CN113388076A - Photocuring film and preparation method and application thereof - Google Patents
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- CN113388076A CN113388076A CN202110715920.1A CN202110715920A CN113388076A CN 113388076 A CN113388076 A CN 113388076A CN 202110715920 A CN202110715920 A CN 202110715920A CN 113388076 A CN113388076 A CN 113388076A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides a photocuring film and a preparation method and application thereof, and relates to the technical field of high polymer materials. The photocuring film mainly comprises polyurethane acrylate, an acrylate monomer, a photoinitiator and an auxiliary agent in a specific percentage. Wherein, the urethane acrylate and the acrylate monomer are used as film forming materials and bear the main performance after film forming. The urethane acrylate constitutes the basic skeleton of the cured product; and the addition of the acrylate monomer can play roles in reducing viscosity, accelerating the curing speed of a system, increasing crosslinking density, controlling the caking property and flexibility of a cured film and the like. Therefore, the light-cured film which has high hardness, high elongation and high strength and also has certain optical performance and can meet the application of a large-angle 3D screen can be prepared by mixing the polyurethane acrylate and the acrylate monomer according to a certain proportion and adding a proper amount of photoinitiator and optional auxiliary agent.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a photocuring film and a preparation method and application thereof.
Background
With the development of novel plastic material technology, the plastic film has more and more powerful functions, is also widely applied to the fields of electronic materials, screen display and the like, and has better and better prospects. At present, intelligent terminals are increasingly popularized, and the appearance and use frequency of screens, circuit boards and the like is also higher and higher. In order to effectively avoid the damage to the glass caused by collision or scratch possibly occurring in the use process, a protective film is generally required to be attached to the surface of the glass.
The existing common protective film mainly comprises a toughened film and a soft film, the toughened film has high hardness, so that the film is difficult to bend and is difficult to be attached to and leveled on the surface with radian; the soft film, although having a high degree of fit, has insufficient hardness and limited protective ability. Meanwhile, in the industry, when the surface energy is low without special surface treatment and the curved surface presents a 3D screen surface film with a large angle, the inward shrinkage design of the protective film is generally required to be increased so as to improve the bonding firmness of the protective film. But the protection film designed by retraction does not protect most cambered surface areas; moreover, the distance between the protective film and the edge of the screen is large (the inner shrinkage is more than 2.0mm), so that certain influence is caused on the appearance and the fineness of electronic equipment such as a display screen and the like.
Therefore, it is necessary and urgent to develop a novel photo-curing film with high hardness, high elongation, high strength, and certain optical properties to be applied to the preparation of a protective film for a large-angle 3D screen, so as to better meet the requirements of the current 3D screen protective film.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a photocuring film, which mainly comprises polyurethane acrylate, acrylate monomer, photoinitiator and auxiliary agent in a specific percentage. The photocuring film has the advantages of high hardness, high elongation, high strength and good optical performance.
The second purpose of the present invention is to provide a method for preparing a photo-curing film, which has the advantages of simple preparation process and easy operation.
The third purpose of the invention is to provide an application of the photocuring film, and the photocuring film can be widely applied to the preparation process of the large-angle 3D screen protection film.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a photocuring film which comprises the following components in percentage by mass:
91-98% of polyurethane acrylate, 1.5-4.57% of acrylate monomer, 0.5-4.1% of photoinitiator and 0-0.33% of auxiliary agent.
Further, the light-cured film comprises the following components in percentage by mass:
97.63% of polyurethane acrylate, 1.95% of acrylate monomer, 0.42% of photoinitiator and 0% of auxiliary agent;
or, the photocuring film comprises the following components in percentage by mass:
91.40% of polyurethane acrylate, 4.57% of acrylate monomer, 4.03% of photoinitiator and 0% of auxiliary agent.
Further, the acrylate monomers include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate, acrylamide, 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, p-neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpentane trimethacrylate, trimethylolpropane pentaerythritol triacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated 1, 6-hexanediol diacrylate and tris (2-acryloxyethyl) isocyanurate.
Further, the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenyl propane-1-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, benzoin dimethyl ether, tolidine, 2-isopropyl thioxanthone and 2, 4, 6- (trimethylbenzoyl) -diphenyl phosphine oxide.
Further, the auxiliary agent comprises a leveling agent and a diluting solvent.
Further, the leveling agent comprises at least one of BYK-103, BYK-333, BYK-307, BYK-377, BYK-378, BYK-394, BYK-UV3500, BYK-UV3505, BYK-UV3510, BYK-306, 9137, tego Glide400, tego Glide100, tego Glide405, tego Glide406, tego Glide450 and tego Flow 370;
preferably, the diluting solvent includes at least one of ethyl acetate, butyl acetate, methanol, ethanol, propanol, isopropanol, isobutanol, n-butanol, methyl isobutyl ketone, isophorone, acetone, butanone, cyclohexanone, toluene, xylene, propylene glycol methyl ether, and dipropylene glycol methyl ether.
The invention provides a preparation method of the photocuring film, which comprises the following steps:
mixing the raw materials uniformly to prepare glue A; then coating the glue A on a substrate; then covering a layer of base material; and finally, sequentially carrying out photocuring and drying to obtain the photocuring film.
Further, the thickness of the coating is 0.050-0.100 mm;
preferably, the substrate is a 30g, 50 μm release film.
Further, the photocuring is UV radiation photocuring, and the intensity of the UV radiation is 1000-1400 mj/cm2；
Preferably, the drying temperature is 140-160 ℃.
The invention provides an application of the photocuring film in preparation of a large-angle 3D screen protection film.
Compared with the prior art, the invention has the beneficial effects that:
the photocuring film provided by the invention mainly comprises 91-98% of polyurethane acrylate, 1.5-4.57% of acrylate monomer, 0.5-4.1% of photoinitiator and 0-0.33% of auxiliary agent by mass percent. Wherein, the urethane acrylate and the acrylate monomer are used as film forming materials and bear the main performance after film forming. The urethane acrylate is a matrix resin of a photocuring formula and forms a basic skeleton of a cured product, namely the basic properties (including hardness, flexibility, adhesive force, optical property, aging resistance and the like) of the cured product are mainly determined by the urethane acrylate; and the addition of the acrylate monomer can play roles in reducing viscosity, accelerating the curing speed of a system, increasing crosslinking density, controlling the caking property and flexibility of a cured film and the like. Therefore, the polyurethane acrylate and the acrylate monomer are mixed according to a certain proportion, and a proper amount of photoinitiator and optional auxiliary agent are added, so that the photocuring film with high hardness, high elongation and high strength and certain optical performance can be prepared, and the effect of the application requirement of the protective film of the large-angle 3D screen is achieved.
The preparation method of the photocuring film provided by the invention comprises the following steps of firstly, uniformly mixing the raw materials to prepare glue A; then coating the glue A on a substrate; and then covering a layer of base material, and finally sequentially carrying out photocuring and drying to obtain the photocuring film. The preparation method has the advantages of simple preparation process and easy operation.
The photocuring film provided by the invention can be widely applied to the preparation process of a large-angle 3D screen protection film.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a flowchart of a process for preparing a photocurable film according to embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention, a photocurable film comprises the following components in percentage by mass:
91-98% of polyurethane acrylate, 1.5-4.57% of acrylate monomer, 0.5-4.1% of photoinitiator and 0-0.33% of auxiliary agent.
The photocuring film provided by the invention mainly comprises 91-98% of polyurethane acrylate, 1.5-4.57% of acrylate monomer, 0.5-4.1% of photoinitiator and 0-0.33% of auxiliary agent by mass percent. Wherein, the urethane acrylate and the acrylate monomer are used as film forming materials and bear the main performance after film forming. The urethane acrylate is a matrix resin of a photocuring formula and forms a basic skeleton of a cured product, namely the basic properties (including hardness, flexibility, adhesive force, optical property, aging resistance and the like) of the cured product are mainly determined by the urethane acrylate; and the addition of the acrylate monomer can play roles in reducing viscosity, accelerating the curing speed of a system, increasing crosslinking density, controlling the caking property and flexibility of a cured film and the like. Therefore, the polyurethane acrylate and the acrylate monomer are mixed according to a certain proportion, and a proper amount of photoinitiator and optional auxiliary agent are added, so that the photocuring film with high hardness, high elongation and high strength and certain optical performance can be prepared, and the effect of the application requirement of the protective film of the large-angle 3D screen is achieved.
Specifically, urethane acrylate (PUA) as an oligomer, which contains a large number of urethane N-H bonds and is very likely to form hydrogen bonds; meanwhile, the long-chain diol unit contained in the molecule can provide flexibility to form a hard-segment micro-phase region and a soft-segment micro-phase region, so that the polyurethane obtains excellent flexibility, high-shear tensile strength, good wear resistance and the like.
And the acrylate monomers with different functionalities can be greatly improved in the aspects of reducing viscosity, improving flexibility, increasing hardness and the like.
The urethane acrylate includes at least one of Eternal 6148J75, Sartomer CN965, Sartomer CN966J, Nippton Taogosei UV300013, and double bonds 5222.
In addition, the common photoinitiators are free radical photoinitiators, which can be classified into the cleavage type and the hydrogen abstraction type. The main principle of the former is as follows: the initiator molecule jumps to an excited singlet state after absorbing light energy and jumps to an excited triplet state through intersystem crossing, at the moment, the molecular structure is in an unstable state, weak bonds can generate homolytic fracture, and primary active free radicals are generated, so that the initiation polymerization is carried out; the latter absorbs light energy and generates bimolecular action with the initiator aid in an excited state to generate active free radicals.
The PUA chain termination reaction rate constant Kt and chain propagation reaction rate constant Kp are plotted against conversion in Table 1 below to guide the selection of urethane acrylates for practical production.
Table 1 PUA prepolymer photocuring reaction rate constants:
thus, by selecting an appropriate PUA, the best curing effect can be obtained under the same conditions; similarly, different types and different dosages of photoinitiators are added, and different irradiation intensities (time) are adopted, so that the fastest photocuring time and the optimal photocuring effect can be obtained under a certain main glue.
In a preferred embodiment of the present invention, the photocurable film comprises the following components in percentage by mass:
97.63% of polyurethane acrylate, 1.95% of acrylate monomer, 0.42% of photoinitiator and 0% of auxiliary agent;
or, the photocuring film comprises the following components in percentage by mass:
91.40% of polyurethane acrylate, 4.57% of acrylate monomer, 4.03% of photoinitiator and 0% of auxiliary agent.
In the invention, the technical effect of the photocuring film is further optimized by further adjusting and optimizing the dosage proportion of the raw materials of each component.
In a preferred embodiment of the present invention, the acrylate monomer comprises pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate, acrylamide, 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, p-neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpentane trimethacrylate, trimethylolpropane pentaerythritol triacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated neopentyl glycol diacrylate, and mixtures thereof, At least one of 1, 6-hexanediol diacrylate and tris (2-acryloxyethyl) isocyanurate is ethoxylated.
In a preferred embodiment, the acrylate monomers HDDA and Di-TMPTA are selected for their low viscosity, high reactivity, high crosslinking density, and high weatherability.
In a preferred embodiment of the present invention, the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenyl propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin bis methyl ether, ditoluenone, 2-isopropyl thioxanthone, 2, 4, 6- (trimethylbenzoyl) -diphenylphosphine oxide.
In a preferred embodiment, the photoinitiators 200 and 184 are selected so that the light curing effect is consistent and the odor can be removed by baking.
In a preferred embodiment of the present invention, the auxiliary agent includes a leveling agent and a diluting solvent.
In the above preferred embodiment, the leveling agent comprises at least one of BYK-103, BYK-333, BYK-307, BYK-377, BYK-378, BYK-394, BYK-UV3500, BYK-UV3505, BYK-UV3510, BYK-306, 9137, tego Glide400, tego Glide100, tego Glide405, tego Glide406, tego Glide450, tego Flow 370;
preferably, the diluting solvent includes at least one of ethyl acetate, butyl acetate, methanol, ethanol, propanol, isopropanol, isobutanol, n-butanol, methyl isobutyl ketone, isophorone, acetone, butanone, cyclohexanone, toluene, xylene, propylene glycol methyl ether, and dipropylene glycol methyl ether.
According to an aspect of the present invention, a method for preparing the above-mentioned photocurable film comprises the steps of:
mixing the raw materials uniformly to prepare glue A; then coating the glue A on a substrate; and then covering a layer of base material, and finally sequentially carrying out photocuring and drying to obtain the photocuring film.
The preparation method of the photocuring film provided by the invention comprises the following steps of firstly, uniformly mixing the raw materials to prepare glue A; then coating the glue A on a substrate; and then covering a layer of base material, and finally sequentially carrying out photocuring and drying to obtain the photocuring film. The preparation method has the advantages of simple preparation process and easy operation.
As a preferred embodiment, in order to reduce the viscosity of the glue during the coating process and reduce the resistance, the uniformly mixed glue needs to be kept at 50 ℃ for a proper time.
In a preferred embodiment of the present invention, the coating has a thickness of 0.050 to 0.100 mm;
in a preferred embodiment of the invention, the substrate is a 30g, 50 μm release film.
In a preferred embodiment of the present invention, the photocuring is UV radiation photocuring, and the intensity of the UV radiation is 1000-1400 mj/cm2The time is 10 to 20 seconds.
As a preferred embodiment, the irradiation intensity is 1100mj/cm2The time is 15 s.
In a preferred embodiment of the present invention, the drying temperature is 140 to 160 ℃.
As a preferred embodiment, the above drying temperature is chosen to be 150 ℃, 5min, to remove the odor of the film and further cure small amounts of incompletely cured glue.
According to one aspect of the invention, the application of the photocuring film in preparing a large-angle 3D screen protection film is provided.
The photocuring film provided by the invention can be widely applied to the preparation process of a large-angle 3D screen protection film.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
A photocured film comprises the following components in percentage by mass:
as shown in fig. 1, the method for preparing the photo-curing film comprises the following steps:
(1) uniformly mixing the raw materials to prepare glue A;
(2) heating the glue A at 50 ℃ for 30min to reach a viscosity suitable for coating; coating the glue A on a release film with the thickness of 0.080mm, and then covering a layer of release film to obtain an intermediate A;
(3)、intermediate A is at 1100mj/cm2And carrying out full-angle UV radiation photocuring by using an annular UV lamp under the irradiation intensity to prepare the photocuring film.
Example 2
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-cured film was the same as that of example 1, and then the cured film was dried in an oven at 150 ℃ for 5min without peeling the release film, to obtain a sample.
Example 3
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-curing film is the same as that of example 1.
Example 4
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-cured film is the same as that of example 3, and then the cured film is dried in an oven at 150 ℃ for 5min without peeling off the release film, so as to obtain a sample.
Example 5
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-curing film is the same as that of example 1.
Example 6
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-cured film is the same as that of example 5, and then the cured film is dried in an oven at 150 ℃ for 5min under the condition that the release film is not peeled off, so that a sample is obtained.
Example 7
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-curing film is the same as that of example 2.
Comparative example 1
A photocured film comprises the following components in percentage by mass:
the preparation method of the photo-curing film is the same as that of example 2.
Experimental example 1
In order to show that the photocuring film prepared by the method has the technical effects of high hardness, high elongation and high strength and certain optical performance, the performance of the photocuring films prepared in the embodiments 1 to 7 and the comparative example 1 is specifically detected, and the specific method is as follows:
(1) testing the strength and the elongation by adopting a universal sample tester, wherein the number of sample bars is 5, the width is 15mm, the gauge length is 50mm, the stretching speed is 100mm/min, and the average of three intermediate values is taken as data;
(2) measuring the Shore hardness by using a Shore durometer, pressing a pin at least 12mm away from the edge, vertically pressing the pin into the sample, keeping the pin stable, and repeating the steps for five times within 1s to obtain an average value;
(3) b, testing the transmittance and the turbidity by using a spectrophotometer, wherein the transmittance and the turbidity adopt a transmission mode, and b adopts a reflection mode, and automatically measuring by using an instrument to obtain a numerical value;
the specific test results are shown in the following table:
according to the experimental examples, the photocuring film prepared by the method has the advantages of high hardness, high elongation and high strength, and simultaneously has good optical performance, and can fully meet the requirements of the existing 3D screen protection film.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A photocurable film, characterized in that the photocurable film comprises the following components in percentage by mass:
91-98% of polyurethane acrylate, 1.5-4.57% of acrylate monomer, 0.5-4.1% of photoinitiator and 0-0.33% of auxiliary agent.
2. The photocurable film according to claim 1, wherein the photocurable film comprises the following components in percentage by mass: 97.63% of polyurethane acrylate, 1.95% of acrylate monomer, 0.42% of photoinitiator and 0% of auxiliary agent;
or, the photocuring film comprises the following components in percentage by mass: 91.40% of polyurethane acrylate, 4.57% of acrylate monomer, 4.03% of photoinitiator and 0% of auxiliary agent.
3. The photocurable film of claim 1 or 2 wherein the acrylate monomer comprises pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate, acrylamide, 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, p-neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpentane trimethacrylate, trimethylolpropane pentaerythritol triacrylate, trimethylolpropane pentaacrylate, trimethylolpropane triacrylate, trimethylolpropane pentaacrylate, and mixtures thereof, At least one of neopentylglycol diacrylate propoxylated, ethoxylated 1, 6-hexanediol diacrylate, tris (2-acryloxyethyl) isocyanurate.
4. The photocurable film according to claim 1 or 2, wherein the photoinitiator comprises at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenyl propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin bis methyl ether, ditoluinone, 2-isopropyl thioxanthone, and 2, 4, 6- (trimethylbenzoyl) -diphenylphosphine oxide.
5. The photocurable film according to claim 1 or 2, wherein the auxiliary agent comprises a leveling agent and a diluting solvent.
6. The photocurable film of claim 5 wherein the leveling agent comprises at least one of BYK-103, BYK-333, BYK-307, BYK-377, BYK-378, BYK-394, BYK-UV3500, BYK-UV3505, BYK-UV3510, BYK-306, 9137, tego Glide400, tego Glide100, tego Glide405, tego Glide406, tego Glide450, tego Flow 370;
preferably, the diluting solvent includes at least one of ethyl acetate, butyl acetate, methanol, ethanol, propanol, isopropanol, isobutanol, n-butanol, methyl isobutyl ketone, isophorone, acetone, butanone, cyclohexanone, toluene, xylene, propylene glycol methyl ether, and dipropylene glycol methyl ether.
7. A method for producing a photocurable film according to any one of claims 1 to 6, wherein the method comprises the steps of:
mixing the raw materials uniformly to prepare glue A; then coating the glue A on a substrate; and then covering a layer of base material, and finally sequentially carrying out photocuring and drying to obtain the photocuring film.
8. The method for producing a photocurable film according to claim 7, wherein the thickness of the coating is 0.050 to 0.100 mm;
preferably, the substrate is a release film.
9. The method for preparing a photocurable film according to claim 7, wherein the photocuring is UV radiation photocuring, and the intensity of the UV radiation is 1000 to 1400mj/cm2；
Preferably, the drying temperature is 140-160 ℃.
10. Use of the photocurable film according to any one of claims 1-6 for the preparation of a large-angle 3D screen protective film.
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