CN109912940B - Scratch-resistant low-warpage transparent BOPET film and preparation method thereof - Google Patents
Scratch-resistant low-warpage transparent BOPET film and preparation method thereof Download PDFInfo
- Publication number
- CN109912940B CN109912940B CN201910202041.1A CN201910202041A CN109912940B CN 109912940 B CN109912940 B CN 109912940B CN 201910202041 A CN201910202041 A CN 201910202041A CN 109912940 B CN109912940 B CN 109912940B
- Authority
- CN
- China
- Prior art keywords
- white graphene
- parts
- scratch
- warpage
- pet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a scratch-resistant low-warpage transparent BOPET film which comprises the following components in percentage by weight: 80-99.5% of PET slices and 0.5-20% of white graphene composite PET slices; the white graphene composite PET slice comprises the following components in parts by weight: 0.01-15 parts of modified white graphene, 65-99.89 parts of PET slices and 0.1-20 parts of compatilizer. The BOPET film selection and utilization technology of the chemical grafting modification of the white graphene material has high hardness and scratch resistance, effectively prevents warping deformation at high temperature, inhibits oligomer precipitation, protects optical performance from being influenced, reduces appearance abnormity in back-end operation, improves yield of a production line, simultaneously enables a PET substrate not to be hardened or only needs single-side hardening before film coating or coating, and saves cost.
Description
Technical Field
The invention relates to a PET material, in particular to a scratch-resistant low-warpage transparent BOPET film and a preparation method thereof.
Background
BOPET polyester film refers to a film made by biaxially stretching a polyethylene terephthalate polymer in the polyester family. 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, because the PET optical film is easy to warp when high temperature is resistant to influence the back-end process, on the other hand, the hardness of the PET substrate used for coating and coating is low and generally ranges from 2H to 3H, the poor scratching on two sides of the PET film is easily caused, the back-end process is greatly influenced, the yield is greatly reduced, and the cost is increased; the defects of low hardness and no wear resistance are not suitable for flexible cover plates which are increasingly popular or screen explosion-proof films.
In order to solve the problems of poor wear resistance, 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 on the upper surface and the lower surface of the PET base material to carry out double-sided hardening treatment, so that 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.
The research that the novel two-dimensional 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-end double-sided coating hardening is only reported.
Disclosure of Invention
The invention aims to provide a scratch-resistant low-warpage transparent BOPET film and a preparation method thereof, wherein the scratch-resistant low-warpage transparent BOPET film is provided for the reason that the optical PET base material used in the photoelectric industry at present is easy to have appearance abnormalities such as scratch, scratch and warpage during baking.
In order to achieve the purpose, the invention adopts the technical scheme that: a transparent BOPET film with scratch resistance and low warpage comprises the following components in percentage by weight: 80-99.5% of PET slices and 0.5-20% of white graphene composite PET slices;
the white graphene composite PET slice comprises the following components in parts by weight: 0.01-15 parts of modified white graphene, 65-99.89 parts of PET slices and 0.1-20 parts of compatilizer.
According to the white graphene composite PET slice, the white graphene is creatively applied to be a single-layer or few-layer two-dimensional material, so that the prepared BOPET film has the characteristics of high mechanical strength, high temperature resistance, high hardness, high wear resistance, flexibility, white color or transparency and the like. When the addition amount of the modified white graphene is more than 15 parts, 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 white graphene comprises the following steps:
(1) activating the white graphene under strong acid to obtain white graphene A;
(2) putting the white graphene A into an ethanol water solution, adding gamma-mercaptopropyl trimethoxysilane, stirring for reaction, taking out, and washing to obtain white graphene B;
(3) adding the white graphene B into a DMF (dimethyl formamide) solvent containing ethylene monomers, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified white graphene.
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 white graphene; the conditions of the activation treatment were: carrying out reflux treatment on the white graphene for 0.5-24 h at 60-300 ℃ by using strong acid.
In the step (2), gamma-mercaptopropyl trimethoxysilane is adopted to carry out surface modification on the white graphene, and the purpose of washing is to remove the gamma-mercaptopropyl trimethoxysilane remained on the surface of the white graphene; the stirring reaction time is 0.5-12 h.
In the step (3), the time of ultraviolet irradiation is 0.1-10 h; the purpose of washing is to wash off residual ethylene monomers on the surface of the white graphene, and the drying temperature is 30-150 ℃.
The modified white graphene is characterized in that a novel sulfydryl-alkene click addition reaction is applied to gently, quickly, controllably and effectively chemically graft alkene high polymers on the surface of the white graphene, so that good compatibility with a PET matrix is really realized, the modified white graphene can be mutually parallel and interpenetrated in the PET matrix to form a compact reticular structure while achieving good uniform dispersion in the PET matrix, the abrasion resistance and scratch resistance of the PET material are greatly enhanced, warping deformation such as upwarp and downwarp can be effectively prevented, and the yield of back-end operation is also greatly improved.
Preferably, the white graphene, the gamma-mercaptopropyltrimethoxysilane, the vinyl monomer and the photoinitiator are prepared from the following components in parts by weight: 1 part of white graphene, 0.5-15 parts of gamma-mercaptopropyl trimethoxy silane, 10-50 parts of ethylene monomer and 0.5-10 parts of photoinitiator. The preparation of the modified white graphene can be realized by adopting the above ratio.
More preferably, the white graphene, the gamma-mercaptopropyltrimethoxysilane, the vinyl monomer and the photoinitiator are prepared from the following components in parts by weight: 1 part of white graphene, 1-10 parts of gamma-mercaptopropyl-trimethoxysilane, 20-40 parts of vinyl monomers and 0.5-5 parts of photoinitiator. By adopting the raw material proportion, the prepared modified white graphene has better performance.
Preferably, the addition amount of the modified white graphene is 0.5-10 parts by weight; the modified white graphene is 1-10 layers of modified white graphene.
When the modified white graphene is added in the above amount, the modified white graphene can fully play a role in a PET (polyethylene terephthalate) slice, is easy to disperse, has no agglomeration phenomenon, and can ensure the performance of the PET slice while controlling the production cost to be lower.
Preferably, the PET slices are 80-99.6 parts by weight, and the compatilizer is 0.1-10 parts by weight. When the proportion is adopted, the material prepared from the PET slice has higher mechanical strength, high temperature resistance, hardness and wear resistance.
Preferably, the vinyl monomer is at least one of methyl acrylate, acrylamide, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate, glycidyl methacrylate, styrene, 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) 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 white graphene composite PET slice comprises the following steps:
(A) starting a high-speed mixer to heat to 60-120 ℃, weighing PET slices, modified white graphene and a compatilizer, and premixing and dispersing for 5-60 min by a high-speed disperser;
(B) and (3) starting the double-screw extruder, wherein the temperature of each zone is 230-290 ℃, 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 white graphene composite 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 scratch-resistant low-warpage transparent BOPET film, which comprises the following steps: adding the white graphene composite 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 scratch-resistant low-warpage transparent BOPET film; the temperature range of each area of the plastic film extruder is 240-300 ℃; the longitudinal stretching ratio is 210-480%, and the longitudinal stretching heat setting temperature is 65-150 ℃; the transverse stretching ratio is 280-560%, and the transverse stretching heat setting temperature is 80-210 ℃.
The white graphene modified PET slices are further prepared into a film through a melt extrusion process, and particularly, a longitudinal and transverse biaxial stretching process is adopted, so that the lamellar white graphene can be uniformly and orderly arranged and spread in a PET matrix in an oriented manner, the phenomenon of micromolecules and oligomers precipitation generated by high-temperature aging of a PET film material can be inhibited, and the optical performance is effectively protected from being influenced.
The invention has the beneficial effects that: the BOPET film creatively selects and exerts a series of excellent characteristics and chemical grafting modification technology of a white graphene material, has high hardness and scratch resistance, effectively prevents warping deformation at high temperature and inhibits oligomer precipitation, protects optical performance from being influenced, reduces appearance abnormity during rear-section operation, improves the yield of a production line, simultaneously enables a PET substrate not to be subjected to hardening treatment or only to be subjected to single-side hardening treatment before film coating or coating, saves cost, is particularly suitable for being used as a film coating or a coated PET substrate in the photoelectric industry and flexible touch display which is popular day by day, and has very wide market prospect.
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 an embodiment of the scratch-resistant and low-warpage transparent BOPET film, the scratch-resistant and low-warpage transparent BOPET film includes 1 part by weight of white graphene composite PET chips and 99 parts by weight of PET chips. The formula of the white graphene composite PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 3 layers of white 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 white graphene; then placing the mixture into an ethanol water solution, adding 6 parts by weight of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 4.5 hours at normal temperature, and washing unreacted KH590 on the surface of the white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent dissolved with 30 parts by weight of vinyl acetate in advance, adding 1.5 parts by weight of photoinitiator 184, irradiating for 2 hours by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted vinyl acetate on the surface of the white graphene for multiple times by using acetone, and drying at 90 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, weighing PET slices with the intrinsic viscosity of 0.83dL/g, modified white graphene and PP-grafted maleic anhydride (PP-g-MAH) according to parts by weight, premixing and dispersing for 15min by using a high-speed stirrer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 245-290 ℃, 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 285r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite PET slice.
The preparation method of the scratch-resistant low-warpage transparent BOPET film comprises the following steps: after the temperature of each area of the plastic film extruder is stabilized at 250-290 ℃, weighing white graphene composite PET slices and PET slices, adding the white graphene composite PET slices and the PET slices into a material cylinder of the plastic film extruder, extruding and air cooling, wherein the longitudinal stretching ratio is 250%, the longitudinal stretching heat setting temperature is 80 ℃, the transverse stretching ratio is 320%, the transverse stretching heat setting temperature is 120 ℃, and then rolling to obtain the scratch-resistant low-warpage transparent BOPET film.
Example 2
According to an embodiment of the scratch-resistant low-warpage transparent BOPET film, the scratch-resistant low-warpage transparent BOPET film comprises 3 parts by weight of white graphene composite PET slices and 97 parts by weight of PET slices. The formula of the white graphene composite PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 3 layers of white 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 white graphene; then placing the mixture 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 white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent in which 40 parts by weight of methyl acrylate monomer is dissolved in advance, adding 5 parts by weight of photoinitiator 184, irradiating for 3 hours by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing the unreacted methyl acrylate monomer on the surface of the white graphene for multiple times by using tetrahydrofuran, and drying at 85 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, weighing PET slices with the intrinsic viscosity of 0.83dL/g, modified white graphene and PP-g-MAH according to parts by weight, premixing and dispersing for 15min by using a high-speed stirrer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 250-290 ℃, 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, bracing and grain cutting to obtain the white graphene composite PET slice.
The preparation method of the scratch-resistant low-warpage transparent BOPET film comprises the following steps: after the temperature of each area of the plastic film extruder is stabilized at 260-290 ℃, weighing white graphene composite PET slices and PET slices, adding the white graphene composite PET slices and the PET slices into a material cylinder of the plastic film extruder, extruding and air cooling, wherein the longitudinal stretching ratio is 320%, the longitudinal stretching heat setting temperature is 100 ℃, the transverse stretching ratio is 400%, the transverse stretching heat setting temperature is 150 ℃, and then rolling to obtain the scratch-resistant low-warpage transparent BOPET film.
Example 3
In an embodiment of the scratch-resistant and low-warpage transparent BOPET film, the scratch-resistant and low-warpage transparent BOPET film includes 5 parts by weight of white graphene composite PET slices and 95 parts by weight of PET slices. The formula of the white graphene composite PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of 2 layers of white graphene is subjected to reflux treatment for 5 hours at a high temperature of 120 ℃ 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 white graphene; then placing the mixture into an ethanol water solution, adding 1 weight part of gamma-mercaptopropyltrimethoxysilane (KH590), mechanically stirring for 8 hours at normal temperature, and washing unreacted KH590 on the surface of the white graphene for multiple times by using tetrahydrofuran; and finally, placing the white graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent in which 20 parts by weight of glycidyl methacrylate is dissolved in advance, adding 3 parts by weight of a photoinitiator 1173, irradiating for 3.5 hours by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted glycidyl methacrylate on the surface of the white graphene for multiple times by using tetrahydrofuran, and drying at 90 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, weighing PET slices with the intrinsic viscosity of 0.83dL/g, modified white graphene and PP-g-MAH according to parts by weight, premixing and dispersing for 15min by using a high-speed stirrer, and discharging;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 250-290 ℃, 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 450r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite PET slice.
The preparation method of the scratch-resistant low-warpage transparent BOPET film comprises the following steps: after the temperature of each area of the plastic film extruder is stabilized at 260-300 ℃, weighing white graphene composite PET slices and PET slices, adding the white graphene composite PET slices and the PET slices into a material cylinder of the plastic film extruder, extruding and air cooling, wherein the longitudinal stretching ratio is 420%, the longitudinal stretching heat setting temperature is 120 ℃, the transverse stretching ratio is 480%, the transverse stretching heat setting temperature is 180 ℃, and then rolling to obtain the scratch-resistant low-warpage transparent BOPET film.
Example 4
The scratch-resistant low-warpage transparent BOPET film described in this example comprises 0.5 parts by weight of white graphene composite PET chips and 99.5 parts by weight of PET chips. The formula of the white graphene composite PET slice is shown in Table 1.
The preparation method of the white graphene composite PET slice is the same as that of the embodiment 1.
The preparation method of the scratch-resistant low-warpage transparent BOPET film is the same as that of the embodiment 1.
Example 5
The scratch-resistant low-warpage transparent BOPET film comprises 20 parts by weight of white graphene composite PET slices and 80 parts by weight of PET slices. The formula of the white graphene composite PET slice is shown in Table 1.
The preparation method of the modified white graphene and white graphene composite PET slice is the same as that of the embodiment 1.
The preparation method of the scratch-resistant low-warpage transparent BOPET film is the same as that of the embodiment 1.
Example 6
In an embodiment of the scratch-resistant and low-warpage transparent BOPET film, the scratch-resistant and low-warpage transparent BOPET film includes 1 part by weight of white graphene composite PET chips and 99 parts by weight of PET chips. The formula of the white graphene composite PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1 part by weight of single-layer white graphene is subjected to reflux treatment for 0.5h at the high temperature of 300 ℃ by nitric acid, so that active groups such as hydroxyl, carboxyl and the like are generated on the surface of the single-layer white graphene; then placing the mixture 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 surface of the white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent in which 50 parts by weight of hydroxyethyl acrylate is dissolved in advance, adding 10 parts by weight of a photoinitiator 1173, irradiating for 10 hours by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted hydroxyethyl acrylate on the surface of the white graphene for multiple times by using toluene, and drying at 100 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the modified white graphene and white graphene composite PET slice is the same as that of the embodiment 1.
The preparation method of the scratch-resistant low-warpage transparent BOPET film is the same as that of the embodiment 1.
Example 7
In an embodiment of the scratch-resistant and low-warpage transparent BOPET film, the scratch-resistant and low-warpage transparent BOPET film includes 1 part by weight of white graphene composite PET chips and 99 parts by weight of PET chips. The formula of the white graphene composite PET slice is shown in Table 1.
In this embodiment, the preparation method of the modified white graphene comprises: 1, refluxing 1 part by weight of 10 layers of white graphene at 60 ℃ for 24 hours by nitric acid to generate active groups such as hydroxyl, carboxyl and the like on the surface of the white graphene; then placing the mixture 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 white graphene for multiple times by using acetone; and finally, placing the white graphene with the chemically modified KH590 on the surface into a DMF (dimethyl formamide) solvent in which 10 parts by weight of hydroxyethyl acrylate is dissolved in advance, adding 0.5 part by weight of a photoinitiator 1173, irradiating for 0.1h by using ultraviolet light, taking out the chemically grafted white graphene after the reaction is finished, washing unreacted hydroxyethyl acrylate on the surface of the white graphene for multiple times by using methylbenzene, and drying at 100 ℃ by using a vacuum oven to obtain the modified white graphene.
The preparation method of the white graphene composite PET slice is the same as that of the embodiment 1.
The preparation method of the scratch-resistant low-warpage transparent BOPET film is the same as that of the embodiment 1.
Examples 8 to 9
The scratch-resistant and low-warpage transparent BOPET film of examples 8 to 9 comprises 1 part by weight of white graphene composite PET slices and 99 parts by weight of PET slices. The formula of the white graphene composite PET slice is shown in Table 1.
The preparation method of the modified white graphene and white graphene composite PET slices in the embodiments 8-9 is the same as that in the embodiment 1.
The preparation method of the transparent BOPET film with scratch resistance and low warpage in the embodiments 8-9 is the same as that in the embodiment 1.
Comparative example 1
The preparation method of the white graphene PET slice comprises the following steps:
(1) after the heating temperature of the high-speed mixer is stabilized at 65 ℃, 85 parts of PET slices with the intrinsic viscosity of 0.81dL/g, 10 parts of unmodified white graphene and 5 parts of PP-g-MAH are weighed according to parts by weight and premixed and dispersed for 15min by a high-speed mixer to be discharged;
(2) and (2) controlling the temperature of each zone of the double-screw extruder to be stable at 245-290 ℃, 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 285r/min, and carrying out mixing, extrusion, water cooling, bracing and grain cutting to obtain the white graphene composite PET slice.
The BOPET film includes 1 part by weight of the white graphene composite PET chip and 99 parts by weight of the PET chip, and the preparation method 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 0.83dL/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 described in this comparative example comprises 1 part by weight of the white graphene composite PET chip and 99 parts by weight of the PET chip. The formulation of the PET chips described in this comparative example is shown in Table 1. The preparation method of the modified white graphene is the same as that of example 1. The preparation method of the PET chips is the same as that of example 1. The preparation method of the BOPET film is the same as that of 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 Performance indices of BOPET films described in examples 1 to 9 and comparative examples 1 to 3
Note: the BOPET films described in examples 1 to 9 and comparative examples 1 to 3 had a thickness of 50 μm without a back surface protective film.
As can be seen from Table 2, compared with comparative examples 1 to 3, the PET chips of examples 1 to 9 have higher hardness, better abrasion resistance and better transmittance. With the increase of the addition amount of the modified white graphene, the transparency of the PET chips is not changed greatly, but the hardness and the wear resistance are both increased greatly, the warping degree is reduced greatly, when the addition amount of the modified graphene is increased to 10 parts, the hardness and the wear resistance are not increased obviously, when the addition amount is more than 15 parts, the hardness and the wear resistance are 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 (9)
1. The transparent BOPET film with scratch resistance and low warpage is characterized by comprising the following components in percentage by weight: 80-99.5% of PET slices and 0.5-20% of white graphene composite PET slices;
the white graphene composite PET slice comprises the following components in parts by weight: 0.5-10 parts of modified white graphene, 65-99.89 parts of PET slices and 0.1-20 parts of compatilizer;
the preparation method of the modified white graphene comprises the following steps:
(1) activating the white graphene under strong acid to obtain white graphene A;
(2) putting the white graphene A into an ethanol water solution, adding gamma-mercaptopropyl trimethoxysilane, stirring for reaction, taking out, and washing to obtain white graphene B;
(3) adding the white graphene B into a DMF (dimethyl formamide) solvent containing ethylene monomers, adding a photoinitiator, irradiating by ultraviolet light, taking out, washing and drying to obtain the modified white graphene.
2. The scratch-resistant low-warpage transparent BOPET film as claimed in claim 1, wherein the white graphene, the gamma-mercaptopropyl-trimethoxysilane, the vinyl monomer and the photoinitiator are prepared from the following components in parts by weight: 1 part of white graphene, 0.5-15 parts of gamma-mercaptopropyl trimethoxy silane, 10-50 parts of ethylene monomer and 0.5-10 parts of photoinitiator.
3. The scratch-resistant low-warpage transparent BOPET film as claimed in claim 1, wherein the modified white graphene is 1-10 layers of modified white graphene.
4. The scratch-resistant low-warpage transparent BOPET film as claimed in claim 3, wherein in the white graphene composite PET slice, 80-99.6 parts by weight of the PET slice and 0.1-10 parts by weight of the compatilizer are used.
5. The scratch-resistant, low-warpage transparent BOPET film of claim 1, wherein the vinyl monomer is at least one of methyl acrylate, acrylamide, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate, glycidyl methacrylate, styrene, acrylonitrile, and vinyl acetate.
6. The scratch-resistant, low-warpage transparent BOPET film according to claim 1, wherein 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) the solvent adopted for washing is at least one of toluene, xylene, acetone, butanone and tetrahydrofuran.
7. The scratch-resistant, low-warpage transparent BOPET film of claim 1, wherein the compatibilizer is PP grafted maleic anhydride.
8. The scratch-resistant low-warpage transparent BOPET film as claimed in any one of claims 1 to 7, wherein the preparation method of the white graphene composite PET slice comprises the following steps:
(A) starting a high-speed mixer to heat to 60-120 ℃, weighing PET slices, modified white graphene and a compatilizer, and premixing and dispersing for 5-60 min by a high-speed disperser;
(B) and (3) starting the double-screw extruder, wherein the temperature of each zone is 230-290 ℃, 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 white graphene composite PET slice.
9. A method for preparing the transparent BOPET film with scratch resistance and low warpage as claimed in any one of claims 1-8, which comprises the following steps: adding the white graphene composite 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 scratch-resistant low-warpage transparent BOPET film; the temperature range of each area of the plastic film extruder is 240-300 ℃; the longitudinal stretching ratio is 210-480%, and the longitudinal stretching heat setting temperature is 65-150 ℃; the transverse stretching ratio is 280-560%, and the transverse stretching heat setting temperature is 80-210 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910202041.1A CN109912940B (en) | 2019-03-15 | 2019-03-15 | Scratch-resistant low-warpage transparent BOPET film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910202041.1A CN109912940B (en) | 2019-03-15 | 2019-03-15 | Scratch-resistant low-warpage transparent BOPET film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912940A CN109912940A (en) | 2019-06-21 |
| CN109912940B true CN109912940B (en) | 2021-05-11 |
Family
ID=66965236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910202041.1A Active CN109912940B (en) | 2019-03-15 | 2019-03-15 | Scratch-resistant low-warpage transparent BOPET film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912940B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111907165A (en) * | 2020-08-17 | 2020-11-10 | 李法雷 | Wear-resistant scratch-resistant antibacterial BOPET film and preparation method thereof |
| CN113372653B (en) * | 2021-08-03 | 2022-06-21 | 苏州度辰新材料有限公司 | Stiffness-increasing master batch for BOPP film, preparation method of stiffness-increasing master batch and BOPP film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014105687A1 (en) * | 2012-12-27 | 2014-07-03 | Peterson Chemical Technology, Inc. | Surface infusion of flexible cellular foams with novel liquid gel mixture |
| CN105860086B (en) * | 2016-03-30 | 2019-05-24 | 南昌航空大学 | A kind of preparation method of the grafted by super branched polymer carbon nanotube based on click chemistry |
| CN107793722A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
-
2019
- 2019-03-15 CN CN201910202041.1A patent/CN109912940B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912940A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109912940B (en) | Scratch-resistant low-warpage transparent BOPET film and preparation method thereof | |
| JP7169411B2 (en) | Stretched film and method for producing stretched film | |
| TW201420662A (en) | Acrylic resin film | |
| EP2856016B1 (en) | Optical reflection films | |
| KR101523804B1 (en) | Method for producing acrylic film and acrylic film produced by the production method | |
| KR20140034929A (en) | Acrylic resin film having excellent resistance to whitening on bending and excellent cracking resistance | |
| CN111073427B (en) | Dual UV (ultraviolet) curing coating for automotive interior parts, preparation method thereof and paint film formed by dual UV curing coating | |
| CN109957221B (en) | Antistatic scratch-resistant transparent BOPET film and preparation method thereof | |
| CN108219608B (en) | White graphene composite resin hardening liquid and preparation method of PET hardened layer | |
| CN109867926B (en) | High-hardness and high-wear-resistance white graphene composite PET (polyethylene terephthalate) slice and preparation method thereof | |
| KR20070077815A (en) | Coating method of electrify prevention goods that use transparency panel's process of manufacture of electrify prevention coating liquid and this | |
| CN108819414B (en) | Self-repairing TPU (thermoplastic polyurethane) protective film base film and preparation method thereof | |
| WO2018168481A1 (en) | Polarizing plate and image display device | |
| CN109880230B (en) | White graphene composite PP material, film and preparation method thereof | |
| JP2022164227A (en) | Transparent conductive film, and manufacturing method of transparent conductive film | |
| CN109912941B (en) | Antistatic high-hardness nano-composite optical grade PET (polyethylene terephthalate) slice and preparation method thereof | |
| JP2018155812A (en) | Polarizer protective film, polarizing plate, and image display device | |
| CN107641455B (en) | Anti-fingerprint UV coating for automotive interior parts, and preparation method and application thereof | |
| CN110537115B (en) | Optical film, polarizing plate and image display device | |
| CN1488670A (en) | Methacrylic acid resin moulded product and its production method and resin compositon for producing said product | |
| WO2018190175A1 (en) | Optical laminate, polarizing plate, and image display device | |
| KR20190130592A (en) | Optical film, polarizer, and image display device | |
| JPS63139742A (en) | Self-supporting polyester sheet, one surface or both surface of which is coated with adhesive assistant layer and which is melt-extruded and oriented, manufacture of said sheet and coating assistant layer | |
| JP6915775B2 (en) | Manufacturing method of double glazing | |
| KR101443974B1 (en) | Resin modifier and optical film using sugar ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |