CN112239550B - Anti-static film and preparation method thereof - Google Patents
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Abstract
The invention provides an anti-static film and a preparation method thereof, belonging to the field of anti-static. According to the invention, a triboluminescent material is doped in an electronegative high molecular polymer, when an external object contacts the surface of the anti-static film and generates relative motion (friction, stretching, twisting and the like), excited electrons in the triboluminescent material can jump between energy levels, and the energy is emitted in a light form to generate fluorescence; meanwhile, the electronegative high molecular polymer is charged (triboelectrically charged) due to contact, electrons in the electronegative high molecular polymer and excited-state electrons in the triboluminescent material generate a superposition effect, so that the luminous intensity is increased, namely, the triboelectric charge is dissipated in the form of light energy, and the purpose of preventing static electricity is achieved.
Description
Technical Field
The invention relates to the technical field of static prevention, in particular to an anti-static film and a preparation method thereof.
Background
With the rapid development of modern scientific and technical electronic industry, the electrostatic hazard is increasingly serious. The instantaneous large current generated by the electrostatic discharge can cause great harm to electronic devices and other electrostatic sensitive systems, and the spark of the electrostatic discharge can ignite and detonate inflammable and explosive gas and dust. Therefore, it is particularly important to develop an effective method for preventing static electricity, controlling the generation and accumulation of static electricity, and eliminating charges due to frictional electrification of materials. In the process of triboelectrification, generation and recombination of triboelectric charges exist at the same time, so that the generation of the triboelectric charges is reduced, the charge dissipation rate is increased, or static electricity is artificially neutralized and eliminated, the accumulation of the static electricity can be effectively inhibited, and the harm caused by the static electricity is reduced.
The traditional antistatic method is to artificially neutralize the charges generated by friction, for example, four long-chain alkyl quaternary ammonium salt naphthenic acids and n-butyl sulfonic acid synthesized by greenhouse Ionic Liquids (ILs) are used as antistatic agents to be added into diesel oil to improve the antistatic property of the diesel oil, the mechanism of quaternary ammonium salt antistatic is that charged particles generated by decomposing quaternary ammonium salt can neutralize the friction charges of target polymers, so that the purpose of antistatic is achieved, and the method has the defect that the application range is narrow, is generally used for antistatic of liquid, and is not suitable for common solid polymers. In addition to neutralization, increasing the rate of dissipation of the surface charge of the polymer can also serve the purpose of antistatic. For example, chinese patent CN 109705383 a discloses that an antistatic film is prepared by doping aqueous carbon nanotubes into aqueous polyurethane, has a surface resistivity of 104 to 105 Ω, and is a static conductive material; CN 107986638A discloses that an antistatic film is prepared by overlapping a niobium pentoxide/silicon dioxide light-transmitting layer, an ITO (indium tin oxide) antistatic layer and an ATO (antimony tin oxide) anticorrosive layer, and the antistatic and anticorrosive effects are obvious; CN 208497837U discloses an antistatic film, inserts the graphite alkene powder that the matrix type distributes between two-layer base film plated with the conductive metal layer, and three-layer conducting layer cooperation is used and is made antistatic effect reliable and stable. The above-mentioned mechanism of the antistatic method is to increase the conductivity of the polymer surface, thereby increasing the dissipation rate of the surface charge of the polymer. These methods have disadvantages in that the preparation method is cumbersome, and the conductive materials (such as carbon nanotubes, graphene, etc.) used are often not easy to prepare.
Disclosure of Invention
In view of the above, the present invention is directed to an antistatic film and a method for preparing the same. The antistatic film provided by the invention is simple in preparation method, the friction luminescent material is simple in source, and energy is emitted in a light form, so that the purpose of antistatic is achieved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an antistatic film which is obtained by curing raw materials comprising an electronegative high-molecular polymer, a curing agent and a triboluminescent material.
Preferably, the electronegative high molecular polymer is polydimethylsiloxane, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyimide, polystyrene, polypropylene, polycarbonate, phenolic resin or polybutylene.
Preferably, the raw materials also comprise a curing agent.
Preferably, the triboluminescence material is ZnS: Mn2+、Sr3Al2O6:Eu3+、SrAl2O6:Eu2+、(Ba,Ca)TiO3:Pr3+、ZnS:Cu2+、CaZnOS:Mn2+、CaAlSi2O8:Eu2+Or CaMgSiO7:Eu2+,Dy3+。
Preferably, the triboluminescent material is spherical or polygonal.
Preferably, the size of the sphere or the polygon is 1-10 μm.
Preferably, the mass ratio of the electronegative high molecular polymer to the triboluminescent material is 100: 1 to 10.
Preferably, the mass ratio of the electronegative high molecular polymer to the triboluminescent material is 100: 3 to 5.
Preferably, the electronegative high molecular polymer is polydimethylsiloxane, and the triboluminescent material is ZnS: Mn2+。
The invention also provides a preparation method of the antistatic film in the technical scheme, which comprises the following steps:
and mixing the electronegative high-molecular polymer, the friction luminescent material and the solvent, coating the mixture on the polyterephthalic acid plastic for curing, and then uncovering the film to obtain the anti-static film.
Preferably, the mixing is carried out under the condition of mechanical stirring, the rotating speed of the mechanical stirring is 100-500 r/min, and the time is 1 h.
The invention provides an antistatic film which is obtained by curing raw materials comprising an electronegative high-molecular polymer and a triboluminescent material. According to the invention, a triboluminescent material is doped in an electronegative high molecular polymer, when an external object contacts the surface of the anti-static film and generates relative motion (friction, stretching, twisting and the like), excited electrons in the triboluminescent material can jump between energy levels, and the energy is emitted in a light form to generate fluorescence; meanwhile, the electronegative high molecular polymer is charged (triboelectrically charged) due to contact, electrons in the electronegative high molecular polymer and excited-state electrons in the triboluminescent material generate a superposition effect, so that the luminous intensity is increased, namely, the triboelectric charge is dissipated in the form of light energy, and the purpose of preventing static electricity is achieved.
The antistatic film provided by the invention has the advantages that: 1. the antistatic method is novel, and the method is a novel antistatic mechanism; 2. the friction luminescent material is simple to prepare, and is mainly produced industrially in the market at present; 3. the anti-static film is simple to prepare, can achieve the aim only by simple compounding, doping and curing of the anti-static film and the anti-static film, does not need to carry out complex structural treatment, and saves the cost; 4. the antistatic film has wide application range, can be used for antistatic floors, antistatic self-leveling coatings, antistatic coatings and the like, and also has great application potential in flexible outer packaging materials.
Furthermore, the additive is a friction luminescent material, is different from other additives of antistatic films, such as carbon nanotubes, lamellar graphene, MXene and the like, does not need to be made into a nano-scale structure, and can prevent static electricity as long as the granular large-size friction luminescent material can emit light after being added.
Drawings
Fig. 1 is a schematic view of an antistatic film provided by the present invention, wherein 1 is an electronegative polymer substrate, and 2 is a triboluminescent material;
FIG. 2 is an electrical signal diagram of the change of current with time obtained by the detection of the nano-generator by rubbing the antistatic film prepared in example 1;
FIG. 3 is a graph showing an electric signal of a change with time of a voltage detected by a nano-generator rubbed by the antistatic film obtained in example 1.
Detailed Description
The invention provides an antistatic film which is obtained by curing raw materials comprising an electronegative high-molecular polymer and a triboluminescent material.
In the present invention, the electronegative polymer is preferably Polydimethylsiloxane (PDMS), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), Polyimide (PI), Polystyrene (PS), polypropylene (PP), Polycarbonate (PC), phenol resin (PF), or Polybutylene (PB). The source of the electronegative polymer is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the raw material may further include a curing agent, and the kind and amount of the curing agent are not particularly limited, and the electronegative polymer may be cured. According to the invention, the triboluminescent material is added into the electronegative high molecular polymer, so that negative charges generated on the surface of the polymer due to friction are superposed with excited electrons in the triboluminescent material, the fluorescence intensity of triboluminescent is increased, and the charges on the surface of the polymer are well scattered in a light energy form, thereby achieving the purpose of preventing static electricity.
In the invention, the triboluminescence material is ZnS: Mn2+、Sr3Al2O6:Eu3+、SrAl2O6:Eu2+、(Ba,Ca)TiO3:Pr3+、ZnS:Cu2+、CaZnOS:Mn2+、CaAlSi2O8:Eu2+Or CaMgSiO7:Eu2+,Dy3+. The triboluminescent material of the present invention is not particularly limited in its source, and may be prepared by a preparation method known to those skilled in the art or may be commercially available. In the invention, the electronegative high molecular polymer is solidified to form an electronegative high molecular polymer substrate, and the triboluminescent material is doped in the electronegative high molecular polymer substrate. Fig. 1 is a schematic view of an antistatic film provided by the present invention, wherein 1 is an electronegative polymer substrate, and 2 is a triboluminescent material.
In the present invention, the triboluminescent material is preferably spherical or polygonal.
In the present invention, the size of the sphere or polygon is preferably 1 to 10 μm.
In the present invention, the mass ratio of the electronegative polymer to the triboluminescent material is preferably 100: 1-10, more preferably 100: 3 to 5.
In the invention, when the electronegative high molecular polymer is polydimethylsiloxane, the triboluminescent material is ZnS: Mn2+。
In the present invention, when the electronegative polymer is preferably PVDF, the triboluminescent material is preferably Sr3Al2O6:Eu3+Preferably, no curing agent is included in the raw materials.
In the invention, when the electronegative high molecular polymer is preferably polyvinyl chloride, the triboluminescent material is preferably CaZnOS: Mn2+Preferably, no curing agent is included in the raw materials.
The invention also provides a preparation method of the antistatic film in the technical scheme, which comprises the following steps:
and mixing the electronegative high-molecular polymer, the friction luminescent material and the solvent, coating the mixture on a poly (terephthalic acid) Plastic (PET) for curing, and then uncovering the film to obtain the anti-static film.
In the present invention, when the electronegative high molecular polymer is PVDF, the solvent is a mixture of N, N-dimethylacetamide and acetone, and the volume ratio of N, N-dimethylacetamide and acetone is 8: 12; when the electronegative high molecular weight polymer is preferably polyvinyl chloride, the solvent is preferably tetrahydrofuran.
In the invention, the mixing is preferably carried out under the condition of mechanical stirring, the rotating speed of the mechanical stirring is preferably 100-500 r/min, more preferably 200-300 r/min, and the time is preferably 1 h.
In the present invention, the application is preferably a uniform application with a spatula.
The present invention does not specifically limit the curing method, and curing can be achieved.
After the curing is completed, the present invention preferably dries the cured product, the drying temperature is preferably 80 ℃, and the drying time is preferably 2 hours.
After the film is uncovered, the invention preferably carries out cutting to obtain the anti-static film. In the present invention, the size after cutting is preferably 4cm × 4 cm.
In a specific embodiment of the present invention, the antistatic performance of the antistatic film is preferably detected by using a friction nanogenerator detection method, the positive electrode material of the friction nanogenerator is the antistatic film, the size of the antistatic film is 4cm × 4cm, a copper electrode is attached to the back of the antistatic film and a copper lead is led out, the negative electrode is a nylon 11 electrode, the size of the antistatic film is 4cm × 4cm, a copper electrode is attached to the back of the antistatic film and a copper lead is led out, and the nylon 11 electrode is obtained by a method comprising the following steps: 2 parts of nylon 11, 9 parts of anhydrous formic acid and 9 parts of dichloromethane are mixed and stirred for 5 hours to be dissolved, the mixture is spin-coated on a copper adhesive tape on a spin coater at the speed of 2000r/min and a copper wire is led out, and the mixture is dried for 1 hour at the temperature of 60 ℃. The traditional antistatic testing method is used for measuring the surface resistivity, the error is large due to the difference of the roughness, the impurities, the water content and the like of the surface of the film, the test is indirect representation of the generation condition of the charges, and the method is not visual.
In order to further illustrate the present invention, the following description will be made in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
The following examples are given by weight parts of the raw materials:
example 1
Accurately weighing 10 parts of PDMS (Sylgard 184), adding 1 part of curing agent Dow Corning 184, and adding 0 part, 0.1 part, 0.3 part and 0.5 part of ZnS: Mn respectively2+Rubbing a luminescent material in a beaker, mechanically stirring for 1h at the rotating speed of 200r/min to uniformly mix the luminescent material, uniformly coating the luminescent material on a PET plastic plate by a scraper, drying for 2h in an oven at the temperature of 80 ℃, taking out the PET plastic plate, cutting the PET plastic plate into a size of 4cm multiplied by 4cm to obtain an antistatic film, attaching a copper electrode on the back of the PET plastic plate, and leading out a lead to obtain a PDMS electrode. Simultaneously, 2 parts of nylon 11 particles and 9 parts ofAnd mixing anhydrous formic acid and 9 parts of dichloromethane, stirring for 5 hours to dissolve the anhydrous formic acid and the dichloromethane, spin-coating on a copper adhesive tape on a spin coater at the speed of 2000r/min, leading out a copper wire, and drying at 60 ℃ for 1 hour to obtain the nylon 11 electrode.
Blank film adding 0 part of ZnS: Mn2+And rubbing the luminescent material to obtain an antistatic film.
And (3) detecting the antistatic performance by a friction nano generator detection method: PDMS electrodes and nylon 11 electrodes are respectively attached to the inner walls of the electric motor and the electromagnetic shielding box, the driving motor makes the two electrodes perform contact-separation motion, and the collected electric signals are shown in fig. 2 (current) and fig. 3 (voltage). The experimental results show that: adding 0.5 part of ZnS: mn2+Then, the output current is reduced from 4.35 muA to 0.18 muA, which is reduced by 24 times; the output voltage is reduced from 147.6V to 11.9V by 12 times, which shows that the addition of the triboluminescent material can obviously reduce the generation of triboelectric charges of the electronegative high molecular polymer, thereby achieving the antistatic effect.
Example 2
Accurately weighing 3 parts of PVDF powder, adding 8 parts of N, N-dimethylacetamide and 12 parts of acetone, and respectively adding 0 part of Sr and 0.3 part of Sr3Al2O6:Eu3+Mechanically stirring at the rotating speed of 100r/min for 1h to dissolve, uniformly mixing, uniformly blade-coating on a PET plastic plate by using a scraper, drying in an oven at the temperature of 80 ℃ for 2h, taking out, cutting into the size of 4cm multiplied by 4cm to obtain an antistatic film, attaching a copper electrode on the back, and leading out a lead to obtain the PVDF electrode. Nylon 11 electrodes were prepared as shown in example 1.
And (3) detecting the antistatic performance by a friction nano generator detection method: attaching the PVDF electrode and the nylon 11 electrode to the inner walls of the motor and the electromagnetic shielding box respectively, driving the motor to collect electric signals, and displaying the result: after 0.3 part of friction luminescent material is added, the current output is reduced by 15 times, and the voltage output is reduced by 9 times.
After the two prepared films are respectively rubbed to be electrified, 100 light foam balls are respectively scattered, and due to the friction electrification, the light foam balls are adsorbed on the surfaces of the two composite films, and the quantity of the two films adsorbing the small balls is respectively checked. The result shows that 99 globules are adsorbed by the PVDF film without the addition of the friction luminescent material, the adsorption rate is 99%, while only 13 globules are adsorbed by the PVDF film with the addition of the friction luminescent material, and the adsorption rate is 13%, which indicates that the PVDF film with the addition of the friction luminescent material has good antistatic capability.
Example 3
Accurately weighing 2 parts of polyvinyl chloride (PVC) powder in a conical flask, adding 10 parts of tetrahydrofuran solution, stirring in an electric heating jacket at 50 ℃ for 1h to completely dissolve, and continuously adding 0.2 part of CaZnOS: Mn2+Rubbing the luminescent material, stirring for 10 minutes, uniformly mixing, spin-coating the solution on a copper adhesive tape on a spin coater with the rotation speed of 1000r/min, and leading out a lead to obtain the antistatic film. According to the method, a PVC electrode without adding a triboluminescent material is prepared. Nylon 11 electrodes were prepared as shown in example 1.
Paste PVC electrode and nylon 11 electrode respectively on the inner wall of motor and electromagnetic shield case, the signal of telecommunication is gathered to the driving motor, and the experimental result shows: compared with a PVC electrode without the addition of the triboluminescent material, the output current of the friction nano generator with the PVC antistatic film added with 0.2 part of the triboluminescent material is reduced from 5.2 muA to 1.4 muA, and the output voltage is reduced from 224V to 68V, which shows that the PVC antistatic film added with the triboluminescent material has good antistatic effect.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (2)
1. An antistatic film, characterized by being prepared by the steps of:
weighing 10 parts of PDMS, adding 1 part of curing agent Dow Corning 184, adding 0.1 part or 0.3 part of ZnS: Mn2+Rubbing the luminescent material in a beaker, mechanically stirring at a rotation speed of 200r/min for 1h to mix uniformly, uniformly coating the material on a PET plastic plate by a scraper, drying in an oven at 80 ℃ for 2h, and taking outAnd cutting into 4cm × 4cm size to obtain the antistatic film.
2. The method for preparing the antistatic film as claimed in claim 1, comprising the steps of:
weighing 10 parts of PDMS, adding 1 part of curing agent Dow Corning 184, adding 0.1 part or 0.3 part of ZnS: Mn2+Rubbing the luminescent material in a beaker, mechanically stirring for 1h at the rotating speed of 200r/min to uniformly mix the luminescent material, uniformly coating the luminescent material on a PET plastic plate by a scraper, drying for 2h in an oven at the temperature of 80 ℃, taking out the PET plastic plate, and cutting the PET plastic plate into the size of 4cm multiplied by 4cm to obtain the antistatic film.
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