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CN113337200B - Carbon nano tube antistatic coating and preparation method and application thereof - Google Patents

Carbon nano tube antistatic coating and preparation method and application thereof Download PDF

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CN113337200B
CN113337200B CN202110575932.9A CN202110575932A CN113337200B CN 113337200 B CN113337200 B CN 113337200B CN 202110575932 A CN202110575932 A CN 202110575932A CN 113337200 B CN113337200 B CN 113337200B
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carbon nanotube
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CN113337200A (en
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张景春
司家林
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Anhui Fulang Optical Materials Co ltd
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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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

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Abstract

本发明涉及新材料技术领域，特别是涉及一种碳纳米管防静电涂层及其制备方法与应用。本发明通过对烘干后的碳纳米管防静电涂层在相对湿度为60％～100％、温度为35℃～80℃的条件下处理，由于湿度发生改变，体系的极性也发生改变，受此影响，修饰在碳纳米管表面的极性表面活性剂发挥作用，使得进行湿度处理前的涂层中原本因溶剂挥发导致微观相分离而形成的孤立碳纳米管团簇舒展开来，形成相互连接的导电网络，从而提升了烘干后的涂层的导电性能，有效降低了涂层表面的电阻。

Figure 202110575932

The invention relates to the technical field of new materials, in particular to a carbon nanotube antistatic coating and a preparation method and application thereof. In the present invention, the dried carbon nanotube antistatic coating is treated under the conditions of relative humidity of 60% to 100% and temperature of 35°C to 80°C. Due to the change of humidity, the polarity of the system also changes. Affected by this, the polar surfactants modified on the surface of carbon nanotubes play a role, so that the isolated carbon nanotube clusters originally formed by the microscopic phase separation caused by solvent volatilization in the coating before humidity treatment are stretched out and formed. The interconnected conductive network improves the conductivity of the dried coating and effectively reduces the resistance of the coating surface.

Figure 202110575932

Description

Carbon nano tube antistatic coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a carbon nano tube antistatic coating and a preparation method and application thereof.
Background
Due to good processability and electrical insulation performance, the polymer material and the product are widely applied to the fields of 3C electronics, integrated circuits, communication, household appliances, lens windows, precision equipment manufacturing and the like. But the polymer material and the product have higher surface resistivity (more than 10)14Omega/m), static electricity is easy to accumulate in the using process, and negative results such as static dust collection, reduction of the manufacturing yield of electronic products, even fire explosion and the like are generated. The antistatic coating is formed by coating transparent antistatic coating on the surface of a polymer product and then curing the coating at high temperature or UV light, so that the antistatic capability can be endowed.
The carbon nano tube is an excellent conductive material and can be used for preparing antistatic coating. The carbon nanotube antistatic coating is generally formed by dispersing carbon nanotubes in a solution and then mixing the solution with a resin and a solvent. However, in practical application, due to the problem of compatibility between the carbon nanotube dispersion and the resin or the solvent, micro-phase separation is easy to occur during the rapid volatilization of the solvent, and a continuous and uniform conductive network cannot be formed, so that the carbon nanotube film has a high resistance, generally 109～1011Ω/m2And the mass application of the antistatic agent in the antistatic field is limited.
Therefore, the conductivity of the carbon nanotube antistatic coating is often improved in the prior art through the following two research directions: 1. improving the compatibility of the carbon nanotube dispersion liquid with resin or solvent; 2. the amount of carbon nanotubes is increased so that the amount of carbon nanotubes is large enough to form a conductive network even if the solvent is rapidly volatilized. However, the first method often requires the addition of additives, which may not only result in the degradation of other properties, but also require a great deal of effort to adjust the formulation; although the second method can simply and directly improve the conductivity of the coating, the cost is greatly increased due to the increase of the using amount of the carbon nanotubes, and the color of the coating is deepened due to the high using amount of the carbon nanotubes, so that the application of the coating in the aspect of transparent coating is limited.
Disclosure of Invention
Accordingly, there is a need for a low-resistance, high-transparency carbon nanotube antistatic coating, and a preparation method and applications thereof.
In one aspect of the invention, a preparation method of a carbon nanotube antistatic coating is provided, which comprises the following steps:
coating the coating containing the carbon nano tube on the surface of a base material, and drying to obtain a dry coating; carrying out humidity treatment on the dry coating to obtain a treated dry coating, and then carrying out curing treatment;
the coating containing the carbon nano tube comprises a carbon nano tube dispersion liquid, resin and a solvent, wherein a polar surfactant is modified on the surface of the carbon nano tube in the carbon nano tube dispersion liquid; the humidity treatment refers to treating the dry coating under the conditions that the relative humidity is 60-100% and the temperature is 35-80 ℃.
According to the invention, the dried carbon nanotube antistatic coating is treated under the conditions that the relative humidity is 60-100% and the temperature is 35-80 ℃, and the polarity of the system is changed due to the change of the humidity, so that the polar surfactant modified on the surface of the carbon nanotube plays a role, isolated carbon nanotube clusters formed by micro-phase separation caused by solvent volatilization in the coating before the humidity treatment are unfolded to form an interconnected conductive network, thereby improving the conductivity of the dried coating and effectively reducing the resistance of the surface of the coating. Because the construction of the interconnected conductive network is established on the basis of polarity regulation and control, rather than relying on the great increase of the using amount of the carbon nanotube conductive agent in the traditional technology, the scheme can realize lower using amount of the carbon nanotube, and is beneficial to improving the transparency of the coating and reducing the production cost; in addition, the introduction of additives for improving the compatibility of the carbon nanotube dispersion liquid with resin or solvent can be avoided, so that the coating has simpler components and more stable performance.
In one embodiment, the humidity treatment is carried out by using damp-heat gas, and the flow rate of the damp-heat gas is 0.5L/min cm2～10L/min·cm2。
In one embodiment, the humidity treatment time is 10s to 80 s.
In one embodiment, the carbon nanotube dispersion liquid is a single-walled carbon nanotube dispersion liquid, and the content of single-walled carbon nanotubes in the single-walled carbon nanotube dispersion liquid is 0.1 to 5 per thousand.
In one embodiment, the single-walled carbon nanotube has a length of 100nm to 100 μm and a diameter of 0.5nm to 2 nm.
In one embodiment, the curing process is a photo-curing process.
In one embodiment, the coating containing carbon nanotubes comprises the following components in percentage by mass: 1.5 to 3 percent of single-walled carbon nanotube dispersion liquid, 1 to 5 percent of photosensitive acrylic resin, 2 to 7 percent of photosensitive monomer, 0.5 to 1.5 percent of photoinitiator and 87 to 95 percent of solvent.
In one embodiment, the coating and drying method further comprises a leveling step after coating and before drying, wherein the leveling temperature is 20-25 ℃, and the relative humidity is less than or equal to 55%.
In one embodiment, the drying temperature is 50-80 ℃ and the drying time is 1-5 min.
In another aspect of the present invention, there is provided a carbon nanotube antistatic coating, which is prepared by the foregoing preparation method.
In another aspect of the present invention, an electronic device is also provided, which includes the carbon nanotube antistatic coating.
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Fig. 1 is a schematic diagram of the principle of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one aspect of the invention, a preparation method of a carbon nanotube antistatic coating is provided, which comprises the following steps:
coating the coating containing the carbon nano tube on the surface of a base material, and drying to obtain a dry coating; carrying out humidity treatment on the dry coating to obtain a treated dry coating, and then carrying out curing treatment;
the coating containing the carbon nano tube comprises a carbon nano tube dispersion liquid, resin and a solvent, wherein a polar surfactant is modified on the surface of the carbon nano tube in the carbon nano tube dispersion liquid; the humidity treatment refers to the treatment of the dry coating under the conditions that the relative humidity is 60-100% and the temperature is 35-80 ℃.
When a coating is applied to a substrate such as an electronic device to prepare an antistatic coating, it is generally desirable that the coating be dried as quickly as possible without affecting the coating properties to improve the processing efficiency. When the coating material is dried to form a coating layer, the solvent is volatilized, and thus the volatilization speed of the solvent directly affects the formation rate of the coating layer. However, for the coating containing carbon nanotubes, if the solvent is volatilized too fast, the solvent which is volatilized fast will be carried with the solvent to move due to the capillary action of the carbon nanotubes, and finally, the small clusters which are dispersed one by one exist in the coating formed after the solvent is volatilized, and the small clusters are not connected with each other, so that a continuous conductive network cannot be formed, the conductive performance of the coating is greatly influenced, the surface resistance is large, and the coating is difficult to adapt to the requirement of practical production.
According to the invention, the dried carbon nanotube antistatic coating is treated under the conditions that the relative humidity is 60-100% and the temperature is 35-80 ℃, and the polarity of the system is changed due to the change of the humidity, so that the polar surfactant modified on the surface of the carbon nanotube plays a role, isolated carbon nanotube clusters formed by micro-phase separation caused by solvent volatilization in the coating before the humidity treatment are unfolded to form an interconnected conductive network, thereby improving the conductivity of the dried coating and effectively reducing the resistance of the surface of the coating.
Therefore, the conditions of the humidity treatment play a crucial role in the carbon nanotube distribution. The humidity is too low, the adjustment of the polarity is limited, and the carbon nano tubes of the clusters are not enough to be stretched to form a conductive network which is connected with each other; if the temperature is too low, enough energy is not available to enable water to be attached, polarity control cannot be performed, and if the temperature is too high, orange peel pockmarks appear on the appearance of the coating, so that use is affected.
Alternatively, the relative humidity of the humidity treatment may be 65%, 70%, 75%, 80%, 85%, 90%, 95%, and the temperature may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃.
Within the preset range, the higher the relative humidity and temperature of the humidity treatment, the better.
In the scheme of the invention, because the construction of the interconnected conductive network is established on the basis of polarity regulation and control, rather than relying on the great increase of the using amount of the carbon nanotube conductive agent in the traditional technology, the scheme can realize lower using amount of the carbon nanotube, and is beneficial to improving the transparency of the coating and reducing the production cost; in addition, the introduction of additives for improving the compatibility of the carbon nanotube dispersion liquid with resin or solvent can be avoided, so that the coating has simpler components and more stable performance.
In some embodiments, the polar surfactant is one or more of sodium dodecyl benzene sulfonate, triton-100, PEG, NH2-PEG, PEG-NHS active ester, and polymeric dispersant containing polar groups, preferably NH2-PEG and PEG-NHS active ester.
In some embodiments, the humidity treatment is performed with a humid hot gas having a flow rate of 0.5L/min cm2～10L/min·cm2. Specifically, the flow rate of the moist heat gas may be, for example, 1L/min cm2、2L/min·cm2、3L/min·cm2、4L/min·cm2、5L/min·cm2、6L/min·cm2、7L/min·cm2、8L/min·cm2、9L/min·cm2. Preferably, the flow rate of the humid heat gas is 4L/min cm2～8L/min·cm2. Within a preset range, the damp-heat gas can be gently and uniformly contacted with the coating, so that the adhesion of water molecules is enough to realize the polarity control of the coating, and the uneven gas distribution caused by overlarge flow can be avoided, thereby causing the appearance defect of the coating and the uneven coating resistance.
In some embodiments, the drying results in a dry coating thickness of 1 μm to 20 μm, preferably a dry coating thickness of 5 μm to 10 μm.
In some embodiments, the time of the humidity treatment is 10s to 80 s. Specifically, the processing time may be, for example, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75 s; preferably, the treatment time is 30s to 60 s. The humidity treatment time is too short, the adhesion of water molecules is insufficient, polarity regulation and control cannot be carried out, the treatment time is too long, the appearance is poor, and the actual use is influenced.
In some embodiments, the carbon nanotube dispersion is a single-walled carbon nanotube dispersion, and the content of single-walled carbon nanotubes in the single-walled carbon nanotube dispersion is 0.1 to 5 per thousand. Specifically, the content of the single-walled carbon nanotube in the single-walled carbon nanotube dispersion may be, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%. Preferably, the content of the single-walled carbon nanotube is 1 to 4 per mill. It will be appreciated that aspects of the present invention allow the present invention to be used with single-walled carbon nanotube content 10-3Or even 10-4Orders of magnitude of single-walled carbon nanotube dispersion are effective in reducing production costs and improving coating transparency, but this does not mean that more amounts of single-walled carbon nanotubes are not suitable for the present invention, and the higher amounts of the solution are relatively less than optimal in terms of cost and transparency than the present invention, and are inferior to the present invention, and should be summarized in the scope of the present invention.
In some embodiments, a method of preparing a single-walled carbon nanotube dispersion comprises the steps of:
weighing single-walled carbon nanotube powder according to the amount, then adding a solvent and a polar surfactant, and fully and uniformly stirring;
coarse grinding in a ball mill for 20-40 min, preferably 30 min;
fine grinding in a sand mill for 1-3 h, preferably 2 h; the grinding medium is zirconia with the diameter of 0.3-0.5 μm; the addition amount of the grinding medium is 75-85 percent of the total mass, preferably 80 percent;
dispersing for 20-40 min to obtain single-wall carbon nanotube dispersion liquid, wherein the preferable dispersing time is 30 min.
In some embodiments, the single-walled carbon nanotubes have a length of 100nm to 100 μm and a diameter of 0.5nm to 2 nm. Specifically, the single-walled carbon nanotube may have a length of, for example, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, or 90 μm, and a diameter of, for example, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm, 1.5nm, 1.6nm, 1.7nm, 1.8nm, or 1.9 nm. Preferably, the single-walled carbon nanotubes have a length of 500nm to 5 μm and a diameter of 1nm to 2 nm. The length is within a preset range, so that the carbon nano tubes can form a conductive network which is connected with each other while having better dispersibility, and cannot be completely intertwined, so that the polar driving force is insufficient and difficult to stretch, and the anti-static coating has reliable anti-static performance; the diameter is within the preset range, so that the method can be more suitable for the humidity regulation condition of the invention, the polarity regulation effect is better, and the coating has better conductivity.
In some embodiments, the solvent used for the single-walled carbon nanotube dispersion is an alcohol solvent.
In some embodiments, it is preferable that the single-walled carbon nanotube is acid-treated and purified, and has a certain amount of-COOH, -COOH and-OH in PEG and PEG-NHS active ester on the surface, so that the polarity adjustment has a sufficient driving force.
In some embodiments, the curing process is a photocuring process. A suitable photocuring treatment has less effect on the surface resistance of the coating.
In some embodiments, a coating containing carbon nanotubes comprises, in mass percent: 1.5 to 3 percent of single-walled carbon nanotube dispersion liquid, 1 to 5 percent of photosensitive acrylic resin, 2 to 7 percent of photosensitive monomer, 0.5 to 1.5 percent of photoinitiator and 87 to 95 percent of solvent.
In some embodiments, the photosensitive acrylic resin is at least one of polyurethane acrylic resin, polyester acrylic resin and epoxy acrylic resin, and the number of functional groups is 2-6, such as but not limited to Yangxing chemical 6145-.
In some embodiments, the photosensitive monomer is a 1-6 functional monomer such as IBOA, HDDA, TMPTA, PETA, DPHA, but is not limited thereto.
In some embodiments, the photoinitiator is 184, 1173, TPO, but is not limited thereto.
In some embodiments, the solvent is one of ethanol, propanol, butanol, ethylene glycol ethyl ether, ethylene glycol plus ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether. Preferably, the solvent is a mixed solvent selected from at least two of the foregoing solvents.
In some embodiments, the coated substrate is at least one of a plastic substrate, a glass substrate, a wood substrate.
In some embodiments, the plastic substrate is at least one of PET, PMMA, PVC, PC.
In some embodiments, the coating process is roll coating, curtain coating, dip coating, or spray coating. The roller coating is suitable for roll-to-roll coating of thin films, the curtain coating and the dip coating are suitable for double-side coating of plates, and the spray coating is suitable for coating of profiled bars.
In some embodiments, a leveling step is further included after coating and before drying.
In some embodiments, the temperature of leveling is from 20 ℃ to 25 ℃ and the relative humidity is 55% or less. The photo-curable resin and the monomer are sensitive to humidity, and when the relative humidity of a leveling zone is higher than 55%, the moisture forms turbid liquid with the resin and the monomer, which causes a whitening phenomenon.
In some embodiments, the leveling time is 30s to 2 min.
In some embodiments, the roll-coating has a leveling angle of 30 ° to 90 °, and the flow-coating, dip-coating, and spray-coating has a leveling angle of 90 °.
In some embodiments, the drying temperature is 50 ℃ to 80 ℃ and the drying time is 1min to 5 min.
In another aspect of the present invention, there is provided a carbon nanotube antistatic coating, which is prepared by the foregoing preparation method. The surface resistance of the coating after the humidity treatment is 1.0 multiplied by 105Ω/m2～1.0×108Ω/m2Has good conductivity, and the resistance does not change obviously after curing, and the formed coating can effectively preventStatic electricity is stopped; the coating has certain hardness and scratch resistance, and the adhesive force is 5B; in addition, the light transmittance is as high as 92% -98%, the haze is only 0-2.5%, and the application prospect is wide.
In another aspect of the present invention, an electronic device is also provided, which includes the carbon nanotube antistatic coating.
The present invention will be described in further detail with reference to specific examples and comparative examples. It is understood that the following examples are specific to the apparatus and materials used, and in other embodiments, the invention is not limited thereto, and may be applied to, for example, dispersion using a three-roll machine.
Preparing single-walled carbon nanotube dispersion liquid:
1) weighing 3g of single-walled carbon nanotube (the pipe diameter is 1-2 nm, the length is 500 nm-5 mu m) powder, adding 1000g of isopropanol, 7g of NH2-PEG (the molecular weight is about 2000) and 1002 g of Triton, and fully and uniformly stirring;
2) placing into a planetary ball mill for coarse grinding for 30 min;
3) adding the mixture into a sand mill for fine grinding for 2 hours; the grinding medium is zirconia beads with the diameter of 0.3-0.5 mu m, and the adding proportion is 80 percent of the total mass of the materials;
4) dispersing the dispersion liquid for 30min by a three-roller machine after the fine grinding is finished, and then filling to obtain the dispersion liquid with the content of the single-walled carbon nano tube of 3 per mill.
For comparison analysis, the examples of the invention all adopt a 1mm PMMA plate as a base material, the coating process is curtain coating, and other base materials and coating processes have no obvious influence on the experimental results.
Example 1
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 8 μm;
4) controlling relative humidity at 70%, adopting temperature of 65 deg.C and flow rate of 8L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 2
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 8 μm;
4) controlling relative humidity at 70%, adopting temperature of 55 deg.C and flow rate of 8L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 3
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 8 μm;
4) controlling relative humidity at 70%, adopting temperature of 45 deg.C and flow rateIs 8L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 4
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 8 μm;
4) controlling relative humidity at 70%, adopting temperature of 35 deg.C and flow rate of 8L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 5
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 5 μm;
4) controlling relative humidity at 100%, adopting temperature of 50 deg.C and flow rate of 4L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) to treat the humidityThe dried coating is subjected to UV light curing with curing energy of 500mj/cm2And obtaining the solidified antistatic coating.
Example 6
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature to be 25 ℃ and the relative humidity to be 50%, and spraying the photocureable coating on the surface of the base material, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 5 μm;
4) controlling relative humidity at 80%, adopting temperature of 50 deg.C and flow rate of 4L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 7
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 5 μm;
4) controlling relative humidity at 60%, adopting temperature of 50 deg.C and flow rate of 4L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 8
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 1 μm;
4) controlling relative humidity at 60%, adopting temperature of 35 deg.C and flow rate of 0.5L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 10 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 9
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 1 μm;
4) controlling relative humidity at 60%, adopting temperature of 35 deg.C and flow rate of 0.5L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 30 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Example 10
1) And (2) taking 10g of the dispersion, adding 500g of mixed solvent (100 g of isopropanol, 300g of propanol and 100g of butanol) for dilution, dispersing at a high speed of 2500RPM, adding 100g of Changxing chemical photo-curing resin 6145-.
2) Controlling the temperature at 25 ℃ and the relative humidity at 50%, coating the photocuring coating on the surface of a substrate, and leveling for 2 min;
3) drying at 60 deg.C for 3min, removing solvent from the wet coating to obtain dry coating with thickness of 1 μm;
4) controlling relative humidity at 60%, adopting temperature of 35 deg.C and flow rate of 0.5L/min cm2The wet and hot gas is used for carrying out humidity treatment on the dry coating, and the treatment time is 60 s;
5) carrying out UV light curing on the dried coating after the humidity treatment, wherein the curing energy is 500mj/cm2And obtaining the solidified antistatic coating.
Comparative example 1
Comparative example 1 is essentially identical to example 4, except that: the treatment temperature in step 4) was 25 ℃.
Comparative example 2
Comparative example 2 is essentially identical to example 4, except that: the treatment temperature in step 4) was 100 ℃.
Comparative example 3
Comparative example 3 is substantially identical to example 7, except that: the relative humidity of step 4) was 50%.
Comparative example 4
Comparative example 4 is essentially identical to example 8, except that: the processing time of step 4) was 5 s.
Comparative example 5
Comparative example 5 is essentially identical to example 4, except that: the processing time of step 4) was 100 s.
Comparative example 6
Comparative example 6 is substantially identical to example 1, except that: the flow rate is 0.1L/min cm2。
Comparative example 7
Comparative example 7 is substantially identical to example 1, except that: the flow rate is 20L/min cm2。
Comparative example 8
Comparative example 8 is substantially identical to the examples, except that: step 4) is eliminated.
Performance testing
The surface resistance of the cured antistatic coatings of examples 1-10 and comparative examples 1-8 was tested, and the appearance of the product was observed, the appearance was uniform and flat, and no orange peel or pockmark was found to be acceptable, otherwise, the product was found to be unacceptable. The surface resistance test is carried out according to SJ-T10694-2006 standard, and the test results are shown in Table 1.
TABLE 1
Figure BDA0003084353350000161
As shown in Table 1, in examples 1 to 4, the relative humidity of the treatment was maintained at 70%, the treatment time was 10 seconds, and the surface resistance of the product tended to increase as the treatment temperature decreased; the data in examples 5-7 show that the surface resistance of the product tends to increase with the decrease of the relative humidity while maintaining the treatment temperature of 50 ℃ and the treatment time of 10 s; in examples 8 to 10, the surface resistance gradually decreased as the treatment time increased while maintaining the treatment temperature and the relative humidity. The surface resistance of each example was maintained at 105Ω/m2～108Ω/m2The coating can meet the actual use requirement, has uniform and flat appearance, and has no appearance of bad appearances such as orange peel, pockmarks and the like.
However, if the processing temperature is far lower than the temperature of the plate after being baked by the oven (comparative example 1), moisture is not easy to attach to the surface of the coating, and the reforming of the carbon nanotube microstructure cannot be realized, so that the resistance is higher; in addition, the coating has the defects that the appearance of the coating is provided with orange peel pock and the use is influenced due to the fact that the treatment temperature is too high (comparative example) or the treatment time is too long (comparative example 5); when the processing humidity is lower than 60% (comparative example 3) or the processing time is too short (comparative example 4), too few water molecules in the environment cannot form adhesion with a certain concentration, resulting in higher resistance; in comparative example 6, the flow rate of the hot and humid gas was too small, and too few water molecules could not form adhesion of a certain concentration, resulting in a higher resistance; in comparative example 7, the flow rate of the hot and humid gas was too large, resulting in poor appearance and non-uniform resistance distribution. However, the surface resistance of the treated products of comparative examples 1 to 5 and 7 was much better than that of the blank control (comparative example 8), although the products could not meet the practical requirements. Therefore, the humidity treatment plays a crucial role in regulating and controlling the single-wall carbon nanotube microstructure in the coating, so that the antistatic performance of the coating is influenced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.

Claims (11)

1.一种碳纳米管防静电涂层的制备方法，其特征在于，包括以下步骤：1. a preparation method of carbon nanotube antistatic coating, is characterized in that, comprises the following steps: 将含有碳纳米管的涂料涂布于基材表面，烘干得到干涂层；对所述干涂层进行湿度处理，得到处理后的干涂层，然后进行固化处理；Coating the coating containing carbon nanotubes on the surface of the substrate, drying to obtain a dry coating; performing humidity treatment on the dry coating to obtain a treated dry coating, and then performing curing treatment; 所述含有碳纳米管的涂料按质量百分含量计，包括：1.5％～3％的单壁碳纳米管分散液、1％～5％的光敏性丙烯酸树脂、2％～7％的光敏性单体、0.5％～1.5％的光引发剂以及87％～95％的溶剂，所述单臂碳纳米管分散液中的单臂碳纳米管表面修饰有极性表面活性剂；所述湿度处理是指将所述干涂层在相对湿度为60％～100％、温度为35℃～80℃的条件下处理10s～80s，所述湿度处理采用湿热气体进行处理，所述湿热气体的流量为0.5L/min·cm2～10L/min·cm2。The coating containing carbon nanotubes, in terms of mass percentage, includes: 1.5% to 3% of single-wall carbon nanotube dispersion, 1% to 5% of photosensitive acrylic resin, and 2% to 7% of photosensitivity monomer, 0.5%-1.5% photoinitiator and 87%-95% solvent, the surface of the single-arm carbon nanotube in the single-arm carbon nanotube dispersion liquid is modified with polar surfactant; the humidity treatment It means that the dry coating is treated for 10s to 80s under the conditions of a relative humidity of 60% to 100% and a temperature of 35°C to 80°C. 0.5L/min·cm 2 to 10L/min·cm 2 . 2.根据权利要求1所述的制备方法，其特征在于，所述单壁碳纳米管分散液中单壁碳纳米管的含量为0.1‰～5‰。2 . The preparation method according to claim 1 , wherein the content of the single-walled carbon nanotubes in the single-walled carbon nanotube dispersion liquid is 0.1‰˜5‰. 3 . 3.根据权利要求1所述的制备方法，其特征在于，所述单壁碳纳米管的长度为100nm～100μm，直径为0.5nm～2nm。3 . The preparation method according to claim 1 , wherein the single-walled carbon nanotubes have a length of 100 nm to 100 μm and a diameter of 0.5 nm to 2 nm. 4 . 4.根据权利要求1所述的制备方法，其特征在于，所述固化处理为光固化处理。4 . The preparation method according to claim 1 , wherein the curing treatment is photocuring treatment. 5 . 5.根据权利要求1所述的制备方法，其特征在于，所述单壁碳纳米管分散液的制备方法包括以下步骤：5. preparation method according to claim 1, is characterized in that, the preparation method of described single-walled carbon nanotube dispersion liquid comprises the following steps: 按量称取单壁碳纳米管粉体，然后加入溶剂和极性表面活性剂，充分搅拌均匀；Weigh the single-walled carbon nanotube powder according to the amount, then add solvent and polar surfactant, and stir well; 在球磨机中进行粗磨，时间为20min～40min；Coarse grinding in a ball mill for 20 to 40 minutes; 在砂磨机中进行细磨，时间为1h～3h；磨介为氧化锆，直径为0.3μm～0.5μm；磨介添加量为总质量的75％～85％；Fine grinding is carried out in a sand mill for 1h-3h; the grinding medium is zirconia with a diameter of 0.3μm-0.5μm; the amount of grinding medium added is 75%-85% of the total mass; 分散20min～40min后得到单壁碳纳米管分散液。The dispersion liquid of single-walled carbon nanotubes is obtained after dispersing for 20-40 minutes. 6.根据权利要求1所述的制备方法，其特征在于，所述单壁碳纳米管分散液采用的溶剂为醇类溶剂。6 . The preparation method according to claim 1 , wherein the solvent used in the single-walled carbon nanotube dispersion liquid is an alcohol solvent. 7 . 7.根据权利要求1所述的制备方法，其特征在于，所述光敏性丙烯酸树脂为聚氨酯丙烯酸树脂、聚酯丙烯酸树脂和环氧丙烯酸树脂中的至少一种。7 . The preparation method according to claim 1 , wherein the photosensitive acrylic resin is at least one of urethane acrylic resin, polyester acrylic resin and epoxy acrylic resin. 8 . 8.根据权利要求1～7任一项所述的制备方法，其特征在于，所述涂布之后、烘干之前还包括流平步骤，所述流平的温度为20℃～25℃，相对湿度小于等于55％。8. The preparation method according to any one of claims 1 to 7, characterized in that, after the coating and before drying, it further comprises a leveling step, and the leveling temperature is 20°C to 25°C, relative to Humidity is less than or equal to 55%. 9.根据权利要求1～7任一项所述的制备方法，其特征在于，所述烘干的温度为50℃～80℃，时间为1min～5min。9 . The preparation method according to claim 1 , wherein the drying temperature is 50° C.˜80° C., and the time is 1 min˜5 min. 10 . 10.一种碳纳米管防静电涂层，其特征在于，由权利要求1～9任一项所述的制备方法制得。10 . An antistatic coating for carbon nanotubes, characterized in that, it is prepared by the preparation method according to any one of claims 1 to 9 . 11.一种电子器件，其特征在于，包括权利要求10所述的碳纳米管防静电涂层。11. An electronic device, comprising the carbon nanotube antistatic coating of claim 10.
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