CN109957221B - Antistatic scratch-resistant transparent BOPET film and preparation method thereof - Google Patents
Antistatic scratch-resistant transparent BOPET film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antistatic scratch-resistant transparent BOPET film which comprises the following components in percentage by weight: 90-99.9% of PET slices and 0.1-10% of nano modified PET slices; the nano modified PET slice comprises the following components in parts by weight: 0.01-10 parts of modified nano functional additive, 85-99.94 parts of PET slice and 0.05-5 parts of compatilizer; the modified nano functional additive is modified graphene and/or modified carbon nano tubes. The BOPET film creatively selects and exerts a series of excellent characteristics and chemical grafting modification technologies of the carbon nano tube and the graphene material, so that a good physical and chemical combination effect between the nano functional material and a PET slice substrate is realized, the prepared PET substrate has excellent antistatic property, high hardness and scratch resistance, meanwhile, the optical performance can be ensured not to be influenced, and the appearance abnormity in the back-end operation is reduced.
Description
Technical Field
The invention relates to a PET material, in particular to an antistatic scratch-resistant transparent BOPET film and a preparation method thereof.
Background
The BOPET polyester film is a film made of polyethylene terephthalate polymer by biaxial stretching. Compared with glass, the BOPET optical film with high flexibility, high light transmittance and low haze is a special main base material for film coating manufacturers. At present, domestic manufacturers mainly import the PET substrate from the sun and the Korean, so that the cost of the substrate is high, and the domestic manufacturers generally have more problems in the production and sale of the PET substrate: on one hand, the hardness of a PET (polyethylene terephthalate) base material used in the processes of film coating, slitting and the like in the photoelectric industry is low and is generally between 2 and 3H, so that the poor scratching of two surfaces of a PET film is easily caused, a subsequent process is greatly influenced, the yield is greatly reduced, and the cost is increased; on the other hand, because the insulating property of the PET substrate is good, the BOPET substrate is in a roll-to-roll operation production mode in the production processes of film coating, slitting and the like, is easy to accumulate, generates a large amount of charges, cannot release the charges, can absorb more dust to cover the surface of the film, influences the appearance quality, and even frequently shocks the risk of personal injury caused by operators.
In order to solve the problems of high static electricity, easy scratching and the like of a PET (polyethylene terephthalate) base material, related personnel in the photoelectric film material industry need to coat a layer of inorganic nano coating and conductive micromolecules on the upper surface and the lower surface of the PET base material to carry out double-sided hardening treatment, but the transmittance of a PET film is influenced; moreover, the adhesion between the coated wear-resistant coating and the substrate is not good, and when the coated film or the coated conductive coating is used as a rear-section touch screen for manufacturing, the whole conductive layer falls off and cracks, the function NG of the touch display device is caused, and the yield is influenced. Moreover, conductive small molecules are easy to lose efficacy when the rear section is subjected to etching, UV and other working sections, and the function NG of the touch display device is also caused, so that the yield is influenced.
The research that the novel one-dimensional and two-dimensional functional nano material is directly adopted to perform composite modification on the PET slice raw material and then the PET slice raw material is subjected to biaxial stretching to prepare the transparent PET base material to replace or reduce the back-section double-sided coating hardening is only reported.
Disclosure of Invention
The invention aims to provide an antistatic scratch-resistant transparent BOPET film and a preparation method thereof, aiming at overcoming the defect of abnormal quality caused by high possibility of scratching, scratching and static electricity of an optical-grade PET substrate used in the photoelectric industry in the working procedures of film coating, slitting and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: an antistatic scratch-resistant transparent BOPE film comprises the following components in percentage by weight: 90-99.9% of PET slices and 0.1-10% of nano modified PET slices;
the nano modified PET slice comprises the following components in parts by weight: 0.01-10 parts of modified nano functional additive, 85-99.94 parts of PET slice and 0.05-5 parts of compatilizer; the modified nano functional additive is modified graphene and/or modified carbon nano tubes.
The antistatic scratch-resistant transparent BOPET film is creatively applied to single-layer, few-layer and two-dimensional materials of carbon nanotubes and graphene, and the carbon nanotubes and the graphene have the characteristics of high mechanical strength, high hardness, ultrahigh conductivity, flexibility and the like. The prepared BOPET film has excellent antistatic property, high hardness and scratch resistance, and meanwhile, the optical performance is not influenced when a small amount of the BOPET film is added, the appearance abnormality in the back-end operation is effectively reduced, and the yield of a production line is improved; the worker is also protected from being damaged by static electricity; meanwhile, the PET substrate does not need to be hardened or only needs to be hardened on one side before film coating or coating, and the cost is saved. When the modified nano functional additive is added in an amount of more than 10 parts, the agglomeration is easy to occur, and the cost is high. The PET slices are dried for 6-24 hours at 100-180 ℃ before use.
Preferably, the preparation method of the modified nano-functional additive comprises the following steps:
(1) activating graphene and/or carbon nanotubes by using strong acid;
(2) dispersing the activated graphene and/or carbon nano tube in an ethanol solution, adding gamma-mercaptopropyl trimethoxysilane, stirring, washing to remove unreacted gamma-mercaptopropyl trimethoxysilane, and obtaining mercapto-grafted graphene and/or carbon nano tube;
(3) and (3) adding the mercapto group grafted graphene and/or the carbon nano tube obtained in the step (2) into a DMF (dimethyl formamide) solvent of an ethylene monomer, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified nano functional additive.
By applying the novel sulfydryl-alkene click addition reaction, alkene high polymers are mildly, quickly, controllably and effectively chemically grafted on the surfaces of graphene and carbon nano tubes, so that good compatibility with a PET matrix is really realized, the PET matrix can be mutually parallel and interpenetrated in the PET matrix to form a compact network structure while achieving good uniform dispersion in the PET matrix, and the scratch resistance and the antistatic effect of the PET material are greatly enhanced.
In the step (1), the purpose of strong acid treatment is to generate active groups such as hydroxyl, carboxyl and the like on the surface of the graphene and/or the carbon nanotube; the conditions of the activation treatment were: and (2) carrying out reflux treatment on the graphene and/or the carbon nano tube by strong acid at the temperature of 60-270 ℃ for 0.5-18 h.
In the step (2), gamma-mercaptopropyl-trimethoxysilane is adopted to carry out surface modification on the graphene and/or the carbon nano tube, and the purpose of washing is to remove the gamma-mercaptopropyl-trimethoxysilane remained on the surface of the graphene and/or the carbon nano tube; the stirring reaction time is 0.5-12 h.
In the step (3), the time of ultraviolet irradiation is 0.1-8 h; the purpose of washing is to wash off residual acrylic monomers on the surfaces of the graphene and/or the carbon nanotubes, and the drying temperature is 30-150 ℃.
Preferably, the graphene and/or the carbon nanotube, the gamma-mercaptopropyl trimethoxysilane, the vinyl monomer and the photoinitiator are prepared from the following components in parts by weight: 1 part of graphene and/or carbon nano tube, 0.1-15 parts of gamma-mercaptopropyltrimethoxysilane, 10-50 parts of ethylene monomer and 0.1-5 parts of photoinitiator. When the proportion is adopted, the preparation of the modified nano functional additive can be realized, and the performance of the additive is ensured.
More preferably, the graphene and/or the carbon nanotube, the gamma-mercaptopropyltrimethoxysilane, the vinyl monomer and the photoinitiator are prepared from the following components in parts by weight: 1 part of graphene and/or carbon nano tube, 1-10 parts of gamma-mercaptopropyltrimethoxysilane, 20-40 parts of vinyl monomer and 0.5-3 parts of photoinitiator. The modified nano functional additive prepared by adopting the raw material proportion has better performance.
Preferably, the addition amount of the modified nano functional additive is 0.05-5 parts by weight; the carbon nanotubes are single-walled carbon nanotubes. When the modified nano functional additive is added in the above amount, the function of the modified nano functional additive can be fully exerted in the PET slices, the modified nano functional additive is easy to disperse, the agglomeration phenomenon is avoided, the production cost is low, and the performance of the PET slices is ensured. Single-walled carbon nanotubes have superior performance to multi-walled carbon nanotubes.
Preferably, the PET slices are 91-99.85 parts by weight, and the compatilizer is 0.1-4 parts by weight. When the proportion is adopted, the material prepared from the PET slice has higher mechanical strength, high temperature resistance, hardness and antistatic property.
Preferably, the vinyl monomer is at least one of styrene, hydroxyethyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, acrylamide, acrylonitrile, and vinyl acetate.
Preferably, at least one of the following (a) to (c):
(a) the strong acid species is nitric acid and/or sulfuric acid;
(b) the photoinitiator species is at least one of 250, 369, 184, 907, 500 and 1173 photoinitiators;
(c) and the solvent adopted for washing is at least one of toluene, xylene, acetone, butanone and tetrahydrofuran.
Preferably, the intrinsic viscosity of the PET slices is 0.6-1 dL/g. The intrinsic viscosity affects the processing performance and the mechanical strength, and the PET slices adopting the intrinsic viscosity can ensure good processing performance and mechanical strength.
Preferably, the compatibilizer is PP grafted maleic anhydride.
Preferably, the preparation method of the nano modified PET chip comprises the following steps:
(A) starting a high-speed mixer, heating to 60-120 ℃, weighing PET slices, the modified nano functional additive and the compatilizer, and premixing and dispersing for 5-45 min by a high-speed disperser;
(B) and (3) starting a double-screw extruder, wherein the temperature of each zone is 235-300 ℃, adding the premixed and dispersed material obtained in the step (A) into a charging barrel of the double-screw extruder, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the nano modified PET slice.
In the step (B), the rotating speed of the main engine is 120-560 r/min.
The invention also aims to provide a preparation method of the antistatic scratch-resistant transparent BOPET film, which comprises the following steps: adding the nano modified PET slices and the PET slices into a charging barrel of a plastic film extruder, and performing extrusion, air cooling, longitudinal and transverse bidirectional stretching, heat setting and rolling to obtain the antistatic scratch-resistant transparent BOPET film; the temperature range of each area of the plastic film extruder is 230-300 ℃; the longitudinal stretching ratio is 180-560%, and the longitudinal stretching heat setting temperature is 70-180 ℃; the transverse stretching ratio is 210-650%, and the transverse stretching heat setting temperature is 90-240 ℃.
The nano modified PET slices are prepared into the film by a melt extrusion process, particularly, a longitudinal and transverse biaxial stretching process is adopted, so that the two-dimensional graphene and the one-dimensional carbon nano tubes can be uniformly and orderly arranged and laid in a PET matrix in an oriented manner, and the optical performance of the PET film material is not influenced when a small amount of the nano modified PET slices are added.
The invention has the beneficial effects that: the invention provides an antistatic scratch-resistant transparent BOPET film and a preparation method thereof, the BOPET film creatively selects and exerts a series of excellent characteristics and chemical grafting modification technologies of carbon nano tubes and graphene materials, good physical and chemical combination effects between nano functional materials and a PET slice substrate are realized, the prepared PET substrate has excellent antistatic property, high hardness and scratch resistance, meanwhile, the optical performance can be ensured not to be influenced, the appearance abnormity in the later-stage operation is effectively reduced, and the yield of a production line is improved; the worker is also protected from being damaged by static electricity; meanwhile, the PET substrate does not need to be hardened or only needs to be hardened on a single surface before film coating or coating, so that the cost is saved, the flexible touch display panel is particularly suitable for being used as a film coating or coating PET substrate in the photoelectric industry and flexible touch display which is popular day by day, and the market prospect is very wide.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film comprises 1 part by weight of nano-modified PET chips and 99 parts by weight of PET chips. The formula of the nano modified PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified nano functional additive comprises: 1 part by weight of 2 layers of graphene is subjected to reflux treatment for 6 hours at a high temperature of 100 ℃ by nitric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the graphene; then placing the graphene into an ethanol water solution, adding 6 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 4 hours at normal temperature, and washing unreacted KH590 on the surface of the graphene for multiple times by using toluene; and finally, placing graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent in which 30 parts by weight of vinyl acetate is dissolved in advance, adding 1.5 parts by weight of a photoinitiator 1173, irradiating for 1.5 hours by using ultraviolet light, taking out the chemically grafted graphene after the reaction is finished, washing unreacted vinyl acetate on the surface of the graphene for multiple times by using ethyl acetate, and drying at 100 ℃ by using a vacuum oven to obtain the modified nano functional additive.
The preparation method of the nano modified PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, weighing PET slices, the modified nano functional additive and PP grafted maleic anhydride (PP-g-MAH) according to parts by weight, premixing and dispersing for 5min by using a high-speed mixer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 240-285 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 245r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the nano modified PET slice.
The preparation method of the antistatic scratch-resistant transparent BOPET film comprises the following steps: and starting the plastic film extruder to stabilize the temperature of each zone at 250-290 ℃, weighing the nano modified PET slices and the PET slices, adding the nano modified PET slices and the PET slices into a charging barrel of the plastic film extruder, extruding and air cooling to obtain the antistatic scratch-resistant transparent BOPET film, wherein the longitudinal stretching ratio is 210%, the longitudinal stretching heat setting temperature is 85 ℃, the transverse stretching ratio is 280%, and the transverse stretching heat setting temperature is 125 ℃, and then rolling.
Example 2
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film of the present embodiment comprises 1.5 parts by weight of nano-modified PET chips and 98.5 parts by weight of PET chips. The formula of the nano modified PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified nano functional additive comprises: 1 part by weight of 2 layers of graphene is subjected to reflux treatment for 5 hours at a high temperature of 120 ℃ by nitric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the graphene; then placing the graphene into an ethanol water solution, adding 10 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 6 hours at normal temperature, and washing unreacted KH590 on the surface of the graphene for multiple times by using acetone; and finally, placing graphene with the chemically modified KH590 surface into a DMF solvent dissolved with 40 parts by weight of hydroxyethyl acrylate in advance, adding 2 parts by weight of photoinitiator 1173, irradiating for 2 hours by using ultraviolet light, taking out the chemically grafted graphene after the reaction is finished, washing unreacted hydroxyethyl acrylate on the surface of the graphene for multiple times by using acetone, and drying at 110 ℃ by using a vacuum oven to obtain the modified nano functional additive.
The preparation method of the nano modified PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 80 ℃, weighing PET slices, the modified nano functional additive and PP-g-MAH according to parts by weight, premixing and dispersing for 8min by using a high-speed mixer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stabilized at 245-290 ℃, controlling the temperature of a machine head to be stabilized at 300 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 360r/min, and carrying out mixing, extrusion, water cooling, strip forming and grain cutting to obtain the nano modified PET slice.
The preparation method of the antistatic scratch-resistant transparent BOPET film comprises the following steps: and starting the plastic film extruder to stabilize the temperature of each zone at 250-290 ℃, weighing the nano modified PET slices and the PET slices, adding the nano modified PET slices and the PET slices into a charging barrel of the plastic film extruder, extruding and air cooling to obtain the antistatic scratch-resistant transparent BOPET film, wherein the longitudinal stretching ratio is 350%, the longitudinal stretching heat setting temperature is 120 ℃, the transverse stretching ratio is 420%, the transverse stretching heat setting temperature is 160 ℃, and then rolling.
Example 3
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film of the present embodiment comprises 3 parts by weight of nano-modified PET chips and 97 parts by weight of PET chips. The formula of the nano modified PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified nano functional additive comprises: 1 part by weight of 2 layers of graphene is subjected to reflux treatment for 5 hours at a high temperature of 100 ℃ by using mixed acid of sulfuric acid and nitric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the graphene; then placing the graphene into an ethanol water solution, adding 1 weight part of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 5 hours at normal temperature, and washing unreacted KH590 on the surface of the graphene for multiple times by using toluene; and finally, placing graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent dissolved with 20 parts by weight of ethyl acrylate in advance, adding 0.6 part by weight of photoinitiator 1173, irradiating for 1h by using ultraviolet light, taking out the chemically grafted graphene after the reaction is finished, washing unreacted ethyl acrylate on the surface of the graphene for multiple times by using toluene, and drying at 120 ℃ by using a vacuum oven to obtain the modified nano functional additive.
The preparation method of the nano modified PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 80 ℃, weighing PET slices, the modified nano functional additive and PP-g-MAH according to parts by weight, premixing and dispersing for 6min by using a high-speed mixer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 250-290 ℃, controlling the temperature of a machine head to be stable at 300 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 460r/min, and carrying out mixing, extrusion, water cooling, strip forming and grain cutting to obtain the nano modified PET slice.
The preparation method of the antistatic scratch-resistant transparent BOPET film comprises the following steps: and starting the plastic film extruder to stabilize the temperature of each zone at 250-290 ℃, weighing the nano modified PET slices and the PET slices, adding the nano modified PET slices and the PET slices into a material cylinder of the plastic film extruder, extruding and air cooling to obtain the antistatic scratch-resistant transparent BOPET film, wherein the longitudinal stretching ratio is 450%, the longitudinal stretching heat setting temperature is 160 ℃, the transverse stretching ratio is 560%, the transverse stretching heat setting temperature is 210 ℃, and rolling.
Example 4
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film of the present embodiment comprises 0.1 parts by weight of nano-modified PET chips and 99.9 parts by weight of PET chips. The formulation of the nano-modified PET chip is the same as in example 1, see table 1.
The preparation methods of the modified nano functional additive and the nano modified PET chip are the same as those of the embodiment 1. The preparation method of the antistatic scratch-resistant transparent BOPE film is the same as that of the example 1.
Example 5
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film comprises 10 parts by weight of nano-modified PET chips and 90 parts by weight of PET chips. The formulation of the nano-modified PET chip is the same as in example 1, see table 1.
The preparation method of the nano modified PET chip is the same as that of the example 1. The preparation method of the antistatic scratch-resistant transparent BOPE film is the same as that of the example 1.
Example 6
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film comprises 1 part by weight of nano-modified PET chips and 99 parts by weight of PET chips. The formula of the nano modified PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified nano functional additive comprises: 1 part by weight of 2-layer graphene and a single-walled carbon nanotube are subjected to high-temperature reflux treatment for 4 hours at 150 ℃ by using nitric acid/sulfuric acid mixed strong acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surfaces of the graphene and the single-walled carbon nanotube; then placing the graphene and the single-walled carbon nanotube into an ethanol water solution, adding 15 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 0.5h at normal temperature, and washing unreacted KH590 on the surfaces of the graphene and the single-walled carbon nanotube for multiple times by using methyl acetate; and finally, placing graphene and single-walled carbon nanotubes of which the surfaces are chemically modified with KH590 in a DMF solvent dissolved with 50 parts by weight of vinyl acetate in advance, adding 5 parts by weight of a photoinitiator 1173, irradiating for 8 hours by using ultraviolet light, taking out the chemically grafted graphene and single-walled carbon nanotubes after the reaction is finished, washing unreacted vinyl acetate on the surfaces of the graphene and the single-walled carbon nanotubes for multiple times by using tetrahydrofuran, and drying at 100 ℃ by using a vacuum oven to obtain the modified nano functional additive.
The preparation methods of the nano modified PET slice and the antistatic scratch-resistant transparent BOPET film are the same as those in the example 1.
Example 7
In one embodiment of the antistatic scratch-resistant transparent BOPET film of the present invention, the antistatic scratch-resistant transparent BOPET film comprises 1 part by weight of nano-modified PET chips and 99 parts by weight of PET chips. The formula of the nano modified PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified nano functional additive comprises: 1 part by weight of single-walled carbon nanotube is firstly treated by nitric acid at high temperature of 60 ℃ for 18 hours in a reflux manner, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the single-walled carbon nanotube; then placing the single-walled carbon nanotube into an ethanol water solution, adding 0.5 weight part of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 12 hours at normal temperature, and washing unreacted KH590 on the surface of the single-walled carbon nanotube for multiple times by using acetone; and finally, placing the single-walled carbon nanotube with the chemically modified KH590 on the surface into a DMF solvent in which 10 parts by weight of hydroxyethyl acrylate is dissolved in advance, adding 0.1 part by weight of a photoinitiator 1173, irradiating for 0.1h by using ultraviolet light, taking out the chemically grafted single-walled carbon nanotube after the reaction is finished, washing unreacted hydroxyethyl acrylate on the surface of the single-walled carbon nanotube for multiple times by using toluene, and drying at 100 ℃ by using a vacuum oven to obtain the modified nano functional additive.
The preparation methods of the nano modified PET slice and the antistatic scratch-resistant transparent BOPET film are the same as those in the example 1.
Examples 8 to 9
The antistatic scratch-resistant transparent BOPET film of examples 8 to 9 comprises 1 part by weight of nano-modified PET chips and 99 parts by weight of PET chips. The formula of the nano modified PET slice is shown in Table 1.
The preparation methods of the modified nano functional additive and the nano modified PET chips in the embodiments 8 to 9 are the same as the embodiment 1.
The preparation method of the antistatic scratch-resistant transparent BOPET film disclosed in the embodiments 8 to 9 is the same as that of the embodiment 1.
Comparative example 1
The preparation method of the graphene modified PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, weighing 98.5 parts by weight of PET slices with the intrinsic viscosity of 98.5 parts and the intrinsic viscosity of 0.85dL/g, 1 part by weight of unmodified graphene and 0.5 part by weight of PP-g-MAH, premixing and dispersing for 5min by using a high-speed mixer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 240-280 ℃, adding the premixed and dispersed mixture obtained in the step (1) into a charging barrel of the double-screw extruder, controlling the rotating speed of a main machine to be 245r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the graphene modified PET slice.
The preparation method of the BOPET film comprises the following steps of 1 part by weight of graphene and/or carbon nanotube composite PET slice and 99 parts by weight of PET slice, and is the same as that of example 1.
Comparative example 2
The preparation method of the PET chip described in this comparative example includes the following steps:
taking 100 parts of PET slices with the intrinsic viscosity of 0.85dL/g, modifying without adding any functional auxiliary agent, and drying for 24 hours in a drying oven at 120 ℃ for later use. The preparation method of the BOPET film is the same as that of example 1.
Comparative example 3
The BOPET film of the comparative example comprises 1 part by weight of nano-modified PET slices and 99 parts by weight of PET slices according to the formula shown in Table 1. The preparation methods of the modified nano functional additive, the nano modified PET slice and the BOPET film are the same as example 1.
TABLE 1 PET chip formulations as described in examples 1-9 and comparative example 3
Example 10
The performance of the PET chips of examples 1-9 and comparative examples 1-3 was tested by the following methods: hardness GB/T6739-.
The test results are shown in Table 2.
TABLE 2 Properties of PET chips described in examples 1 to 9 and comparative examples 1 to 3
As can be seen from Table 2, the PET chips of examples 1 to 9 have better hardness and antistatic property and maintain better optical properties than those of comparative examples 1 to 3. The hardness and the antistatic property are both greatly increased along with the increase of the addition amount of the modified nano functional additive, when the addition amount of the modified nano functional additive is increased to 5 parts, the hardness and the antistatic property are not obviously increased, the optical performance is slightly reduced, and when the addition amount is more than 10 parts, the hardness and the antistatic property are both reduced to a certain degree, and are agglomerated to a certain degree, so that the cost is high.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. The antistatic scratch-resistant transparent BOPET film is characterized by comprising the following components in percentage by weight: 90-99% of PET slices and 1-10% of nano modified PET slices;
the nano modified PET slice comprises the following components in parts by weight: 1-10 parts of modified nano functional additive, 91-98.5 parts of PET slice and 0.5-5 parts of compatilizer; the modified nano functional additive is modified graphene and/or modified carbon nano tubes;
the preparation method of the modified nano functional additive comprises the following steps:
(1) activating graphene and/or carbon nanotubes by using strong acid;
(2) dispersing the activated graphene and/or carbon nano tube in an ethanol solution, adding gamma-mercaptopropyl trimethoxysilane, stirring, washing to remove unreacted gamma-mercaptopropyl trimethoxysilane, and obtaining mercapto-grafted graphene and/or carbon nano tube;
(3) adding the mercapto-grafted graphene and/or the carbon nano tube obtained in the step (2) into a DMF (dimethyl formamide) solvent of an ethylene monomer, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified nano functional additive;
the weight ratio of the graphene and/or the carbon nano tube, the gamma-mercaptopropyl trimethoxy silane, the vinyl monomer and the photoinitiator is as follows: graphene and/or carbon nanotubes: gamma-mercaptopropyl trimethoxysilane: ethylene monomer: the photoinitiator =1: 0.1-15: 10-50: 0.1-5.
2. The antistatic scratch-resistant transparent BOPET film according to claim 1, wherein the vinyl monomer is at least one of styrene, hydroxyethyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, acrylamide, acrylonitrile, and vinyl acetate.
3. The antistatic scratch-resistant transparent BOPET film according to claim 1, wherein at least one of the following (a) to (c):
(a) the strong acid is nitric acid and/or sulfuric acid;
(b) the photoinitiator is at least one of 250, 369, 184, 907, 500 and 1173 photoinitiator;
(c) the solvent adopted for washing is at least one of toluene, xylene, acetone, butanone, tetrahydrofuran, methyl acetate and ethyl acetate.
4. The antistatic scratch resistant transparent BOPET film of claim 1 wherein the compatibilizer is PP grafted maleic anhydride.
5. The antistatic scratch-resistant transparent BOPET film as claimed in any one of claims 1 to 4, wherein the preparation method of the nano modified PET slice comprises the following steps:
(A) starting a high-speed mixer, heating to 60-120 ℃, weighing PET slices, the modified nano functional additive and the compatilizer, and premixing and dispersing for 5-45 min by a high-speed disperser;
(B) and (3) starting a double-screw extruder, wherein the temperature of each zone is 235-300 ℃, adding the premixed and dispersed material obtained in the step (A) into a charging barrel of the double-screw extruder, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the nano modified PET slice.
6. The preparation method of the antistatic scratch-resistant transparent BOPET film as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps: adding the nano modified PET slices and the PET slices into a charging barrel of a plastic film extruder, and performing extrusion, air cooling, longitudinal and transverse bidirectional stretching, heat setting and rolling to obtain the antistatic scratch-resistant transparent BOPET film; the temperature range of each area of the plastic film extruder is 230-300 ℃; the longitudinal stretching ratio is 180-560%, and the longitudinal stretching heat setting temperature is 70-180 ℃; the transverse stretching ratio is 210-650%, and the transverse stretching heat setting temperature is 90-240 ℃.
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