WO2015139385A1 - 汽车电气电子设备用持续单向透湿的涂层膜及其制造方法 - Google Patents

汽车电气电子设备用持续单向透湿的涂层膜及其制造方法 Download PDF

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WO2015139385A1
WO2015139385A1 PCT/CN2014/081376 CN2014081376W WO2015139385A1 WO 2015139385 A1 WO2015139385 A1 WO 2015139385A1 CN 2014081376 W CN2014081376 W CN 2014081376W WO 2015139385 A1 WO2015139385 A1 WO 2015139385A1
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coating
manufacturing
coating film
expanded polytetrafluoroethylene
film
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PCT/CN2014/081376
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English (en)
French (fr)
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张云
丁荣华
昌建忠
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常州市泛亚微透科技有限公司
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Publication of WO2015139385A1 publication Critical patent/WO2015139385A1/zh

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

Definitions

  • the present invention relates to the field of coating films, and more particularly to a continuous unidirectional moisture permeable coating film for automotive electrical and electronic equipment and manufacturing thereof method. Background technique
  • European Union car headlights, venting holes, fog, decondensation theory There is a sponge inside the dust, and the air inside the lamp can be greatly increased with the change of the temperature inside the lamp, so that the fog in the lamp can be quickly condensed. Dew, the light pipe of the bent pipe is used for a short time after the dust and electrical components in the casing are rusted. Gore's theory of fog-to-condensation in the United States: The lamp is ventilated through the inside of the lamp and the outside of the lamp to establish a pressure balance. The water vapor in the lamp is discharged outside the lamp as the temperature inside the lamp rises. A larger gas permeable film patch method achieves fogging and de-condensation.
  • Nitto Denko Nito's theory of fog-to-condensation The headlights form air convection through the venting holes in the upper and lower positions of the lamp. The water vapor in the lamp rises out from the venting hole in the upper position with the temperature inside the lamp. The venting holes constantly replenish the air outside the lamp. Therefore, the phenomenon that the scattering of water by the water is blurred is unclear.
  • the theory uses a large number of gas permeable plugs, which cannot solve the condensation problem in the lower air temperature region of the casing.
  • SUMMARY OF THE INVENTION The technical problem to be solved by the present invention is to provide a continuous unidirectional moisture permeable coating film for a vehicle electrical and electronic device and a manufacturing method thereof, which can ensure the occurrence of no fog condensation in the casing of an automobile electrical and electronic device.
  • Making electrical performance unaffected by the humid air environment, within the housing of automotive electrical and electronic equipment The surface of the mirror or smooth electronic components will not be foggy, which makes the performance of automotive electrical and electronic equipment play out. It completely overturns the traditional methods of adjusting the humidity control in the housing in Europe and America, and can block the infiltration of dust.
  • one technical solution adopted by the present invention is to provide a continuous unidirectional moisture permeable coating film for automotive electrical and electronic equipment, comprising: an expanded polytetrafluoroethylene microporous film and a hydrophilic group.
  • the coating of the group, the surface of the expanded polytetrafluoroethylene microporous film is coated with a coating containing a hydrophilic group.
  • the thickness of the hydrophilic group-containing coating is
  • Another technical solution for the present invention is to provide a method for manufacturing a continuous unidirectional moisture permeable coating film for automotive electrical and electronic equipment, comprising the following steps:
  • a coating agent containing a hydrophilic group a mixture of a polyaminophthalic acid ester, a dimethyl hydrazide amide solvent, a hydrophilic group solvent, and a SiO 2 fine powder is uniformly emulsified and stirred to form a hydrophilic group.
  • the expanded polytetrafluoroethylene microporous film is manufactured by mixing a polytetrafluoroethylene dispersion resin and a liquid auxiliary agent in proportion, and keeping the temperature at 30 ° C to 35 ° C.
  • the column blank is sliced by calendering, heated at 90 ⁇ 110 °C to remove the extrusion agent, and uniaxially stretched at 190 ⁇ 210 °C, at 190 ⁇ 210 °C Biaxial stretching, sintering at 330 ⁇ 350 °C for 15 ⁇ 20min heat setting Type, cooling, winding.
  • the mass ratio of the polyaminophthalic acid ester, the dimercaptophthalamide solvent, the hydrophilic group solvent, and the SiO 2 fine powder is 5:12:1:1.
  • the coating film is manufactured: pre-coating preparation, a coating agent containing a hydrophilic group is added in a spot roll coater, and the thickness of the coating is adjusted to 0.05 to 0.1 mm.
  • the expanded polytetrafluoroethylene microporous film is unwound and contacted with the spot roller.
  • the lower process roller heats and dries the coating film at 80 ° C ⁇ 100 ° C while volatilizing to remove the dimercapto amide solvent and solvent. Recycling, winding, storage at 25 ⁇ 35 °C for 24h, curing, packaging.
  • the viscosity index of the coating agent containing a hydrophilic group is 33
  • the hydrophilic group solvent is a solvent containing a -OH, -NHCOO- or -COOH group, and the particle size of the SiO 2 powder is ⁇ . ⁇ ! ⁇ 12 ⁇ .
  • the liquid squeezing agent is aviation kerosene.
  • the mass ratio of the polytetrafluoroethylene dispersion resin to the liquid extrusion agent is 4-6:1.
  • the invention has the beneficial effects that the invention can ensure the occurrence of no fog condensation in the casing of the automobile electrical and electronic equipment, so that the electrical performance is not affected by the humid air environment, and the humidity in the casing of the automobile electrical and electronic equipment is greatly reduced. Therefore, the conditions of condensation are not provided, so that the air in the casing is dried, and the surface of the mirror or the smooth electronic component in the casing of the automobile electrical and electronic equipment is not foggy, so that the performance of the automobile electrical and electronic equipment can be exerted. It completely overturns the traditional methods of adjusting the humidity control in the casing in Europe and the United States, and can block the infiltration of dust, so that the interior of the car electrical and electronic equipment reaches a dust-free level.
  • FIG. 1 is a continuous one-way moisture permeable coating for automotive electrical and electronic equipment of the present invention.
  • an embodiment of the present invention includes: a continuous unidirectional moisture permeable coating film for an automotive electrical and electronic device, comprising: an expanded polytetrafluoroethylene microporous film 1 and a coating layer containing a hydrophilic group 2
  • the surface of the expanded polytetrafluoroethylene microporous film 1 is coated with a coating 2 containing a hydrophilic group.
  • the hydrophilic group-containing coating layer 2 has a thickness of 0.05 to 0.1 mm.
  • the expanded polytetrafluoroethylene microporous film 1 is prepared by mixing a polytetrafluoroethylene dispersion resin and a liquid auxiliary agent in a ratio of 30 ° C to 35 ° C, and pre-pressing the column.
  • the blank body is formed into a thin sheet by calendering, heated by 90 ⁇ 110 °C to remove the auxiliary agent, uniaxially stretched at 190 ⁇ 210 °C, and stretched at 190 ⁇ 210 °C in two directions. Sintered at ⁇ 350 °C for 15 ⁇ 20min heat setting, cooling, winding.
  • the mass ratio of the polyaminophthalic acid ester, the dimercaptophthalamide solvent, the hydrophilic group solvent and the SiO 2 fine powder is 5:12:1:1.
  • the coating film is manufactured: pre-coating preparation, a coating agent containing a hydrophilic group is added in a spot roll coater, and the thickness of the coating layer is adjusted to 0.05 to 0.1 mm, expanded polytetrafluoroethylene.
  • the microporous film is unwound and contacted with the spot roller.
  • the lower process roller heats and dries the coating film at 80 ° C ⁇ 100 ° C while volatilizing to remove the dimercapto amide solvent and solvent recovery, winding, in Store at 25 ⁇ 35°C for 24h, cure and package.
  • the viscosity index of the coating agent containing a hydrophilic group is 28 ⁇ 33 Pa.s.
  • the hydrophilic group solvent is a solvent containing a -OH, -NHCOO- or -COOH group, and the particle size of the SiO 2 powder is ⁇ . ⁇ ! ⁇ 12 ⁇ .
  • the liquid squeezing agent is aviation kerosene.
  • the mass ratio of the polytetrafluoroethylene dispersion resin to the liquid extrusion agent is 4-6:1.
  • Expanded polytetrafluoroethylene microporous film material referred to as "ePTFE film”, “ePTFE” is the abbreviation of expanded polytetrafluoroethylene (expanded polytetrafluorethylene); expanded polytetrafluoroethylene microporous film is a special function
  • the high value-added polymer new material film is made by biaxial stretching by a special process.
  • the microfiber of the film constitutes a microporous pore having a pore size of 0.1 ⁇ to 18 ⁇ which is transparent inside and outside, and is a true gas permeable membrane.
  • the surface of the membrane can reach several billion micropores per square inch, and the diameter of each micropore is smaller than the minimum value of light mist droplets (20 ⁇ 100 ⁇ ), which is much larger than the diameter of water vapor molecules (0.0003 ⁇ 0.0004 ⁇ ). Water vapor passes through and the water droplets cannot pass due to the large surface tension.
  • This microporous structure can achieve excellent waterproof and moisture permeable function.
  • the hole is extremely small and the longitudinal non-standard curved arrangement is used, it is used in the protection of automotive electrical and electronic equipment.
  • Polyaminophthalate in a polyaminophthalate emulsion coating contains a polymer compound of -NHCOO- unit in its molecular structure. Its main principle is to introduce it on the polymer chain. An appropriate amount of hydrophilic groups spontaneously disperse to form an emulsion under certain conditions.
  • PU macromolecules contain a large number of polar groups, and the intermolecular force is strong, resulting in excellent film formation and formation of toughness and durability on the fabric.
  • the film also has a certain moisture permeability.
  • the polar groups or hydrophilic groups in the PU such as -OH, -NHCOO-, -COOH, and silicone micro-powders, and the interaction between the molecules, so that the water vapor molecules along The ladder migrates from the high humidity side to the low humidity side; in theory, the polymer chain mainly has hydrophilic groups, and as long as the hydrophilic group content and arrangement are appropriate, they can interact with water molecules. Hydrogen bonds and other intermolecular forces, after adsorbing moisture on the high-humidity side, are desorbed by the hydrophilic groups on the polymer chain to the low-humidity side.
  • moisture permeability is essentially a process of "adsorption-diffusion-transfer-desorption".
  • the continuous unidirectional moisture permeable coating film for automotive electrical and electronic equipment is coated on the one side of the expanded polytetrafluoroethylene microporous film with a hydrophilic group polyurethane urethane emulsion coating, which is 80 ° C -100 The coating is dried at a temperature of °C.
  • the coating After storage for 24 hours at room temperature, the coating is cured on the surface of the expanded polytetrafluoroethylene microporous film to form a dense and durable coating containing hydrophilic groups, and The action of water molecules, by means of hydrogen bonding and other intermolecular forces, adsorbs water on the high-humidity side, and then desorbs through the hydrophilic group on the polymer chain to the low-humidity side.
  • the moisture permeability is essentially a "adsorption" of water vapor molecules on the surface of the hydrophilic group polyaminophthalate coating - the water molecules "diffuse" to the outside within the hydrophilic group polyaminophthalate coating - the water molecules are in pro Water-based polyaminophthalate coating and "expanded" interface on the interface of expanded polytetrafluoroethylene microporous film - water molecules enter the micropores of the expanded polytetrafluoroethylene microporous film to discharge moisture to the external environment the process of.
  • a continuous one-way moisture permeable coating film for automotive electrical and electronic equipment comprising: an expanded polytetrafluoroethylene microporous film 1 and a coating layer 2 containing a hydrophilic group, said expanded polytetrafluoroethylene micro
  • the surface of the aperture film 1 is coated with a coating 2 containing a hydrophilic group, and the manufacturing method thereof specifically comprises the following steps:
  • a coating agent containing a hydrophilic group a polyaminophthalic acid ester, a dimethyl hydrazide amide solvent, a solvent containing a hydrophilic group, and a particle size of ⁇ . ⁇ !
  • the mixture of ⁇ 12 ⁇ SiO 2 powder is uniformly emulsified and stirred to form a coating agent having a hydrophilic group, the polyaminophthalic acid ester, the dimercapto amide amide solvent, the hydrophilic group solvent and the particle size of ⁇ . ⁇ !
  • the mass ratio of the SiO2 2 micropowder of 12 ⁇ is 5:12:1:1, the viscosity index of the coating agent containing the hydrophilic group is 28-33 Pa.s, and the nonvolatile matter is 25-35%;
  • (3) Manufacture of coating film Preparation before coating, coating agent containing hydrophilic group is added in a point roll coater to adjust the thickness of the coating to 0.05 ⁇ 0.1mm, expanded polytetrafluoroethylene microporous film Unwinding, moving linear speed is 8 ⁇ 10m/min, and contact with the spot roller. The next process roller heats the coating film at 80 °C ⁇ 100 °C while volatilizing to remove the dimercapto amide solvent and solvent. Recycling, winding, storage at 25 ⁇ 35 °C for 24h, curing, packaging.
  • the test results show that the moisture permeability of water vapor from the side of the coating to the expanded polytetrafluoroethylene microporous film side is greater than that of water vapor.
  • the amount of moisture permeation in the lateral casing of the ethylene microporous film is about 30%.
  • the coating film is applied to the casing of the automobile electrical and electronic equipment.
  • the side of the coating is directed into the casing of the automotive electrical and electronic equipment, and the expanded polytetrafluoroethylene film of the coating film faces the outside atmosphere; thus the water vapor in the casing of the automotive electrical and electronic equipment is continuously discharged, which is manifested by the inside of the casing.
  • the external environment continuously discharges the characteristics of water vapor.
  • the specific advantages of the continuous one-way moisture permeable coating film for automotive electrical and electronic equipment of the present invention include: 1) The invention can ensure the occurrence of no fog condensation in the casing of the automobile electrical and electronic equipment, so that the electrical performance is protected from humid air. The influence of the environment, the humidity in the casing of the automobile electrical and electronic equipment is greatly reduced, and thus the conditions of condensation are not provided, so that the air in the casing is dry, and the surface of the mirror or the smooth electronic component in the casing of the automobile electrical and electronic equipment does not have The phenomenon of fog water is generated, making the electric motor of the car The performance of the sub-devices has been exerted, completely overturning the traditional methods of adjusting the humidity control in the housing in Europe and America;
  • the invention can block the infiltration of dust, so that the dust-proof level of the pollution-free dust is achieved in the casing of the automobile electrical and electronic equipment;
  • the invention fully satisfies the reliable performance of automobile electrical and electronic equipment and other small precision electronic equipment (mobile phone, navigation terminal, microcomputer, etc.), and can meet the waterproof, dustproof, oil proof, moisture permeable, anti-oxidation solution corrosion, etc. Comprehensive requirements for protection;
  • the invention can further reduce the design and manufacturing cost of the automobile electrical and electronic equipment in eliminating the influence of water vapor on its performance, so that the shape of the casing is simplified;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

一种汽车电气电子设备用持续单向透湿的涂层膜及其制造方法，该涂层膜包括：膨体聚四氟乙烯微孔薄膜（1）和含有亲水基团的涂层（2），膨体聚四氟乙烯微孔薄膜（1）表面涂覆有含有亲水基团的涂层（2）。其制造方法：膨体聚四氟乙烯微孔薄膜的制造；含有亲水基团的涂层剂的制备；涂层膜的制造：涂前准备，含有亲水基团的涂层剂加入滚涂机，涂层厚度调节，膨体聚四氟乙烯微孔薄膜放卷，与滚筒接触涂胶，下道工序滚筒加热烘干涂层膜，收卷，存放熟成固化，包装。该涂层膜能够确保汽车电气电子设备的壳体内无结雾凝露现象的产生，使得电气性能不受潮湿空气环境的影响，又能够阻挡灰尘的渗入，使得汽车电气电子设备的壳体内达到无污染的尘密级。

Description

汽车电气电子设备用持续单向透湿的涂层膜及其制造方法 技术领域 本发明涉及涂层膜领域， 特别是涉及一种汽车电气电子设备用持续单向透 湿的涂层膜及其制造方法。 背景技术
欧盟汽车车灯的弯管透气孔散雾去凝露理论： 内有海绵防尘， 也接灯内空 气随灯内温度的变化可以大出大进， 从而较快的实现灯内散雾去凝露， 弯管透 气的车灯使用不久后壳体内积尘和电气元件锈蚀。 美国 Gore公司的散雾去凝露理论： 车灯是通过灯内与灯外透气对流， 建立 一种气压平衡， 灯内水蒸气随灯内的温度升高而排出灯外， 壳体上使用面积大 一点的透气膜贴片方法实现散雾去凝露。 从而减少水蒸气对灯光的散射模糊不 清的现象发生， 车灯不工作时外部环境潮湿空气会进入壳体内。 该理论使用的 透气膜贴片数量多， 没法解决壳体内空气温度较低区域的凝露问题。 日东电工 nito公司的散雾去凝露理论： 车灯是通过灯具的上下位置透气孔 形成空气对流， 灯内水蒸气随灯内的温度升高从上位置的透气孔排出灯外， 下 位置的透气孔不断补充灯外空气。 从而减少水蒸气对灯光的散射模糊不清的现 象发生， 该理论使用的透气栓数量多， 没法解决壳体内空气温度较低区域的凝 露问题。 发明内容 本发明主要解决的技术问题是提供一种汽车电气电子设备用持续单向透湿 的涂层膜及其制造方法， 能够确保汽车电气电子设备的壳体内无结雾凝露现象 的产生， 使得电气性能不受潮湿空气环境的影响， 汽车电气电子设备的壳体内 的镜面上或光滑的电子元件表面就不会有雾水现象产生， 使得汽车电气电子设 备的性能得以发挥出来， 彻底颠覆了欧美日对壳体内湿度控制调节的传统方法， 又能够阻挡灰尘的渗入， 使得汽车电气电子设备的壳体内达到无污染的尘密级。 为解决上述技术问题， 本发明釆用的一个技术方案是： 提供一种汽车电气 电子设备用持续单向透湿的涂层膜， 包括： 膨体聚四氟乙烯微孔薄膜和含有亲 水基团的涂层， 所述的膨体聚四氟乙烯微孔薄膜表面涂覆有含有亲水基团的涂 层。
在本发明一个较佳实施例中， 所述的含有亲水基团的涂层的厚度为
0.05~0.1mm。 为解决上述技术问题， 本发明釆用的另一个技术方案是： 提供一种汽车电 气电子设备用持续单向透湿的涂层膜的制造方法， 包括以下步骤：
( 1 )膨体聚四氟乙烯微孔薄膜的制造： 将聚四氟乙烯分散树脂与液体助挤 剂按比例混合， 保温熟成， 予压成柱体毛坯， 将柱体毛坯制成薄片， 经加热脱 去助挤剂， 单向拉伸， 双向拉伸， 热定型， 冷却， 收卷；
( 2 )含有亲水基团的涂层剂的制备： 将聚氨基曱酸酯、二曱基曱酰胺溶剂、 亲水基团溶剂和 Si02微粉的混合物搅拌乳化均匀， 形成有亲水基团的涂层剂；
( 3 )涂层膜的制造： 涂前准备， 含有亲水基团的涂层剂加入滚涂机， 涂层 厚度调节， 膨体聚四氟乙烯微孔薄膜放卷， 与滚筒接触涂胶， 下道工序滚筒加 热烘干涂层膜， 收卷， 存放熟成固化， 包装。 在本发明一个较佳实施例中， 所述的膨体聚四氟乙烯微孔薄膜的制造： 将 聚四氟乙烯分散树脂与液体助挤剂按比例混合，在 30°C~35°C保温熟成， 予压成 柱体毛坯， 通过压延法将柱体毛坯制成薄片， 经 90~110°C加热脱去助挤剂， 在 190~210°C单向拉伸， 在 190~210°C双向拉伸， 在 330~350°C烧结 15~20min热定 型， 冷却， 收卷。
在本发明一个较佳实施例中， 所述的聚氨基曱酸酯、 二曱基曱酰胺溶剂、 亲水基团溶剂和 Si02微粉的质量比为 5: 12: 1 : 1。
在本发明一个较佳实施例中， 所述的涂层膜的制造： 涂前准备， 含有亲水 基团的涂层剂在点式滚涂机加料， 将涂层厚度调节到 0.05~0.1mm, 膨体聚四氟 乙烯微孔薄膜放卷， 与点式滚筒接触涂胶， 下道工序滚筒在 80°C~100°C加热烘 干涂层膜同时挥发去除二曱基曱酰胺溶剂及溶剂回收处理， 收卷，在 25~35 °C存 放 24h熟成固化， 包装。
在本发明一个较佳实施例中， 所述的含有亲水基团的涂层剂的粘度指数 33
Pa. s„
在本发明一个较佳实施例中， 所述的亲水基团溶剂为含有 -OH、 -NHCOO- 或 -COOH基团的溶剂， 所述的 Si02微粉的粒径为 Ο.ΐμπ！〜 12μπι。
在本发明一个较佳实施例中， 所述的液体助挤剂为航空煤油。
在本发明一个较佳实施例中， 所述的聚四氟乙烯分散树脂与液体助挤剂的 质量比为 4~6： 1。
本发明的有益效果是： 本发明能够确保汽车电气电子设备的壳体内无结雾 凝露现象的产生， 使得电气性能不受潮湿空气环境的影响， 在汽车电气电子设 备的壳体内的湿度大大降低因而不具备凝露的条件， 使得壳体内空气干燥， 汽 车电气电子设备的壳体内的镜面上或光滑的电子元件表面就不会有雾水现象产 生， 使得汽车电气电子设备的性能得以发挥出来， 彻底颠覆了欧美日对壳体内 湿度控制调节的传统方法， 又能够阻挡灰尘的渗入， 使得汽车电气电子设备的 壳体内达到无污染的尘密级。 附图说明
为了更清楚地说明本发明实施例中的技术方案， 下面将对实施例描述中所 需要使用的附图作简单地介绍， 显而易见地， 下面描述中的附图仅仅是本发明 的一些实施例， 对于本领域普通技术人员来讲， 在不付出创造性劳动的前提下， 还可以根据这些附图获得其它的附图， 其中： 图 1 是本发明汽车电气电子设备用持续单向透湿的涂层膜一较佳实施例的 结构示意图； 附图中各部件的标记如下： 1、 膨体聚四氟乙烯微孔薄膜， 2、 含有亲水基 团的涂层。 具体实施方式
下面将对本发明实施例中的技术方案进行清楚、 完整地描述， 显然， 所描 述的实施例仅是本发明的一部分实施例， 而不是全部的实施例。 基于本发明中 的实施例， 本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其 它实施例， 都属于本发明保护的范围。 请参阅图 1 , 本发明实施例包括： 一种汽车电气电子设备用持续单向透湿的涂层膜， 包括： 膨体聚四氟乙烯 微孔薄膜 1和含有亲水基团的涂层 2,所述的膨体聚四氟乙烯微孔薄膜 1表面涂 覆有含有亲水基团的涂层 2。 优选的， 所述的含有亲水基团的涂层 2的厚度为 0.05~0.1mm。 汽车电气电子设备用持续单向透湿的涂层膜的制造方法， 包括以下步骤：
( 1 )膨体聚四氟乙烯微孔薄膜 1的制造： 将聚四氟乙烯分散树脂与液体助 挤剂按比例混合， 保温熟成， 予压成柱体毛坯， 将柱体毛坯制成薄片， 经加热 脱去助挤剂， 单向拉伸， 双向拉伸， 热定型， 冷却， 收卷； ( 2 )含有亲水基团的涂层剂的制备： 将聚氨基曱酸酯、二曱基曱酰胺溶剂、 亲水基团溶剂和 Si02微粉的混合物搅拌乳化均匀， 形成有亲水基团的涂层剂；
( 3 )涂层膜的制造： 涂前准备， 含有亲水基团的涂层剂加入滚涂机， 涂层 厚度调节， 膨体聚四氟乙烯微孔薄膜 1放卷， 与滚筒接触涂胶， 下道工序滚筒加 热烘干涂层膜， 收卷， 存放熟成固化， 包装。
优选的， 所述的膨体聚四氟乙烯微孔薄膜 1 的制造： 将聚四氟乙烯分散树 脂与液体助挤剂按比例混合， 在 30°C~35°C保温熟成， 予压成柱体毛坯， 通过压 延法将柱体毛坯制成薄片， 经 90~110°C加热脱去助挤剂， 在 190~210°C单向拉 伸， 在 190~210°C双向拉伸, 在 330~350°C烧结 15~20min热定型, 冷却， 收卷。
优选的， 所述的聚氨基曱酸酯、 二曱基曱酰胺溶剂、 亲水基团溶剂和 Si02 微粉的质量比为 5: 12: 1 : 1。
优选的， 所述的涂层膜的制造： 涂前准备， 含有亲水基团的涂层剂在点式 滚涂机加料， 将涂层厚度调节到 0.05~0.1mm, 膨体聚四氟乙烯微孔薄膜放卷， 与点式滚筒接触涂胶， 下道工序滚筒在 80°C~100°C加热烘干涂层膜同时挥发去 除二曱基曱酰胺溶剂及溶剂回收处理， 收卷， 在 25~35°C存放 24h熟成固化， 包 装。
优选的， 所述的含有亲水基团的涂层剂的粘度指数 28~33 Pa.s„
优选的，所述的亲水基团溶剂为含有 -OH、 -NHCOO-或 -COOH基团的溶剂， 所述的 Si02微粉的粒径为 Ο.ΐμπ！〜 12μπι。
优选的， 所述的液体助挤剂为航空煤油。
优选的， 所述的聚四氟乙烯分散树脂与液体助挤剂的质量比为 4~6： 1。 膨体聚四氟乙烯微孔薄膜材料简称 "ePTFE膜"， "ePTFE" 是膨体聚四氟乙 烯英文单词 (expanded polytetrafluorethylene)的缩写； 膨体聚四氟乙烯微孔薄膜是 一种具有特殊功能高附加值的高分子新材料薄膜， 是经特殊工艺经双向拉伸制 成的， 该薄膜的微纤维构成了里外通透的 0.1μπι~18μπι孔径的微孔， 是真正意义 的透气膜。 膜表面每平方英寸能达到几十亿个微孔， 每个微孔直径小于轻雾水 珠的最小值（ 20μπι~100μπι ), 而远大于水蒸气分子直径（ 0.0003μπι~0.0004μπι ), 可以使水蒸气通过而水滴因表面涨力大不能通过， 利用这种微孔结构可达到优 秀的防水透湿功能； 另外因为该孔极度细小和纵向不规格的弯曲排列， 用在汽 车电气电子设备防护方面， 虽能使得汽车电气电子设备内的空气通过此膜对流 调节压力平衡， 达到无污染的尘密， 但是当汽车停开时没法阻止或减少环境中 的水蒸气进入壳体内， 滞留在壳体内的水蒸气湿度过高将严重影响汽车电气电 子设备的性能的发挥。
含有亲水基团的涂层透湿原理： 聚氨基曱酸酯乳液涂层中的聚氨基曱酸酯 分子结构中含有 -NHCOO-单元的高分子化合物， 其主要原理是在聚合物链上引 入适量的亲水基团， 在一定条件下自发分散形成乳液， PU大分子中含有大量的 极性基团， 分子间力很强， 致使其具有优良成膜性， 能够在织物上形成坚韧而 耐久的薄膜， 它还具有一定透湿性。 其原因是： 一方面 PU中的极性基团或亲水 基团， 如 -OH、 -NHCOO-、 -COOH和有机硅微粉等的氢键和分子间的作用力， 使水蒸气分子沿着阶梯从高湿度一侧迁移到低湿度一侧； 从理论上讲， 高分子 链上主要有亲水基团， 且只要亲水基团含量和排列合适， 则它们便可以和水分 子作用， 借助氢键和其它分子间作用力， 在高湿度一侧吸附水份后， 通过高分 子链上亲水基团传递到低湿度一侧解吸。 因此， 透湿实质上是一个 "吸附-扩散- 转移-解吸" 的过程。 汽车电气电子设备用持续单向透湿的涂层膜是在膨体聚四氟乙烯微孔薄膜 的一侧表面涂覆含有亲水基团聚氨基曱酸酯乳液涂层， 经 80 °C -100 °C温度烘干 涂层， 室温存放 24h后， 涂层就固化在膨体聚四氟乙烯微孔薄膜面上， 形成一层 致密的耐久的涂层， 该涂层含有亲水基团， 和水分子作用， 借助氢键和其它分 子间作用力， 在高湿度一侧吸附水份后， 通过高分子链上亲水基团传递到低湿 度一侧解吸。 因此， 透湿实质上是一个在亲水基团聚氨基曱酸酯涂层表面 "吸 附" 水蒸汽分子 -水分子在亲水基团聚氨基曱酸酯涂层内向外侧 "扩散" -水分子 在亲水基团聚氨基曱酸酯涂层与膨体聚四氟乙烯微孔薄膜的结合界面面上 "解 吸" -水分子进入膨体聚四氟乙烯微孔薄膜密布的微孔向外部环境排出湿气的过 程。
实施例：
一种汽车电气电子设备用持续单向透湿的涂层膜， 包括： 膨体聚四氟乙烯 微孔薄膜 1和含有亲水基团的涂层 2,所述的膨体聚四氟乙烯微孔薄膜 1表面涂 覆有含有亲水基团的涂层 2, 其制造方法具体包括以下步骤：
( 1 )膨体聚四氟乙烯微孔薄膜的制造： 将聚四氟乙烯分散树脂与航空煤油 溶剂按 5: 1的质量比混合， 在 30°C~35 °C保温熟成， 予压成柱体毛坯， 通过压 延法将柱体毛坯制成薄片， 经 90~110°C加热脱去助挤剂， 在 190~210°C单向拉 伸， 在 190 210 °C双向拉伸， 在 330~350°C烧结 15~20min热定型, 冷却， 收卷；
( 2 )含有亲水基团的涂层剂的制备： 将聚氨基曱酸酯、二曱基曱酰胺溶剂、 含有亲水基团的溶剂和粒径为 Ο.ΐμπ！〜 12μπι的 Si02微粉的混合物搅拌乳化均匀， 形成有亲水基团的涂层剂， 所述的聚氨基曱酸酯、 二曱基曱酰胺溶剂、 亲水基 团溶剂和粒径为 Ο.ΐμπ！ 〜 12μπι的 Si02微粉的质量比为 5: 12: 1 : 1 , 所述的含 有亲水基团的涂层剂的粘度指数 28-33 Pa.s, 不挥发物达 25~35%； ( 3 )涂层膜的制造： 涂前准备，含有亲水基团的涂层剂在点式滚涂机加料， 将涂层厚度调节到 0.05~0.1mm, 膨体聚四氟乙烯微孔薄膜放卷， 移动线速度为 8~10m/min, 与点式滚筒接触涂胶， 下道工序滚筒在 80°C~100 °C加热烘干涂层 膜同时挥发去除二曱基曱酰胺溶剂及溶剂回收处理， 收卷， 在 25~35 °C存放 24h 熟成固化， 包装。
经过对汽车电气电子设备用持续单向透湿的涂层膜的大量试验， 试验结果 表明水蒸气从涂层侧向膨体聚四氟乙烯微孔薄膜侧排出的透湿量大于水蒸气从 膨体聚四氟乙烯微孔薄膜侧向涂层侧排出的透湿量， 水蒸汽透湿方向的不同导 致透湿量的不同， 从涂层侧向外透湿的量比从膨体聚四氟乙烯微孔薄膜侧向壳 体内透湿量大 30%左右， 利用此两个方向的透湿量的巨大差异， 将此涂层膜应 用在汽车电气电子设备的壳体上， 此涂层膜的涂层侧面向汽车电气电子设备的 壳体内， 此涂层膜的膨体聚四氟乙烯膜朝向外部大气； 这样汽车电气电子设备 的壳体内的水蒸气源源不断的排出， 表现出由壳体内向外部环境单向持续排出 水蒸汽的特性， 当汽车电气电子设备工作时， 壳体内的温度较高时， 涂层的亲 水高分子链段越活跃， 吸附、 扩散和解吸排出水蒸气分子的速度越快， 在汽车 电气电子设备的壳体内的湿度大大降低因而不具备凝露的条件， 使得壳体内空 气干燥， 汽车电气电子设备的壳体内的镜面上或光滑的电子元件表面就不会有 雾水现象产生， 使得汽车电气电子设备的性能得以发挥出来。
本发明汽车电气电子设备用持续单向透湿的涂层膜的具体优点包括： 1 )本发明能够确保汽车电气电子设备的壳体内无结雾凝露现象的产生， 使 得电气性能不受潮湿空气环境的影响， 在汽车电气电子设备的壳体内的湿度大 大降低因而不具备凝露的条件， 使得壳体内空气干燥， 汽车电气电子设备的壳 体内的镜面上或光滑的电子元件表面就不会有雾水现象产生， 使得汽车电气电 子设备的性能得以发挥出来， 彻底颠覆了欧美日对壳体内湿度控制调节的传统 方法；
2 )本发明既能阻挡灰尘的渗入， 使得汽车电气电子设备的壳体内达到无污 染的尘密级；
3 )本发明完全满足了汽车电气电子设备和其它小型的精密电子设备（手机、 导航终端、 微型电脑等）性能可靠发挥， 能够满足防水、 防尘、 防油、 透湿、 抗氧化溶液腐蚀等防护综合性要求；
4 )本发明能够进一步的降低汽车电气电子设备在消除水蒸气对其性能影响 的设计制造成本， 使得壳体造型简洁化；
5 )本发明不透气体（允许水蒸气分子排出）及耐渗水压力高的特性， 耐水 压已达到 10000mm高度水柱（相对压力 lOOKPa压强） 以上， 能够 4氏挡深坑积 水浸泡或行驶中冲击水的影响， 使得壳体内保持干燥而不会浸水。
以上所述仅为本发明的实施例， 并非因此限制本发明的专利范围， 凡是利 用本发明说明书内容所作的等效结构或等效流程变换， 或直接或间接运用在其 它相关的技术领域， 均同理包括在本发明的专利保护范围内。

Claims

权 利 要 求 书
1、 一种汽车电气电子设备用持续单向透湿的涂层膜， 其特征在于， 包括： 膨体聚四氟乙烯微孔薄膜和含有亲水基团的涂层， 所述的膨体聚四氟乙烯微孔 薄膜表面涂覆有含有亲水基团的涂层。
2、 根据权利要求 1所述的汽车电气电子设备用持续单向透湿的涂层膜， 其 特征在于， 所述的含有亲水基团的涂层的厚度为 0.05~0.1mm。
3、根据权利要求 1所述的涂层膜的制造方法， 其特征在于， 包括以下步骤：
( 1 )膨体聚四氟乙烯微孔薄膜的制造： 将聚四氟乙烯分散树脂与液体助挤 剂按比例混合， 保温熟成， 予压成柱体毛坯， 将柱体毛坯制成薄片， 经加热脱 去助挤剂， 单向拉伸， 双向拉伸， 热定型， 冷却， 收卷；
( 2 )含有亲水基团的涂层剂的制备： 将聚氨基曱酸酯、二曱基曱酰胺溶剂、 亲水基团溶剂和 Si02微粉的混合物搅拌乳化均匀， 形成有亲水基团的涂层剂；
( 3 )涂层膜的制造： 涂前准备， 含有亲水基团的涂层剂加入滚涂机， 涂层 厚度调节， 膨体聚四氟乙烯微孔薄膜放卷， 与滚筒接触涂胶， 下道工序滚筒加 热烘干涂层膜， 收卷， 存放熟成固化， 包装。
4、 根据权利要求 3所述的制造方法， 其特征在于， 所述的膨体聚四氟乙烯 微孔薄膜的制造： 将聚四氟乙烯分散树脂与液体助挤剂按比例混合，在 30°C~35 °C保温熟成， 予压成柱体毛坯， 通过压延法将柱体毛坯制成薄片， 经 90〜： 110°C 加热脱去助挤剂， 在 190~210°C单向拉伸， 在 190~210°C双向拉伸， 在 330 350 °C烧结 15~20min热定型， 冷却， 收卷。
5、 根据权利要求 3所述的制造方法， 其特征在于， 所述的聚氨基曱酸酯、 二曱基曱酰胺溶剂、 亲水基团溶剂和 Si02微粉的质量比为 5: 12: 1 : 1。
6、 根据权利要求 3所述的制造方法， 其特征在于， 所述的涂层膜的制造： 涂前准备， 含有亲水基团的涂层剂在点式滚涂机加料， 将涂层厚度调节到 0.05-0. lmm, 膨体聚四氟乙烯微孔薄膜放卷， 移动线速度为 8~10m/min, 与点 式滚筒接触涂胶， 下道工序滚筒在 80°C~100°C加热烘干涂层膜同时挥发去除二 曱基曱酰胺溶剂及溶剂回收处理， 收卷， 在 25~35 °C存放 24h熟成固化， 包装。
7、 根据权利要求 3所述的制造方法， 其特征在于， 所述的含有亲水基团的 涂层剂的粘度指数 28~33 Pa.s„
8、 根据权利要求 3所述的制造方法， 其特征在于， 所述的亲水基团溶剂为 含有 -OH、 -NHCOO-或 -COOH基团的溶剂， 所述的 Si02微粉的粒径为 Ο.ΐμπι ~12μπι。
9、 根据权利要求 3所述的制造方法， 其特征在于， 所述的液体助挤剂为航 空煤油。
10、 根据权利要求 3或 4所述的制造方法， 其特征在于， 所述的聚四氟乙 烯分散树脂与液体助挤剂的质量比为 4~6： 1。
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