WO2020082681A1 - 一种高透明低色差纳米涂层及其制备方法 - Google Patents

一种高透明低色差纳米涂层及其制备方法 Download PDF

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WO2020082681A1
WO2020082681A1 PCT/CN2019/079116 CN2019079116W WO2020082681A1 WO 2020082681 A1 WO2020082681 A1 WO 2020082681A1 CN 2019079116 W CN2019079116 W CN 2019079116W WO 2020082681 A1 WO2020082681 A1 WO 2020082681A1
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monomer
coating
discharge
plasma
nano
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PCT/CN2019/079116
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French (fr)
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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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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the invention relates to the technical field of plasma chemical vapor deposition, in particular to a high-transparent low-color-difference nano protective coating and a preparation method thereof.
  • the intrusion of liquid and moisture is one of the most important causes of PCB board corrosion and short circuit in electronic devices.
  • Polymer coatings are often used for the protection of material surfaces due to their advantages such as economy, easy coating, wide application range, and good chemical resistance.
  • the polymer coating blocks the intrusion of liquids, especially water and steam, thereby improving the adaptability of electronic devices in a humid environment, and making important product indicators such as quality stability and reliability, service life of electronic devices to a great extent improve.
  • Liquid phase coating such as three-proof paint
  • the construction method can use dipping method, brushing method, spraying method and other processes, the liquid phase raw material is applied on the surface of the substrate and then thermally cured, light cured and other means to form dense, cross-linked Polymer coating.
  • the liquid-phase coating method generates a large amount of exhaust gas and waste liquid, and the raw material utilization rate is low.
  • the solvent used often causes certain damage to the PCB of the electronic device; in addition, the thickness of the three anti-paint is more than tens of microns The uniformity of the thickness is poor, which has a great impact on the functions of some electronic devices that require heat dissipation and signal transmission.
  • the vapor deposition method especially the plasma chemical vapor deposition method, is a method that uses plasma to activate the reactive gas and perform chemical vapor deposition on the substrate surface. This method is suitable for the protection requirements of various substrate surfaces: vapor-phase coating can be uniformly deposited on substrates of different shapes; the coating preparation temperature is low, suitable for the protection of temperature-sensitive devices; the coating is thin and the stress is small, Less damage to PCB.
  • the protective material on the PCB is mainly fluorocarbon resin, but the coefficient of friction of the fluorocarbon resin is very low, it is easy to slide and deform under the action of external force, and it is not resistant to friction.
  • the fluorocarbon resin layer can be improved.
  • the force of the coating makes the coating more dense and enhances the protective ability of the coating to resist wear and corrosion.
  • CN107058979 "Preparation method of waterproof and electrical breakdown resistant coating"
  • multifunctional unsaturated hydrocarbon derivatives are introduced to improve the product's resistance to corrosion and underwater energization.
  • the coating formed by the selected multifunctional saturated hydrocarbon derivatives is generally high in crystallinity.
  • the present invention provides a high-transparency, low-color-difference nano-coating and a preparation method thereof to solve the problem of discoloration of the nano-coating on the product surface.
  • a nano-coating on the surface of high-transparency and low-color-difference products which exposes the substrate to the atmosphere of monomer vapor, and a chemical reaction occurs on the surface of the substrate through plasma discharge to form a protective coating;
  • the monomer vapor is vaporized monomer 1 or monomer 2, or a mixture of monomer 1 and monomer 2, that is, monomer vapor is one or a mixture of vaporized monomer 1 and monomer 2 ;
  • the monomer 1 has the structure represented by the following formula (I); the monomer 2 has the structure represented by the following formula (II);
  • R 1 and R 2 are groups connected to the vinyl group, and conventional organic groups can be selected, preferably hydrogen, alkyl, aryl, halogen or haloalkyl.
  • Y and Z are bridging groups, which can be non-polar groups such as alkyl subunits or strong polar groups to improve the adhesion between the coating and the substrate, preferably -O-, -CO -, -COO- and -CONH- one or several connected groups.
  • R 3 is a group containing a large steric hindrance group.
  • the presence of the large steric hindering group reduces the crystallinity of the coating. It may be a fatty alkane subunit containing 2 or more branched carbon atoms, an aryl subunit, and a cycloalkane subunit. Groups, or aliphatic alkyl subunits, aryl subunits, cycloalkane subunits substituted with hydroxyl, halogen, or carbonyl.
  • R 4 , R 5 and R 6 are groups connected to the double bond, and may be electron-donating groups or electron-withdrawing groups, preferably independently selected from hydrogen, alkyl, aryl, halogen, haloalkyl, Alkenyl or haloalkenyl, X is hydrogen or halogen.
  • X is a fluorine element, and the fluorinated alkyl group contains a CF bond. The bond energy is much higher than the CO and CC bonds, which can greatly improve the hydrophobicity and chemical resistance of the monomer.
  • n, and k are integers of 0-8; l is an integer of 1-20.
  • R 3 is a group having a cyclic structure, preferably an aryl subunit or a cyclohexane subunit.
  • m, n, k are 0, 1, 2 or 3.
  • Y and Z are oxygen atom-containing groups with high adhesion to the substrate, and can be independently selected from one of -O-, -CO-, and -COO-, or a combination bond of several connections.
  • the coating can be applied to a substrate with a smooth surface or a substrate with a rough surface.
  • the substrate may be an optical instrument, a metal surface, an electronic device, a fabric, or the like.
  • the invention also discloses a method for preparing the above nano-coating, which includes the following steps:
  • the monomer 1 and the monomer 2 When the monomer 1 and the monomer 2 are introduced into the reaction chamber, they can be introduced separately or at the same time; one monomer can be introduced first and then two monomers can be introduced simultaneously. Moreover, the molar ratio of monomer 1 and monomer 2 can be introduced in any ratio. Monomer 1 and monomer 2 are passed into the reaction chamber after being atomized and vaporized below one atmospheric pressure.
  • the plasma source gas in step (2) may be one or a mixture of several kinds of helium, argon, nitrogen, and hydrogen.
  • the volume of the reaction chamber of the plasma chamber is 1L-5000L
  • the flow rate of the plasma source gas is 5-1000 sccm
  • the flow rate of the monomer vapor is 1-2000 ⁇ L / min.
  • a plasma discharge step for pretreatment of the substrate is further included.
  • the pretreatment is started to perform pretreatment on the substrate with plasma discharge.
  • the power of plasma discharge in this pretreatment stage is 2-500W, and the continuous discharge time is 1-5400s.
  • the pretreatment phase After the pretreatment phase ends, it enters the deposition phase (the plasma discharge for pretreatment is converted to the plasma discharge for deposition).
  • the plasma discharge method and parameters of the two phases may be the same or different.
  • the power of the plasma discharge for deposition is 2-500 W, and the continuous discharge time is 600-20000s.
  • the plasma discharge (plasma discharge for pretreatment and / or plasma discharge for deposition) is radio frequency discharge, microwave discharge, intermediate frequency discharge, Penning discharge or electric spark discharge.
  • the plasma discharge (plasma discharge for pretreatment and / or plasma discharge for deposition) is a radio frequency discharge
  • the energy output method for controlling the plasma radio frequency during the radio frequency discharge is pulse or continuous output, and the plasma radio frequency
  • the pulse width is 10 ⁇ s-50ms and the repetition frequency is 20Hz-10kHz.
  • the introduction of large-volume groups in the monomer destroys the crystal order of the polymer chain during the polymerization process, reduces the crystallinity of the overall coating, and reduces the scattering, reflection, and The degree of anisotropy is refracted, which further reduces the color appearance of the product surface coating, and also increases the contact angle of the substrate surface and improves the hydrophobicity of the coating surface.
  • a method for preparing a nano-coating on the surface of a product with high transparency and low color difference undergoes the following steps:
  • the monomer 1a and the monomer 2a are vaporized and introduced into the reaction chamber for chemical vapor deposition reaction; the flow rate of the monomer 1a is 200 ⁇ L / min for 1000s; after the end, the flow rate of the monomer 2a is 100 ⁇ L / min for 400s.
  • the plasma discharge for pretreatment is adjusted to the plasma discharge for deposition.
  • the plasma in the deposition stage is generated by radio frequency discharge, the output mode is pulse, the pulse width is 2 ⁇ s, the repetition frequency is 500 Hz, the discharge power is 50 W, and the discharge time is the same as the monomer inflow time.
  • the radio frequency is turned off, nitrogen gas is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the optical lens is taken out.
  • the device for plasma discharge for pretreatment and the device for plasma discharge for deposition may be one set or two separate sets of devices.
  • the plasma discharge device (for example, electrode) for pretreatment is preferably arranged in the reaction chamber and around the base material, so as to facilitate the quick connection with the coating process after pretreatment;
  • the plasma discharge device for deposition can be arranged in the reaction chamber It is placed outside and away from the reaction chamber, so that the negative impact of plasma discharge on the substrate during the coating process can be selectively or as far as possible avoided.
  • a method for preparing a nano-coating on the surface of a product with high transparency and low color difference undergoes the following steps:
  • the monomer 1b and monomer 2b are vaporized and then introduced into the reaction chamber for chemical vapor deposition reaction; the monomer 1b and 2b are simultaneously introduced, the monomer 1b flow rate is 250 ⁇ L / min, and the monomer 2b flow rate is 150 ⁇ L / min For 1000s.
  • the plasma discharge for pretreatment is adjusted to the plasma discharge for deposition.
  • the plasma in the chamber is generated by radio frequency discharge
  • the output mode is pulse
  • the pulse width is 1ms
  • the repetition frequency is 400Hz
  • the discharge power is 50W
  • the discharge time is the same as the monomer pass-through time.
  • the radio frequency is turned off, nitrogen gas is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the metal magnesium sheet is taken out.
  • a method for preparing a nano-coating on the surface of a product with high transparency and low color difference undergoes the following steps:
  • the plasma discharge for pretreatment is adjusted to the plasma discharge for deposition.
  • the plasma in the chamber is generated by radio frequency discharge
  • the output mode is pulse
  • the pulse width is 1ms
  • the repetition frequency is 400Hz
  • the discharge power is 50W
  • the discharge time is the same as the monomer pass-through time.
  • the radio frequency is turned off, nitrogen gas is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the copper sheet is taken out.
  • the monomers 1a and 2a in step (3) were replaced with 1d and 2d, respectively, the monomer 1d passage time was 2500s, and the monomer 2d passage time was 500s.
  • the monomers 1a and 2a of step (3) were replaced with 1e and 2e, respectively, the monomer 1e introduction time was 3500s, and the monomer 2e introduction time was 700s.
  • Example 1 Compared with Example 1, the vacuum degree of the reaction chamber in step (1) was changed to 50 mTorr, and other conditions were unchanged.
  • step (4) 1c is not introduced, and the replacement is: the monomer 2c is introduced with a flow rate of 250 ⁇ L / min for 2000 s; then the monomer 2c is introduced with a flow rate of 50 ⁇ L / min for 600 s. Other conditions are not changed.
  • step (4) 2c is not introduced, and the replacement is: the monomer 1c is introduced with a flow rate of 250 ⁇ L / min for 2000 s; then the monomer 1c is introduced with a flow rate of 50 ⁇ L / min for 600 s. Other conditions are not changed.
  • the substrates after the plating in the above embodiments were subjected to the measurement of coating thickness, water contact angle, crystallinity, color difference, and abrasion resistance.
  • the thickness of the nano-coating is tested using the US Filmetrics-F20-UV-film thickness measuring instrument.
  • Nano-coating water contact angle is tested according to GB / T 30447-2013 standard.
  • the color difference test method is calculated according to the GB 11186.3-1989 standard.
  • the Minolta CR-10 portable color difference meter is used to detect the total color difference ⁇ E.
  • the abrasion resistance test is conducted in an alcohol abrasion tester, and the eraser test fixture is selected for the test.
  • the test condition is a load of 100g and a rotation speed of 40rpm.
  • the invention utilizes the introduction of a large steric hindrance monomer in the preparation process of the coating to prepare a hydrophobic nanocomposite coating, which reduces the crystallinity of the coating, the total color difference is ⁇ E ⁇ 2.0, and the hydrophobicity and abrasion resistance of the coating are less Fluorocarbon resin coating is excellent.

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Abstract

一种高透明低色差产品表面纳米涂层，将基材暴露于单体蒸汽氛围中，通过等离子体放电在基材表面发生化学反应形成保护涂层；单体蒸汽为汽化的式(I)所示的单体1或者式(II)所示的单体2，或者单体1和单体2的混合物。涂层的制备方法为将基材置于等离子体室的反应腔体内，通入等离子体源气体，开启沉积用等离子体放电，将单体经汽化后导入反应腔体进行化学气相沉积反应，关闭沉积用等离子体放电，通入洁净的压缩空气或惰性气体恢复至常压，打开腔体，取出基材。

Description

一种高透明低色差纳米涂层及其制备方法 技术领域
本发明涉及等离子体化学气相沉积技术领域，具体涉及到一种高透明低色差纳米防护涂层及其制备方法。
背景技术
液体、湿气的侵入是造成电子器件中PCB板腐蚀、短路等最主要原因之一。聚合物涂层由于经济、易于涂覆、适用范围广、耐化学腐蚀性好等优点常用于材料表面的防护。聚合物涂层阻隔了液体尤其是水及蒸汽的侵入，从而提高了电子器件在潮湿环境中的适应性，使电子器件的质量稳定性和可靠性、使用寿命等重要产品指标得到很大程度的改善。
目前在PCB板上施加防护层的方法根据材料的状态主要有两种，液相涂覆和气相沉积。液相涂覆，比如三防漆，施工方式可采用浸渍法、刷涂法、喷涂法等工艺，将液相原料施加在基材表面然后利用热固化、光固化等手段，形成致密、交联的聚合物涂层。但液相涂覆的方法产生大量的废气、废液，原料利用率较低，同时使用的溶剂往往会对电子器件PCB板造成一定的损伤；此外，三防漆厚度多为几十微米以上，厚度的均匀性比较差，对一些需要散热和信号传输的电子器件功能影响很大。与之相比，气相沉积的方法，尤其是等离子体化学气相沉积法，是利用等离子体活化反应气体并 在基材表面进行化学气相沉积的方法。这种方法适用于各种基材表面的防护要求：气相镀膜可均匀沉积在不同形貌的基材上；涂层制备温度低，适用于对温度敏感的器件防护；涂层薄、应力小，对PCB损伤小。现在PCB上的防护材料主要氟碳树脂，但氟碳树脂摩擦系数很低，在外力作用下易于滑动和变形，不耐摩擦，通过添加交联剂的方法可提高氟碳树脂层与层之间的作用力，使涂层更加致密，增强涂层耐磨、耐腐蚀的防护能力。CN107058979《一种防水耐电击穿涂层的制备方法》在氟碳树脂单体中，引入了多官能度不饱烃类衍生物，提高了产品耐腐蚀和耐水下通电的性能。但由于所选的多官能度的饱和烃类衍生物所形成的涂层结晶性一般较高，涂层达到一定厚度时，光的反射、折射、双折射等异色现象明显，出现表面彩虹情况，这往往使产品的外观受到严重影响。如何通过分子设计，降低涂层的结晶度，减少施镀后由于涂层导致的异色现象，是目前纳米涂层在电子产品应用领域急需解决的技术问题之一。
发明内容
本发明是为了克服以上缺点，提供了一种高透明低色差纳米涂层及其制备方法，解决产品表面纳米涂层异色的问题。
本发明是通过以下技术方案实现的：
一种高透明低色差产品表面纳米涂层，将基材暴露于单体蒸汽氛围中，通过等离子体放电在基材表面发生化学反应形成保护涂层；
所述单体蒸汽为汽化的单体1或者单体2，或者单体1和单体2的混合物，即单体蒸汽为汽化的单体1和单体2中的一种或两者的混合；
所述单体1具有如下的式(I)所示结构；所述单体2具有如下的式(II)所 示结构；
单体1：
Figure PCTCN2019079116-appb-000001
单体2：
Figure PCTCN2019079116-appb-000002
其中，R 1、R 2是与乙烯基相连的基团，可选择常规的有机基团，优选氢、烷基、芳基、卤素或卤代烷基。
Y、Z是桥联基团，可以是非极性基团如烷基亚基，也可以是极性较强的基团，提高涂层与基材的粘接性能，优选-O-、-CO-、-COO-和-CONH-中的一种或者若干种连接而成的基团。
R 3为含大位阻的基团，大位阻基团的存在降低了涂层结晶度，可以是含有支链碳原子数2个以上的脂肪烷烃亚基，芳基亚基，环烷烃亚基，或者被羟基、卤素、羰基取代的脂肪烷基亚基、芳基亚基、环烷烃亚基等。
R 4、R 5、R 6是与双键相连的基团，可以是供电子基团，也可以是吸电子基团，优选独立地选自氢、烷基、芳基、卤素、卤代烷基、烯基或卤代烯基，X为氢或卤素。优选X为氟元素，氟化烷基含有C-F键，键能比C-O、C-C键高得多，能够大幅提高单体的疏水性、耐化学性。
m、n、k为0-8的整数；l为1-20的整数。
进一步地，R 3为环状结构的基团，优选芳基亚基或环己烷亚基。
优选地，m、n、k为0、1、2或3。
优选地，Y、Z是具有与基材高粘结性的含氧原子基团，可以独立地选自-O-、-CO-和-COO-中的一种或者若干种连接的组合键。
涂层可施加于具有光洁表面的基材上，也可以施加于粗糙表面的基材上。所述基材可以是光学仪器、金属表面、电子设备或织物等。
另外，本发明还公开了一种上述纳米涂层的制备方法，其包括以下步骤：
(1)将基材置于等离子体室的反应腔体内，反应腔体内的真空度为0.0001-1000毫托；
(2)通入等离子体源气体，开启沉积用等离子体放电，将单体1和/或单体2经汽化后导入反应腔体进行化学气相沉积反应；
(3)关闭沉积用等离子体放电，通入洁净的压缩空气或者惰性气体恢复至常压，打开腔体，取出基材。
单体1、单体2通入反应腔体时可以分别通入，也可以同时通入；还可以先通入一种单体再同时通入两种单体。且单体1、单体2通入的摩尔量比例可以任意比例通入。单体1、单体2是经过在低于一个大气压进行雾化、汽化后再通入反应腔体的。
步骤(2)所述的等离子体源气体可以是氦气、氩气、氮气、氢气中的一种或者若干种的混合物。
优选地，所述等离子体室反应腔体的容积为1L-5000L，等离子体源气体流量为5～1000sccm，通入单体蒸汽的流量为1-2000μL/min。
优选地，所述步骤(2)中，在通入所述等离子体源气体后以及在所述沉积用等离子体放电之前，还包括对基材进行预处理用等离子体放电工序。
步骤(2)中通入等离子体源气体后，开启预处理用等离子体放电对基材进行预处理。该预处理阶段等离子体放电的功率为2-500W，持续放电时间为1-5400s。
预处理阶段结束后进入沉积阶段(预处理用等离子体放电转换为沉积用等离子体放电)，两个阶段的等离子体放电方式以及参数可以相同也可以不同。
进一步地，所述步骤(2)中，所述沉积用等离子体放电的功率为2-500W，持续放电时间为600-20000s。
其中，所述等离子体放电(预处理用等离子体放电和/或沉积用等离子体放电)方式为射频放电、微波放电、中频放电、潘宁放电或电火花放电。
进一步地，所述等离子体放电(预处理用等离子体放电和/或沉积用等离子体放电)为射频放电，射频放电过程中控制等离子体射频的能量输出方式为脉冲或连续输出，等离子体射频的能量输出方式为脉冲输出时，脉宽为10μs-50ms、重复频率为20Hz-10kHz。
相比于现有技术，通过在单体中引入大体积的基团，破坏了聚合过程中的高分子链结晶有序性，降低了整体涂层的结晶度，减少产品表面光的散射、反射、折射各向异性的程度，进而达到降低产品表面涂层出现彩色的效果，同时还提高了基材表面的接触角，改善了涂层表面的疏水性。
具体实施方式
实施例1
一种高透明低色差产品表面纳米涂层的制备方法，所述的纳米涂层制备方法经过以下步骤：
(1)将光学镜片置于等离子体室的反应腔体内，对反应腔体连续抽真空，将反应腔体内的真空度抽到100毫托，通入氩气，流量为100sccm；
(2)开启射频方式的等离子体放电对光学镜片基材进行预处理(即开启射频方式的预处理用等离子体放电)，该预处理阶段放电功率为10W，持续放电100s；
(3)将单体1a、单体2a经汽化后导入反应腔体进行化学气相沉积反应；单体1a通入流量为200μL/min，持续1000s；结束后，通入单体2a，流量为100μL/min，持续400s。预处理用等离子体放电调整为沉积用等离子体放电。该沉积阶段腔体内等离子体的产生采用射频放电方式，输出方式为脉冲，脉冲宽度为2μs，重复频率为500Hz，放电功率为50W，放电时间与单体通入时间相同。
(4)涂层制备结束后，关闭射频，通入氮气，使反应腔体恢复至常压，打开腔体，取出光学镜片。
Figure PCTCN2019079116-appb-000003
其中，预处理用等离子体放电的装置和沉积用等离子体放电的装置可以是一套，也可以为独立的两套装置。预处理用等离子体放电装置(例如 电极)优选地设置在反应腔体内，且围绕基材设置，从而便于预处理后快速与涂层工艺衔接；沉积用等离子体放电装置可以布设在反应腔体之外且远离反应腔体设置，从而可选择地或尽可能地避免涂层过程中等离子体放电对基材的消极影响。
实施例2
一种高透明低色差产品表面纳米涂层的制备方法，所述的纳米涂层制备方法经过以下步骤：
(1)将金属镁片置于等离子体室的反应腔体内，对反应腔体连续抽真空，将反应腔体内的真空度抽到20毫托，通入氩气，流量为50sccm；
(2)开启射频方式的等离子体放电对金属镁片基材进行预处理(即开启射频方式的预处理用等离子体放电)，该预处理阶段放电功率为30W，持续放电200s；
(3)将单体1b、单体2b经汽化后导入反应腔体进行化学气相沉积反应；单体1b、2b同时通入，单体1b流量为250μL/min，单体2b流量为150μL/min，持续1000s。预处理用等离子体放电调整为沉积用等离子体放电。
该沉积阶段腔体内等离子体的产生采用射频放电方式，输出方式为脉冲，脉冲宽度为1ms，重复频率为400Hz，放电功率为50W，放电时间与单体通入时间相同。
(4)涂层制备结束后，关闭射频，通入氮气，使反应腔体恢复至常压，打开腔体，取出金属镁片。
Figure PCTCN2019079116-appb-000004
实施例3
一种高透明低色差产品表面纳米涂层的制备方法，所述的纳米涂层制备方法经过以下步骤：
(1)将金属铜片置于等离子体室的反应腔体内，对反应腔体连续抽真空，将反应腔体内的真空度抽到900毫托，通入氩气，流量为800sccm；
(2)开启射频方式的等离子体放电对金属铜片基材进行预处理(即开启射频方式的预处理用等离子体放电)，该预处理阶段放电功率为60W，持续放电200s；
(3)将单体1c、单体2c经汽化后导入反应腔体进行化学气相沉积反应；单体1c通入流量为250μL/min，持续2000s；结束后，通入单体2c，流量为50μL/min，持续600s。
预处理用等离子体放电调整为沉积用等离子体放电。该沉积阶段腔体内等离子体的产生采用射频放电方式，输出方式为脉冲，脉冲宽度为1ms，重复频率为400Hz，放电功率为50W，放电时间与单体通入时间相同。
(5)涂层制备结束后，关闭射频，通入氮气，使反应腔体恢复至常压，打开腔体，取出铜片。
Figure PCTCN2019079116-appb-000005
实施例4
与实施例1相比，将步骤(3)单体1a、2a分别替换为1d、2d，单体1d通入时间为2500s，单体2d通入时间为500s。
Figure PCTCN2019079116-appb-000006
实施例5
与实施例1相比，将步骤(3)单体1a、2a分别替换为1e、2e，单体1e通入时间为3500s，单体2e通入时间为700s。
Figure PCTCN2019079116-appb-000007
实施例6
与实施例1相比，将步骤(1)中的反应腔体真空度更换为抽到50毫托，其他条件不变。
实施例7
与实施例2相比，将步骤(4)中单体1b通入流量更换为400μL/min，其他条件不变。
实施例8
与实施例2相比，将步骤(4)中单体通入持续时间更换为1500s，其他条件不变。
实施例9
与实施例3相比，步骤(4)中不通入1c，更换为：单体2c通入流量为250μL/min，持续2000s；接着通入单体2c，流量为50μL/min，持续600s。其他条件不改变。
实施例10
与实施例3相比，步骤(4)中不通入2c，更换为：单体1c通入流量为250μL/min，持续2000s；接着通入单体1c，流量为50μL/min，持续600s。其他条件不改变。
将上述各实施例施镀后的基材，进行涂层厚度、水接触角、结晶度、色差、耐磨性的测量。
纳米涂层厚度，使用美国Filmetrics-F20-UV-薄膜厚度测量仪进行检测。
纳米涂层水接触角，根据GB/T 30447-2013标准进行测试。结晶度测试方法，采用日本理学D/MAX-3B型自动X射线衍射仪，Cu、Kα射线，λ＝154.06pm，扫描速度3°/min,扫描范围(2θ)为5°-65°。
色差测试方法，根据GB 11186.3-1989标准进行计算，使用美能达CR-10便携式色差仪检测，计算出总色差ΔE。
耐磨性测试，在酒精耐磨试验机进行，选择橡皮擦测试夹具进行测试，测试条件为载荷100g，转速40rpm。
表1
Figure PCTCN2019079116-appb-000008
本发明利用了在涂层制备过程中引入了大位阻单体制备疏水纳米复合涂层，使涂层的结晶度下降，总色差ΔE<2.0,涂层的疏水性、耐磨性均比单一氟碳树脂涂层优异。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (14)

  1. 一种高透明低色差产品表面纳米涂层，将基材暴露于单体蒸汽氛围中，通过等离子体放电在基材表面发生化学反应形成保护涂层；
    所述单体蒸汽为汽化的单体1和单体2中的一种或者两者的混合物；所述单体1具有如下的式(I)所示结构；所述单体2具有如下的式(II)所示结构；
    单体1：
    Figure PCTCN2019079116-appb-100001
    单体2：
    Figure PCTCN2019079116-appb-100002
    其中，R 1、R 2独立地选自氢、烷基、芳基、卤素或卤代烷基；Y、Z独立地选自键、-O-、烷基亚基、-CO-、-COO-和-CONH-中的一种或者若干种连接而成的基团；
    R 3为含有支链碳原子数2个以上的脂肪烷烃亚基、芳基亚基或环烷烃亚基，或者被羟基、卤素、羰基取代的含支链脂肪烷基亚基、芳基亚基或环烷烃亚基；
    R 4、R 5、R 6独立地选自氢、烷基、芳基、卤素、卤代烷基、烯基或卤代烯基；X选自氢或者卤素；
    m、n、k为0-8整数；l为1-20的整数。
  2. 根据权利要求1所述的高透明低色差产品表面纳米涂层，其特征在于，R 3为芳基亚基或环己烷亚基。
  3. 根据权利要求1所述的高透明低色差产品表面纳米涂层，其特征在 于，m、n、k为0、1、2或3。
  4. 根据权利要求1所述的高透明低色差产品表面纳米涂层，其特征在于，所述基材为光学仪器、金属表面、电子设备或织物。
  5. 一种权利要求1-4任一项所述的高透明低色差产品表面纳米涂层的制备方法，其特征在于，其包括以下步骤：
    (1)将基材置于等离子体室的反应腔体内，反应腔体内的真空度为0.0001-1000毫托；
    (2)通入等离子体源气体，开启沉积用等离子体放电，将所述单体蒸汽导入反应腔体进行化学气相沉积反应；
    (3)关闭沉积用等离子体放电，通入洁净的压缩空气或者惰性气体恢复至常压，打开腔体，取出基材。
  6. 根据权利要求5所述的纳米涂层的制备方法，其特征在于，所述单体蒸汽包括单体1和单体2；
    所述单体1和单体2分别通入反应腔体；
    或者，所述单体1和单体2同时通入反应腔体；
    或者，先将所述单体1和单体2中的一种先通入反应腔体，后再同时通入单体1和单体2。
  7. 根据权利要求5所述的纳米涂层的制备方法，其特征在于，将所述单体1和/或单体2通过加料泵进行雾化、挥发形成所述单体蒸汽。
  8. 根据权利要求5所述的纳米涂层的制备方法，其特征在于，步骤(2)中所述的等离子体源气体可以是氦气、氩气、氮气和氢气中的一种或者若干种的混合物。
  9. 根据权利要求5所述的纳米涂层的制备方法，其特征在于，所述等离子体室反应腔体的容积为1L-5000L，等离子体源气体流量为5-1000sccm，单体蒸汽通入反应腔体时的流量为1-2000μL/min。
  10. 根据权利要求5所述的纳米涂层的制备方法，其特征在于，所述 步骤(2)中，在通入所述等离子体源气体后以及在所述沉积用等离子体放电之前，还包括对基材进行预处理用等离子体放电工序。
  11. 根据权利要求10所述的纳米涂层的制备方法，其特征在于，所述步骤(2)中，所述预处理用等离子体放电的功率为2-500W，持续放电时间为1-5400s。
  12. 根据权利要求5所述的纳米涂层的制备方法，其特征在于，所述步骤(2)中，所述沉积用等离子体放电的功率为2-500W，持续放电时间为600-20000s。
  13. 根据权利要求5或者10所述的纳米涂层的制备方法，其特征在于，所述等离子体放电方式为射频放电、微波放电、中频放电、潘宁放电或电火花放电。
  14. 根据权利要求5或者10所述的纳米涂层的制备方法，其特征在于，所述等离子体放电方式为射频放电，射频放电过程中控制等离子体射频的能量输出方式为脉冲或连续输出；等离子体射频的能量输出方式为脉冲输出时，脉宽为10μs-50ms、重复频率为20Hz-10kHz。
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