3,5- Difluorobenzene, the first monomer vapor is introduced to atomize and volatilize the monomer through a feed pump, and is introduced into the reaction chamber from a low pressure of 40 mTorr, and the flow rate of the first monomer vapor is 300 ⁇ L/ Min ;
  • the second monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; the polyfunctional unsaturated hydrocarbon derivative is diethylene glycol divinyl ether, The second monomer vapor is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the second monomer vapor is 0 ⁇ L/min.
  • the third monomer steam inlet flow rate is increased, the increasing rate is 3 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the third monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; and the polyfunctional unsaturated hydrocarbon derivative is polyethylene glycol diacrylate.
  • the third monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the third monomer vapor is 0 ⁇ L/min.
  • the third monomer steam inlet flow rate is increased, the increasing rate is 10 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the glow discharge is performed on the substrate by bombardment pretreatment to clean the surface impurities of the substrate and activate the surface of the substrate.
  • the power of the plasma discharge in step (2) is 100W, and the continuous discharge time is 400s.
  • the plasma discharge mode is a spark discharge.
  • step (3) keep the vacuum of the reaction chamber at 50 mTorr for 2 min and then pass to the atmosphere to an atmospheric pressure.
  • the substrate in step (1) is a solid material, and the solid material is a garment, and the vacuum in the reaction chamber is drawn to 150.
  • an inert gas is introduced; the plasma chamber volume is 600 liters, the plasma chamber temperature is controlled at 45 °C; the inert gas flow rate is 150 sccm
  • the inert gas is a mixture of argon and helium.
  • step (2) 1.
  • the first monomer vapor is: a monofunctional unsaturated fluorocarbon resin, and the monofunctional unsaturated fluorocarbon resin is 2-(perfluorohexyl) Ethyl methacrylate, the first monomer vapor is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the first monomer vapor is 550. ⁇ L/min ;
  • the second monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; the polyfunctional unsaturated hydrocarbon derivative is diethylene glycol divinyl ether,
  • the second monomer vapor is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the initial flow rate of the second monomer vapor is 0 ⁇ L/min.
  • the second monomer steam inlet flow rate is increased, the increasing rate is 8 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the third monomer vapor is: a polyfunctional unsaturated hydrocarbon derivative; and the polyfunctional unsaturated hydrocarbon derivative is 1,6-
  • the hexanediol diacrylate is introduced into the third monomer vapor to atomize and volatilize the monomer through the feed pump, and is introduced into the reaction chamber from a low pressure of 100 mTorr.
  • the initial flow rate of the third monomer vapor is 0 ⁇ L/min; the third monomer steam inlet flow rate is increased, the increasing rate is 1 ⁇ L/min, and the maximum inlet flow rate is 500 ⁇ L/min;
  • the glow discharge is performed on the substrate by bombardment pretreatment to clean the surface impurities of the substrate and activate the surface of the substrate.
  • step (2) the plasma discharge power is 250W, and the continuous discharge time is 450s.
  • the plasma discharge mode is an intermediate frequency discharge.
  • step (3) keep the vacuum of the reaction chamber at 100 mTorr for 3 min and then pass to the atmosphere to an atmospheric pressure.
  • Embodiment 1 to Embodiment 4 above The coating prepared by the method has excellent hydrophobicity, oleophobicity, low adhesion, resistance to organic solvent dissolution, and water-resistant electrical conductivity.
  • the test results are as follows:
  • Example 1 Example 2
  • Example 3 Example 4 Water contact angle 95° 113° 105° 125° Adhesion High adhesion, water droplets slip easily Low adhesion, water droplets are easy to slip Low adhesion, water droplets are easy to slip Low adhesion, water droplets slip easily Oil contact angle 33° 70° 75° 95°

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Physical Vapour Deposition (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Cette invention concerne un procédé de préparation d'un revêtement étanche aux liquides ayant une structure à gradient croissant, comprenant les étapes suivantes : (1) placer le matériau de base dans la cavité de réaction d'une chambre à plasma, mettre la cavité de réaction sous vide en continu jusqu'à ce que le degré de vide dans la cavité de réaction soit de 10 à 200 milliTorrs, et introduire un gaz inerte ou de l'azote ; (2) introduire les premier, deuxième et troisième monomères en phase vapeur en même temps, et démarrer la décharge plasma pour procéder au dépôt chimique en phase vapeur ; (3) après la décharge, arrêter la source d'énergie plasma, arrêter l'introduction des trois monomères en phase vapeur, pratiquer une mise sous vide en continu, et après que le degré de vide de la cavité de réaction est maintenu à 10-200 milliTorrs pendant 1-5 min, ramener l'atmosphère à la pression atmosphérique, puis retirer le matériau de base, où le premier monomère en phase vapeur est une résine fluorocarbonée insaturée monofonctionnelle introduite à un flux de 10-1000 µL/min ; le deuxième monomère en phase vapeur est un dérivé d'hydrocarbure insaturé polyfonctionnel introduit à un flux initial de 0 µL/min, qui est porté à 1-10 µL/min, le flux maximal étant de 500 µL/min ; et le troisième monomère en phase vapeur est un dérivé d'hydrocarbure insaturé polyfonctionnel introduit à un flux initial de 0 µL/min, et est porté à 1-10 µL/min, le flux maximal étant de 500 µL/min.
PCT/CN2017/081786 2017-01-23 2017-04-25 Procédé de préparation d'un revêtement étanche aux liquides ayant une structure à gradient croissant WO2018133234A1 (fr)

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CN201710049183.XA CN106835075B (zh) 2017-01-23 2017-01-23 一种梯度递增结构防液涂层的制备方法
CN201710049183.X 2017-01-23

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CN107587120B (zh) * 2017-08-23 2018-12-18 江苏菲沃泰纳米科技有限公司 一种具有调制结构的高绝缘纳米防护涂层的制备方法
CN109267039B (zh) * 2018-10-24 2019-11-29 江苏菲沃泰纳米科技有限公司 一种聚氨酯纳米涂层及其制备方法
CN111621208B (zh) * 2020-05-18 2021-11-05 江苏菲沃泰纳米科技股份有限公司 防水膜层及其制备方法、应用和产品
CN116673273B (zh) * 2023-08-03 2023-10-27 北京奇峰蓝达光学科技发展有限公司 一种氟化钙原料表面去杂方法及其装置

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CN1539896A (zh) * 2003-10-30 2004-10-27 复旦大学 一种改进高分子基底水阻隔性的方法
US20090130330A1 (en) * 2005-07-26 2009-05-21 Fraunhofer-Gesellschaft Zur Foerderung Der Angerwandten Forschung E.V. Method for producing Functional Fluorocarbon Polymer Layers by Means of Plasma Polymerization of Perfluorocycloalkanes
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CN1322264A (zh) * 1998-09-07 2001-11-14 宝洁公司 具有超级疏水涂层的纺织品和衣服
CN1539896A (zh) * 2003-10-30 2004-10-27 复旦大学 一种改进高分子基底水阻隔性的方法
US20090130330A1 (en) * 2005-07-26 2009-05-21 Fraunhofer-Gesellschaft Zur Foerderung Der Angerwandten Forschung E.V. Method for producing Functional Fluorocarbon Polymer Layers by Means of Plasma Polymerization of Perfluorocycloalkanes
CN104718258A (zh) * 2012-08-13 2015-06-17 欧洲等离子公司 表面涂层

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