WO2020082679A1 - 一种环氧纳米涂层及其制备方法 - Google Patents

一种环氧纳米涂层及其制备方法 Download PDF

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WO2020082679A1
WO2020082679A1 PCT/CN2019/079114 CN2019079114W WO2020082679A1 WO 2020082679 A1 WO2020082679 A1 WO 2020082679A1 CN 2019079114 W CN2019079114 W CN 2019079114W WO 2020082679 A1 WO2020082679 A1 WO 2020082679A1
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plasma
discharge
coating
coating according
epoxy nano
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PCT/CN2019/079114
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English (en)
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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment

Definitions

  • the invention relates to the technical field of plasma chemical vapor deposition, in particular to an epoxy nano-coating and a preparation method thereof.
  • Epoxy compounds refer to compounds containing oxirane. After the ring-opening polymerization, the main chain contains ether bonds, which has excellent chemical resistance, especially acid resistance, alkali resistance and oxidation resistance. In addition, the epoxy compound has good adhesion to many substrate surfaces, especially the metal surface. After crosslinking, it has strong rigidity, heat resistance and wear resistance; the compound contains a three-membered ring ether structure, high tension, and thermodynamic ring opening The tendency is very large, and it is easy to form polymers, so epoxy resins are widely used in the coating industry.
  • CN102229777A "A hydrophobic oleophobic epoxy coating and its preparation and use method” by introducing low surface energy substances and nanoparticles, using the principle of micro-phase separation, the prepared epoxy coating has strong hydrophobic oleophobicity and contact with water The angle can reach 149 °, and the contact angle to oil is up to 101 °.
  • the preparation method and use method are as follows: In the first step, the fluorine-containing acrylate, vinyl-containing triethoxysilane, styrene and other raw materials are mixed according to a certain quality ratio and prepared through multiple processes such as demulsification, water washing and drying.
  • the second step is to mix the epoxy paint, the prepared fluorosilicone copolymer, mixed solvent, nano calcium dioxide, curing agent and other raw materials according to the mass ratio of the preparation to obtain a low surface energy epoxy coating;
  • the low surface energy epoxy coating is coated on the surface of the substrate, and cured at 50 ° C for 1 to 5 hours, and then heated to 120 ° C to 200 ° C for 1 to 5 hours.
  • the preparation process of this method is complex, and the use of multiple organic solvents in the formulation is prone to pollution.
  • CN “107694881” "A Method for Improving the Bonding Strength of Epoxy Coatings” provides a method for improving the bonding strength of epoxy coatings, that is, applying atmospheric air plasma to the substrate before applying epoxy resin The treatment will bombard the surface of the substrate with oil stains, adsorbents, etc. away from the surface, increase the roughness of the surface of some materials, increase the effective adhesion area and wetting surface area of the coating and the substrate. Within 2 hours after plasma treatment of the substrate surface, the epoxy coating was prepared by brush coating, spray coating or fluidized bed method.
  • the current epoxy resin construction process is to apply liquid coating on the surface of the substrate, and then use curing means to further crosslink the coating material to form a protective coating
  • the film thickness is generally in the tens of dozens Micron or more.
  • the barrier properties of the coating itself can easily lead to poor heat dissipation and conductivity of the substrate.
  • the construction process also determines the presence of these epoxy coatings The situation where the surface coverage is uneven and part of the device cannot be effectively protected by the coating.
  • the thickness of the epoxy polymer coating can be accurately controlled in the range of nanometers and micrometers while maintaining the strength and bonding force of the epoxy polymer coating.
  • the present invention provides a method for preparing epoxy resin nano-coating using plasma chemical vapor deposition technology and the nano-coating obtained by using the method.
  • the invention also provides a method for preparing a high-adhesion coating under low power.
  • An epoxy nano-coating characterized in that the substrate is exposed to a monomer having the structure represented by formula (I), and a chemical reaction occurs on the surface of the substrate by plasma means to form a protective coating:
  • R 1 , R 2 and R 3 are groups connected to the three-membered ring, and are independently selected from hydrogen, alkyl, aryl, halogen, haloalkyl or hydroxy; m is an integer of 0-8 and n is 1- An integer of 15.
  • the power supply characteristics and the size of the groups R 1 , R 2 , and R 3 on the three-membered ring have an important influence on the stability and ring-opening tendency of the three-membered ring.
  • Alkyl, aryl, haloalkyl can be used as a power supply group to stabilize the three-membered ring, while hydroxyl, halogen and other electron-withdrawing groups will further enhance the electron-positive carbon atoms in the three-membered ring.
  • the ring-opening polymerization can be rapidly initiated under the plasma.
  • R 1 , R 2 and R 3 are hydrophobic groups and are independently selected from hydrogen, alkyl, halogen or haloalkyl.
  • the halogen is fluorine
  • the halogenated alkyl group is a perfluoroalkyl group with a carbon number of 1-10.
  • the fluoroalkyl group may be linear or may contain branched chains.
  • X is hydrogen or halogen
  • the carbon-hydrogen and carbon-halogen bond energies are high, the monomer structure is relatively stable and the chemical resistance is excellent.
  • X is preferably fluorine
  • the interaction force between fluorine atoms is large, the C-F bond is symmetrically distributed around the entire molecule, so that the surface energy of the molecule is very low, and the coating obtained by polymerization has good hydrophobicity.
  • n 10
  • the boiling point of the monomer is higher, which is not conducive to vaporization.
  • m is 0, 1, 2, or 3
  • n is an integer of 1-8.
  • the epoxy nano-coating can be used to protect the surfaces of different substrates against chemical corrosion and hydrophobicity.
  • the substrate can be solid materials such as metals, optical instruments, clothing fabrics, electronic devices, medical devices, etc.
  • the invention also discloses a preparation method of the nano coating layer including the following steps:
  • the monomer is introduced into the reaction chamber after being vaporized under reduced 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 plasma chamber is 1L-2000L
  • the flow rate of the plasma source gas is 1-1000sccm
  • 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 plasma discharge is turned on and the substrate is pretreated first.
  • the power of plasma discharge in this pretreatment stage is 1-1000W, and the continuous discharge time is 1-6000s.
  • 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 during the introduction of the monomer into the cavity is 2-500W, and the continuous discharge time is 600-18000s.
  • the plasma discharge power for deposition is preferably 2-50W.
  • 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 monomer polymerization mechanism of the present invention is mainly based on epoxy ring opening, the plasma power required for excitation is low, and the destruction of monomer molecular structure integrity by high-power discharge means is avoided.
  • the invention adopts an epoxy compound with good adhesion performance to the substrate, which greatly improves the binding force between the nano coating and the substrate.
  • the invention uses the plasma technology to initiate the polymerization reaction of the epoxy compound. By controlling the process conditions such as the monomer flow rate and plasma discharge power, the problem of difficulty in heat dissipation caused by the explosion polymerization of the epoxide is avoided.
  • the monomer S1 is passed through to perform chemical vapor deposition on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the monomer is 150 ⁇ L / min.
  • 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 5 ⁇ s, the repetition frequency is 3000 Hz, the discharge power is 10 W, and the discharge time is 2000 s.
  • Test the protective properties of the sample coating including the coating thickness, hydrophobicity (water contact angle), chemical resistance, coating adhesion, and contact resistance.
  • the plasma discharge device for pretreatment and the plasma discharge device for deposition may be one set or two separate sets.
  • 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.
  • the monomer S2 was passed through the chemical vapor deposition on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the monomer was 300 ⁇ L / min. After 10 mTorr high vacuum vaporization, it was passed into the reaction chamber for 2500s.
  • 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 100 ⁇ s, the repetition frequency is 5000 Hz, the discharge power is 20 W, and the discharge time is 2500 s.
  • nitrogen gas is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the magnesium alloy is taken out.
  • Test the protective properties of the sample coating including the thickness of the coating, hydrophobicity (water contact angle), chemical resistance, coating adhesion, and contact resistance.
  • step (1) was evacuated to 100 mtorr; in step (2), the monomer S1 was replaced with a monomer S3, and the step (3) monomer inlet time and discharge time were replaced with 3000s, other conditions the same.
  • step (1) was evacuated to 150 mTorr; in step (2), the monomer S1 was replaced with the monomer S4, and the step (3) the monomer inlet time and discharge time were replaced with 3500s, other conditions the same.
  • step (2) helium was changed to nitrogen; in step (2), monomer S1 was replaced with monomer S5, and step (3) monomer inlet time and discharge time were replaced with 4000s, and other conditions were the same .
  • Example 2 Compared with Example 2, the substrate is replaced with a mobile phone PCB board, and other conditions are the same.
  • Example 2 Compared with Example 2, the monomer inflow time and discharge time in step (3) were changed to 12000s, and the other conditions were the same.
  • the monomer flow rate in step (3) was changed to 800 ⁇ L / min, and other conditions were the same.
  • the substrates after the plating in the above embodiments were tested for coating thickness, water contact angle, alkali corrosion resistance, and adhesion contact 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.
  • test method of contact resistance refer to GB / T5095.2-1997 for testing.
  • the process of preparing epoxy coating by this technical solution does not require the use of environmental pollutants such as curing agents and organic solvents, and the coating prepared by this technology can achieve alkali resistance and high viscosity in the nanometer range. Attached, while the contact resistance is very low.
  • the coating has excellent conductivity is a key indicator; the coating prepared by traditional methods is up to tens of microns thick, the resistance is very large, can not be used in the connection of electronic products.

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  • Engineering & Computer Science (AREA)
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Abstract

一种环氧纳米涂层，将基材暴露于具有式(I)所示结构的单体蒸汽中，通过等离子体放电在基材表面发生化学反应而形成的保护涂层。涂层的制备方法为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，打开反应腔体，取出基材。

Description

一种环氧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，具体涉及到一种环氧纳米涂层及其制备方法。
背景技术
环氧化合物是指含氧杂环丙烷的化合物，经开环聚合后主链中含有醚键，具有优良的抗化学品性能，特别是耐酸耐碱、耐氧化。此外，环氧化合物对众多基材表面的附着力很好，尤其是金属表面，经交联之后，刚性强、耐热、耐磨；化合物含有三元环醚结构，张力大，热力学上开环倾向很大，容易形成聚合物，因此环氧树脂在涂料工业中得到了广泛应用。CN102229777A《一种疏水疏油性环氧涂料及其制备和使用方法》通过引入低表面能物质和纳米粒子，利用微相分离原理，制备出的环氧涂层具有强疏水疏油性，对水的接触角可达到149°，对油的接触角高达101°。其制备方法和使用方法如下：第一步，先将含氟丙烯酸酯、含乙烯基三乙氧基硅烷、苯乙烯等原料按照一定质量配比混合经破乳、水洗和干燥等多项工艺制备氟硅共聚物；第二步将环氧色漆、制备的氟硅共聚物、混合溶剂、纳米二氧化钙、固化剂等原料按照投料质量配比混合制备得到低表面能环氧涂料；第三步，将该低表面能环氧涂料涂覆在基材表面上上，置于50℃下固化1～5h，再升温至120℃～200℃下固化 1～5h。该方法制备过程复杂，配方中使用多种有机溶剂容易产生污染。CN 107694881 A《一种提高环氧涂层结合强度的方法》提供了一种提高环氧涂层结合强度的方法，即在基体表面进行涂敷环氧树脂之前，对其进行常压空气等离子体处理，将基体表面的油渍、吸附物等轰击离开表面，增加一些材料基体表面的粗糙度，提高涂层与基体的有效附着面积和浸润表面积。基体表面经等离子体处理之后2h内，采用刷涂法、喷涂法或流化床法进行环氧涂层的制备。如这两篇专利所述，目前环氧树脂的施工工艺都是在基材表面进行液相涂敷，然后采用固化手段使涂层材料进一步交联形成保护涂层，膜厚一般都在几十微米以上。但在这个厚度下，涂层本身的阻隔性容易导致基体散热性、导电性等性能变差。尤其是使用在电子元器件接口等对电子信号要求较高的位置上时，容易出现被处理产品的电子信号大幅衰减，不能正常使用的情况；施工的工艺还决定了这些环氧涂层存在基体表面覆盖不均匀、器件的部分位置未能被涂层有效保护的情况。利用等离子体成膜方法，可在保持环氧聚合物涂层强度和结合力情况下，实现其厚度在纳米和微米级范围内精确可控。
发明内容
本发明是为了克服以上缺点，提供了利用等离子体化学气相沉积技术制备环氧树脂纳米涂层的方法及采用该方法获得的纳米涂层。本发明还提供了一种低功率下制备高粘接力涂层的方法。
本发明是通过以下技术方案实现的：
一种环氧纳米涂层，其特征在于，将基材暴露于具有式(I)所示 结构单体，通过等离子体手段在基材表面发生化学反应形成保护涂层：
单体：
Figure PCTCN2019079114-appb-000001
其中，R 1、R 2、R 3是与三元环相连的基团，独立地选自氢、烷基、芳基、卤素、卤代烷基或羟基；m为0-8整数，n为1-15的整数。三元环上的基团R 1、R 2、R 3供电特性及基团大小对三元环的稳定性及开环倾向有重要的影响。烷基、芳基、卤代烷基可作为供电基团稳定三元环，而羟基、卤素等为吸电子基团则会使三元环中缺电子的碳原子电正性进一步加强，在更低功率等离子体引发下即可迅速开环聚合。
进一步地，R 1、R 2、R 3为疏水性基团，独立地选自氢、烷基、卤素或卤代烷基。
进一步地，所述卤素为氟，卤代烷基为碳数在1-10的全氟烷基，所述氟代烷基可以是直链，也可以是含有支链。
进一步地，所述X为氢或卤素时，由于碳-氢、碳-卤素键能均较高，单体结构较为稳定、耐化学腐蚀优良。此外，当X优选为氟时，氟原子间作用力大，C-F键对称分布在整个分子周围，使分子的表面能很低，聚合得到的涂层具有很好的疏水性。
当m>5、n>10时，单体沸点较高，不利于汽化。优选地，m为0、1、2或3，n为1-8的整数。
所述的环氧纳米涂层可用于对不同基材的表面进行耐化学腐 蚀疏水进行防护，基材可以是金属、光学仪器、衣服织物、电子器件、医疗器械等固体材料。
本发明还公开了一种所述纳米涂层的制备方法包括以下步骤：
(1)将基材置于等离子体室的反应腔体内，将反应腔体内的真空度抽到0.1-1000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。
所述单体是经过减压汽化后引入反应腔体的。
进一步地，步骤(2)中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。
进一步地，所述等离子体室的容积为1L-2000L，等离子体源气体流量为1-1000sccm，通入单体蒸汽的流量为1-2000μL/min。
进一步地，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，开启预处理等离子体放电先对基材进行预处理。该预处理阶段等离子体放电的功率为1-1000W，持续放电时间为1-6000s。
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，单体导入腔体的过程中沉积用等 离子体放电的功率为2-500W，持续放电时间为600-18000s。
更为优选地，沉积用等离子体放电功率优选2-50W。
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)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。
与现有技术相比，本发明单体聚合机理为以环氧开环为主，所需激发的等离子体功率低，避免了大功率放电手段对单体分子结构完整性的破坏。本发明采用了与基材的粘接性能很好的环氧化合物，大大提高了纳米涂层与基材的结合力。本发明利用等离子体技术引发环氧化合物的聚合反应，通过控制单体流量、等离子体放电功率等工艺条件，避免了环氧化物爆聚导致散热困难的问题。
具体实施方式
实施例1
一种环氧纳米涂层及其制备方法，经过如下步骤：
(1)将铁块放置于200L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到0.8毫托。
(2)通入氦气，流量为50sccm，开启射频等离子体放电对铁块基材进行预处理(即开启射频方式的预处理用等离子体放电)，预处理阶段放电功率为20W，持续放电100s。
(3)通入单体S1在基材表面进行化学气相沉积制备纳米涂层，单体流量为150μL/min，经过1毫托高真空汽化后通入反应腔体，通入时间为2000s。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5μs，重复频率为3000Hz，放电功率为10W，放电时间为2000s。
(4)涂层制备结束后，通入氮气，使反应腔体恢复至常压，打开腔体，取出金属铁块。
(5)对样品涂层防护性能进行检测，检测内容包括涂层厚度、疏水性(水接触角)、耐化学腐蚀情况、涂层附着力、接触电阻。
Figure PCTCN2019079114-appb-000002
其中，预处理用等离子体放电装置和沉积用等离子体放电装置可以是一套，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
一种环氧纳米涂层及其制备方法，经过如下步骤：
(1)将镁合金放置于800L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到50毫托。
(2)通入氦气，流量为50sccm，开启射频等离子体放电对镁 合金基材进行预处理(即开启射频方式的预处理用等离子体放电)，预处理阶段放电功率为20W，持续放电100s。
(3)通入单体S2在基材表面进行化学气相沉积制备纳米涂层，单体流量为300μL/min，经过10毫托高真空汽化后通入反应腔体，通入时间为2500s。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100μs，重复频率为5000Hz，放电功率为20W，放电时间为2500s。(4)涂层制备结束后，通入氮气，使反应腔体恢复至常压，打开腔体，取出镁合金。(5)对样品涂层防护性能进行检测，检测内容包括涂层厚度、疏水性(水接触角)、耐化学腐蚀、涂层附着力、接触电阻。
Figure PCTCN2019079114-appb-000003
实施例3
与实施例1相比，步骤(1)抽真空至100毫托；步骤(2)中单体S1更换为单体S3，步骤(3)单体通入时间、放电时间更换为3000s，其他条件相同。
Figure PCTCN2019079114-appb-000004
实施例4
与实施例1相比，步骤(1)抽真空至150毫托；步骤(2)中单体S1更换为单体S4，步骤(3)单体通入时间和放电时间更换为3500s，其他条件相同。
Figure PCTCN2019079114-appb-000005
实施例5
与实施例2相比，步骤(2)氦气改为氮气；步骤(2)中单体S1更换为单体S5，步骤(3)单体通入时间、放电时间更换为4000s，其他条件相同。
Figure PCTCN2019079114-appb-000006
实施例6
与实施例1相比，将单体S1更换为S2，其他条件相同。
实施例7
与实施例2相比，将基材更换为手机PCB板，其他条件相同。
实施例8
与实施例2相比，将步骤(3)中的放电功率更换为5W，其他条件相同
实施例9
与实施例2相比，将步骤(3)中的单体通入时间、放电时间 均更换为12000s，其他条件相同。
实施例10
与实施例2相比，将步骤(3)中的单体流量更换为800μL/min，其他条件相同。
将上述各实施例施镀后的基材，进行涂层厚度、水接触角、耐碱性锈蚀、附着力接触阻值的测试。
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。
耐化学腐蚀，参照GB1763-79(89)漆膜耐化学试剂性测定法标准进行测试。附着力测试方法，根据GB/T 9286-1998标准进行百格刀划格试验。
接触阻值的测试方法，参照GB/T5095.2-1997进行测试。
表1
Figure PCTCN2019079114-appb-000007
采用本技术方案制备环氧涂层过程，与传统液相法相比，不需 要使用固化剂、有机溶剂等环境污染物，且本技术制备得到的涂层可在纳米尺度范围实现耐碱、高粘附，同时接触电阻非常低。在电子产品连接处，所涂覆的涂层具有优良的导通性是一个关键性指标；传统方法制备的涂层厚达几十微米，电阻很大，不能应用于电子产品的连接部位。
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. 一种环氧纳米涂层，其特征在于，将基材暴露于具有式(I)所示结构的单体蒸汽中，通过等离子体放电在基材表面发生化学反应而形成保护涂层：
    Figure PCTCN2019079114-appb-100001
    其中，R 1、R 2、R 3为独立地选自氢、烷基、芳基、卤素、卤代烷基或羟基；X为氢或卤素，m为0-8整数，n为1-15的整数。
  2. 根据权利要求1所述的一种环氧纳米涂层，其特征在于，R 1、R 2、R 3独立地选自氢、烷基、卤素或卤代烷基。
  3. 根据权利要求2所述的一种环氧纳米涂层，其特征在于，所述卤素为氟，所述卤代烷基为碳数在1-10的直链或含有支链的全氟烷基。
  4. 根据权利要求1所述的一种环氧纳米涂层，其特征在于，所述X为氟，m为0、1、2或3，n为1-8的整数。
  5. 根据权利要求1所述的一种环氧纳米涂层，其特征在于，所述基材为金属、光学仪器、衣服织物、电子器件或医疗器械。
  6. 权利要求1-5任一项所述的一种环氧纳米涂层的制备方法，包括以下步骤：
    (1)将基材置于等离子体室的反应腔体内，将反应腔体内的真空度抽到0.1-1000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。
  7. 如权利要求6所述的环氧纳米涂层的制备方法，其特征在于，所述单体是经过减压汽化后引入反应腔体的。
  8. 如权利要求6所述的环氧纳米涂层的制备方法，其特征在于，步骤(2)所述的等离子体源气体是氦气、氩气、氮气、氢气中的一种或者若干种的混合物。
  9. 如权利要求6所述的环氧纳米涂层的制备方法，其特征在于，所述等离子体室的容积为1L-2000L，所述等离子体源气体流量为1-1000sccm，通入单体蒸汽的流量为1-2000μL/min。
  10. 如权利要求6所述的环氧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. 如权利要求10所述的环氧纳米涂层的制备方法，其特征在于，所述预处理等离子体放电功率为1-1000W，持续放电时间为1-6000s。
  12. 如权利要求6所述的环氧纳米涂层的制备方法，其特征在于，所述步骤(2)中，沉积用等离子体放电的功率为2-500W，持续放电时间为600-18000s。
  13. 如权利要求6或10所述的环氧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. 如权利要求6或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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