CN109810647B - Membrane material for eye-protecting computer screen - Google Patents
Membrane material for eye-protecting computer screen Download PDFInfo
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- CN109810647B CN109810647B CN201910081796.0A CN201910081796A CN109810647B CN 109810647 B CN109810647 B CN 109810647B CN 201910081796 A CN201910081796 A CN 201910081796A CN 109810647 B CN109810647 B CN 109810647B
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 title claims abstract description 5
- 239000010410 layer Substances 0.000 claims abstract description 122
- 230000031700 light absorption Effects 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 42
- 238000005342 ion exchange Methods 0.000 claims abstract description 27
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004677 Nylon Substances 0.000 claims abstract description 18
- PAVQGHWQOQZQEH-UHFFFAOYSA-N adamantane-1,3-dicarboxylic acid Chemical compound C1C(C2)CC3CC1(C(=O)O)CC2(C(O)=O)C3 PAVQGHWQOQZQEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- VQKLRVZQQYVIJW-UHFFFAOYSA-N dihydralazine Chemical compound C1=CC=C2C(NN)=NN=C(NN)C2=C1 VQKLRVZQQYVIJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960002877 dihydralazine Drugs 0.000 claims abstract description 18
- 229920001778 nylon Polymers 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 18
- 239000012790 adhesive layer Substances 0.000 claims abstract description 15
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- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- NIJMZBWVSRWZFZ-UHFFFAOYSA-N 4-[2-[3,5-bis[2-(4-carboxyphenyl)ethynyl]phenyl]ethynyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC1=CC(C#CC=2C=CC(=CC=2)C(O)=O)=CC(C#CC=2C=CC(=CC=2)C(O)=O)=C1 NIJMZBWVSRWZFZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyethylene terephthalate Polymers 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
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- MNVHWUKQUVXKDJ-UHFFFAOYSA-L disodium 2,9-dimethyl-4,7-diphenyl-1H-1,10-phenanthroline-2-sulfonate Chemical compound [Na+].[Na+].CC1(NC2=C3N=C(C=C(C3=CC=C2C(=C1)C1=CC=CC=C1)C1=CC=CC=C1)C)S(=O)(=O)[O-].CC1(NC2=C3N=C(C=C(C3=CC=C2C(=C1)C1=CC=CC=C1)C1=CC=CC=C1)C)S(=O)(=O)[O-] MNVHWUKQUVXKDJ-UHFFFAOYSA-L 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 claims description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 9
- GKQLYSROISKDLL-UHFFFAOYSA-N EEDQ Chemical compound C1=CC=C2N(C(=O)OCC)C(OCC)C=CC2=C1 GKQLYSROISKDLL-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 claims description 9
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 9
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
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- 238000000967 suction filtration Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- JLXXLCJERIYMQG-UHFFFAOYSA-N phenylcyanamide Chemical compound N#CNC1=CC=CC=C1 JLXXLCJERIYMQG-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a film material for an eye-protecting computer screen, which comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride as a base material, then carrying out ion exchange, and adding an additive; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine. The invention also discloses a preparation method of the membrane material for the eye-protecting computer screen. The prepared film material for the eye-protecting computer screen has the advantages of obvious eye-protecting effect and good friction resistance, and can effectively reduce the transmittance of harmful blue light while ensuring the high transmittance of beneficial blue light.
Description
Technical Field
The invention relates to the technical field of film display, in particular to an optical film applied to a computer screen for protecting eyes and preventing blue light.
Background
With the progress of science and technology and the popularization of electronic digital products, electronic equipment has become an indispensable article for daily life of people, and the electronic equipment is generally provided with a liquid crystal display screen which utilizes the physical characteristics of liquid crystal, so that the arrangement is ordered when the electronic equipment is electrified, light can pass through the liquid crystal display screen easily, and the arrangement is disordered when the electronic equipment is not electrified, so that the light can be prevented from passing through the liquid crystal display screen. The computer is the most common one of the electronic devices, when the computer is used, a computer screen can emit a large amount of high-energy short-wave blue light, the blue light continuously irradiates the eyes of people to cause the dysfunction of the eyes, and the blue light with extremely high energy can penetrate through crystalline lens to reach retina to cause photochemical damage to the retina and directly or indirectly cause damage to cells in a macular area. Therefore, it is very beneficial to protect the skin and eyes how to filter out some of the blue light emitted by the screens of these devices.
Blocking blue light for a long time is the most effective method for reducing damage, and the eye protection film can effectively solve the problem. However, the existing blue-light-proof eye-protecting protective film generally has the defects of complex process, high cost, low blue light and ultraviolet absorption rate and low transmittance, and in addition, the film can reflect or absorb beneficial blue light while absorbing harmful blue light, so that the display distortion of object color is caused.
Chinese patent document with application number 201410238605.4 reports a blue-proof film for lenses, which comprises the following components in percentage by weight: 30% -60% of tin oxide; 10% -40% of rubidium; 10 to 40 percent of platinum. Through adding metallic element, can effectual isolation ultraviolet and can filter the harmful blue light of part, alleviate the stimulation of blue light to eyes, eliminate uncomfortable symptoms such as eyes acerbity, generate heat or pain, alleviate eye fatigue. However, the blue light prevention film of the lens is formed by a vacuum evaporation method, the process is expensive, and the adsorption force between the metal and the oxide component thereof and the lens is not strong and the lens is easy to fall off.
Chinese patent CN 106366608B discloses a blue-light-proof polycarbonate film and a preparation method thereof, the blue-light-proof polycarbonate film comprises the following components in parts by weight: 75-90 parts of polycarbonate powder, 5-15 parts of blue-light-proof nano particles, 2-5 parts of a compatilizer and 2-5 parts of other additives; a preparation method of a blue-light-proof polycarbonate film comprises the following process steps: A) mechanically premixing; B) melting and mixing; C) cooling and pelletizing; D) and (4) extrusion molding, and finally realizing the preparation of the product. The invention has simple process flow, high production efficiency, low cost, good absorption performance of the film on blue light and ultraviolet light and high transmittance, can well protect eyes from being damaged by high-energy short-wave blue light when being used on electronic products, but the blue light-proof nano particles in the film have poor compatibility with a polymer matrix and uneven dispersion, can generate an exosmosis phenomenon in the long-term use process, and has limited blue light absorption effect, thereby influencing the eye protection effect.
Therefore, the computer shielding protective film which has an obvious eye protection effect and good friction resistance, can effectively reduce the transmittance of harmful blue light while ensuring the high transmittance of beneficial blue light meets the market demand, and has wide market value and application prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a film material for an eye-protecting computer screen, which overcomes the technical problems of complicated process, high cost, low blue light and ultraviolet absorption rate and transmittance, and object color display distortion caused by the fact that harmful blue light is absorbed and beneficial blue light is reflected or absorbed simultaneously in the traditional blue light-preventing eye-protecting protective film, and has the advantages of obvious eye-protecting effect, good friction resistance, and capability of effectively reducing the transmittance of harmful blue light while ensuring the high transmittance of the beneficial blue light.
In order to achieve the aim of the invention, the invention adopts the technical scheme that,
a film material for an eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
Further, the preparation material of the transparent adhesive layer comprises at least one of acrylate adhesive, polyurethane adhesive and silicon rubber adhesive.
Further, the preparation material of the release protective film layer comprises at least one of polymethyl methacrylate, polycarbonate, polystyrene and polyethylene terephthalate.
Preferably, the method for preparing the blue light absorption layer includes the following steps:
i preparation of addition polymer: adding tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt into a high boiling point solvent, adding an initiator into the solvent, stirring the mixture for reaction for 3 to 5 hours at 75 to 85 ℃ under the atmosphere of nitrogen or inert gas, then precipitating the mixture in water, washing the precipitated product for 3 to 5 times by using ethanol, and then drying the product in a vacuum drying oven at 80 to 90 ℃ to constant weight;
II, ion exchange: soaking the addition polymer prepared in the step I in 10-20% by mass of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline disodium sulfonate salt solution, performing ion exchange for 20-30 hours at 50-60 ℃, washing for 3-5 times, and drying in a vacuum drying oven at 80-90 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, p-cyananiline, 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline into ethanol, stirring and reacting at room temperature for 20-24 hours, then carrying out suction filtration to remove the solvent, washing the product with diethyl ether for 3-5 times, and then carrying out rotary evaporation to remove residual diethyl ether;
IV Tb-Eu-Re-O preparation: terbium nitrate, europium nitrate, rhenium (III) chloride and sodium hydroxide are added into deionized water, ultrasonic dispersion is carried out for 15-30 minutes, then citric acid is added, magnetic stirring is carried out for 10-15 minutes to obtain a mixed solution, then the mixed solution is placed into a microwave oven, continuous reaction is carried out for 25-30 minutes under the condition that the microwave power is 300-500W, then cooling is carried out to room temperature, centrifugal separation is carried out, deionized water is used for washing for 3-5 times, and drying is carried out to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: and (3) adding the addition polymer after ion exchange prepared in the step (II), the paracyanoaniline modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step (III), Tb-Eu-Re-O prepared in the step (IV) and a silane coupling agent KH560 into a double-screw extruder, melting and extruding at the temperature of 220-250 ℃, cooling and solidifying, and rolling by using a roller to obtain the blue light absorption layer.
Preferably, the mass ratio of the tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, the acrylonitrile, the ethylene carbonate, the 1-allyl-3-vinyl imidazole chloride salt, the high boiling point solvent and the initiator in the step I is 0.5:1:1:0.3 (10-15: 0.01).
Preferably, the high boiling point solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile; the inert gas is selected from helium, neon and argon.
Preferably, the mass ratio of the addition polymer to the 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline disodium sulfonate salt solution in the step II is 1 (20-30).
Preferably, the mass ratio of the 1,3, 5-tri (4-carboxyphenylethynyl) benzene, the p-cyanoaniline, the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline and the ethanol in the step III is 1:1.44 (0.2-0.4) to (10-12).
Preferably, the mass ratio of terbium nitrate, europium nitrate, rhenium (III) chloride, sodium hydroxide, deionized water and citric acid in the step IV is 1:1:1:0.5 (20-30) to 0.25.
Preferably, the mass ratio of the addition polymer after ion exchange, the 1,3, 5-tri (4-carboxyphenylethynyl) benzene modified by the paracyano aniline, Tb-Eu-Re-O and the silane coupling agent KH560 in the step V is 1:0.01:0.01: 0.005.
Preferably, the preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1, 3-adamantanedicarboxylic acid and dihydrazino phthalazine into N-methylpyrrolidone, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine into the N-methylpyrrolidone, stirring and reacting for 2-3 hours at 95-105 ℃ in a nitrogen atmosphere, stirring and reacting for 8-10 hours at 125-135 ℃, separating out the product in water after the reaction is finished, washing the separated product with ethanol for 4-6 times, and drying the product in a vacuum drying oven at 85-95 ℃ to constant weight;
step S2: adding the transparent nylon, the polycondensate prepared in the step S1 and the compatilizer into a double-screw extruder, performing melt extrusion at the temperature of 220-250 ℃, cooling and solidifying, and performing roller calendering to obtain the wear-resistant layer.
Preferably, the mass ratio of the 1, 3-adamantanedicarboxylic acid, the dihydrazino-phthalazine, the N-methylpyrrolidone, the dicyclohexylcarbodiimide and the 4-dimethylaminopyridine in the step S1 is 1.18:1 (10-12) to 0.2-0.4) to 0.5.
Preferably, the mass ratio of the nylon, the polycondensate and the compatilizer in the step S2 is 1:0.1: 0.01; the compatilizer is selected from one or more of PE-g-ST, PP-g-ST, ABS-g-MAH and PE-g-MAH.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the film material for the eye-protecting computer screen provided by the invention has the advantages of easily available raw materials and low price, overcomes the technical problems of complicated process, high cost, low blue light and ultraviolet ray absorption rate and transmittance, and object color display distortion caused by the fact that the film material prepared by the film material can reflect or absorb beneficial blue light while absorbing the harmful blue light in the traditional blue light-preventing eye-protecting protective film, and has the advantages of obvious eye-protecting effect, good friction resistance and capability of effectively reducing the transmittance of the harmful blue light while ensuring the high transmittance of the beneficial blue light.
2) The film material for the eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release type protective film layer multi-layer film structure, so that the comprehensive performance of the film material is improved, and the cost is reduced; the wear-resistant layer is formed by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine, so that the weather resistance, the wear resistance and the fingerprint and dust resistance of the film layer are improved on the premise of not influencing the haze; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, performing ion exchange with 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyanoaniline, combines the advantages of an inorganic blue light absorbent and an organic absorbent, and has stronger harmful blue light prevention performance by synergistic action, particularly the first use of Tb-Eu-Re-O alloy oxide and the cyanoaniline with a conjugated structure is modified by 1,3, 5-tri (4-carboxyphenylethynyl) benzene together significantly improves the performance of preventing harmful blue light; the Tb-Eu-Re-O is dispersed more uniformly and has better compatibility by adding the coupling agent; the film material has high transmittance, good absorption of blue light and ultraviolet light, excellent comprehensive performance and long service life due to the synergistic effect of the film layers.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials used in the following examples of the present invention were purchased from Mobei (Shanghai) Biotech Co., Ltd.
Example 1
A film material for an eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
The transparent adhesive layer is prepared from an acrylate adhesive.
The release protective film layer is prepared from polymethyl methacrylate.
The preparation method of the blue light absorption layer comprises the following steps:
i preparation of addition polymer: adding 0.5kg of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, 1kg of acrylonitrile, 1kg of ethylene carbonate and 0.3kg of 1-allyl-3-vinyl imidazole chloride salt into 10kg of dimethyl sulfoxide, adding 0.01kg of azobisisobutyronitrile into the dimethyl sulfoxide, stirring the mixture for reaction for 3 hours at 75 ℃ in a nitrogen atmosphere, then precipitating the mixture in water, washing the precipitated product for 3 times by using ethanol, and then placing the product in a vacuum drying oven to dry the product to constant weight at 80 ℃;
II, ion exchange: soaking 1kg of the addition polymer prepared in the step I in 20kg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt solution with the mass fraction of 10%, performing ion exchange for 20 hours at 50 ℃, washing with water for 3 times, and then placing in a vacuum drying oven for drying at 80 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: adding 1kg of 1,3, 5-tri (4-carboxyphenylethynyl) benzene, 1.44kg of p-cyanoaniline and 0.2kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline into 10kg of ethanol, stirring and reacting for 20 hours at room temperature, then removing the solvent by suction filtration, washing the product for 3 times by using diethyl ether, and then removing the residual diethyl ether by rotary evaporation;
IV Tb-Eu-Re-O preparation: adding 100g of terbium nitrate, 100g of europium nitrate, 100g of rhenium (III) chloride and 50g of sodium hydroxide into 2000g of deionized water, ultrasonically dispersing for 15 minutes, then adding 25g of citric acid, magnetically stirring for 10 minutes to obtain a mixed solution, then placing the mixed solution into a microwave oven, continuously reacting for 25 minutes under the condition that the microwave power is 300W, then cooling to room temperature, centrifugally separating, washing for 3 times by using deionized water, and drying to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: adding 1kg of the ion-exchanged addition polymer prepared in the step II, 0.01kg of the paracyanoaniline-modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step III, 0.01kg of Tb-Eu-Re-O prepared in the step IV and 0.005kg of silane coupling agent into a double-screw extruder, carrying out melt extrusion at 220 ℃, cooling and solidifying, and rolling to obtain the blue light absorption layer.
The preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1.18kg of 1, 3-adamantanedicarboxylic acid and 1kg of dihydralazine into 10kg of N-methylpyrrolidone, adding 0.2kg of dicyclohexylcarbodiimide and 0.5kg of 4-dimethylaminopyridine into the mixture, stirring the mixture to react for 2 hours at 95 ℃ under the nitrogen atmosphere, stirring the mixture to react for 8 hours at 125 ℃, separating out the product in water after the reaction is finished, washing the separated product for 4 times by using ethanol, and drying the product in a vacuum drying oven at 85 ℃ to constant weight;
step S2: adding 1kg of transparent nylon, 0.1kg of polycondensate prepared in the step S1 and 0.01kg of compatilizer PE-g-ST into a double-screw extruder, carrying out melt extrusion at 220 ℃, cooling and solidifying, and rolling by using a roller to obtain the wear-resistant layer.
Example 2
A film material for an eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
The transparent adhesive layer is prepared from a polyurethane adhesive.
The preparation material of the release protective film layer is polycarbonate.
The preparation method of the blue light absorption layer comprises the following steps:
i preparation of addition polymer: adding 0.5kg of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, 1kg of acrylonitrile, 1kg of ethylene carbonate and 0.3kg of 1-allyl-3-vinyl imidazole chloride salt into 11kg of N, N-dimethylformamide, adding 0.01kg of azobisisoheptonitrile into the mixture, stirring the mixture for reaction for 3 to 5 hours at 75 to 85 ℃ under the atmosphere of helium, then precipitating the mixture in water, washing the precipitated product for 3 to 5 times by using ethanol, and then drying the product in a vacuum drying oven at 80 to 90 ℃ to constant weight;
II, ion exchange: soaking 1kg of the addition polymer prepared in the step I in 22kg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt solution with the mass fraction of 12%, performing ion exchange for 22 hours at 52 ℃, washing with water for 4 times, and drying in a vacuum drying oven at 82 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: 1kg of 1,3, 5-tri (4-carboxyphenylethynyl) benzene, 1.44kg of p-cyanoaniline and 0.25kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline are added into 10.5kg of ethanol, stirred and reacted for 21 hours at room temperature, then the solvent is removed by suction filtration, the product is washed for 4 times by diethyl ether, and the residual diethyl ether is removed by rotary evaporation;
IV Tb-Eu-Re-O preparation: adding 100g of terbium nitrate, 100g of europium nitrate, 100g of rhenium (III) chloride and 50g of sodium hydroxide into 2300g of deionized water, ultrasonically dispersing for 18 minutes, then adding 25g of citric acid, magnetically stirring for 11 minutes to obtain a mixed solution, then placing the mixed solution into a microwave oven, continuously reacting for 26 minutes under the condition that the microwave power is 350W, then cooling to room temperature, centrifugally separating, washing for 4 times with deionized water, and drying to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: adding 1kg of the ion-exchanged addition polymer prepared in the step II, 0.01kg of the paracyanoaniline-modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step III, 0.01kg of Tb-Eu-Re-O prepared in the step IV and 0.005kg of silane coupling agent into a double-screw extruder, carrying out melt extrusion at 230 ℃, cooling and solidifying, and rolling by using a roller to obtain the blue light absorption layer.
The preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1.18kg of 1, 3-adamantanedicarboxylic acid and 1kg of dihydralazine into 10.5kg of N-methylpyrrolidone, adding 0.25kg of dicyclohexylcarbodiimide and 0.5kg of 4-dimethylaminopyridine into the mixture, stirring the mixture to react for 2.3 hours at the temperature of 97 ℃ under the nitrogen atmosphere, stirring the mixture to react for 8.5 hours at the temperature of 127 ℃, separating out the product in water after the reaction is finished, washing the separated product for 5 times by using ethanol, and drying the product in a vacuum drying oven at the temperature of 87 ℃ to constant weight;
step S2: adding 1kg of transparent nylon, 0.1kg of polycondensate prepared in the step S1 and 0.01kg of compatilizer PP-g-ST into a double-screw extruder, carrying out melt extrusion at 230 ℃, cooling and solidifying, and rolling by using a roller to obtain the wear-resistant layer.
Example 3
A film material for an eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
The transparent adhesive layer is prepared from a silicone rubber adhesive.
The release protective film layer is made of polystyrene.
The preparation method of the blue light absorption layer comprises the following steps:
i preparation of addition polymer: adding 0.5kg of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, 1kg of acrylonitrile, 1kg of ethylene carbonate and 0.3kg of 1-allyl-3-vinyl imidazole chloride salt into 12kg of N-methyl pyrrolidone, adding 0.01kg of azobisisobutyronitrile into the mixture, stirring the mixture for reaction for 4 hours at the temperature of 80 ℃ under the atmosphere of neon, then precipitating the mixture in water, washing the precipitated product for 4 times by using ethanol, and then drying the product in a vacuum drying oven at the temperature of 85 ℃ until the weight is constant;
II, ion exchange: soaking 1kg of the addition polymer prepared in the step I in 25kg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline disodium sulfonate salt solution with the mass fraction of 15%, performing ion exchange for 25 hours at 55 ℃, washing with water for 4 times, and drying in a vacuum drying oven at 85 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: adding 1kg of 1,3, 5-tri (4-carboxyphenylethynyl) benzene, 1.44kg of p-cyanoaniline and 0.3kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline into 11kg of ethanol, stirring and reacting for 22 hours at room temperature, then removing the solvent by suction filtration, washing the product for 4 times by using diethyl ether, and then removing the residual diethyl ether by rotary evaporation;
IV Tb-Eu-Re-O preparation: adding 100g of terbium nitrate, 100g of europium nitrate, 100g of rhenium (III) chloride and 50g of sodium hydroxide into 2700g of deionized water, ultrasonically dispersing for 25 minutes, then adding 25g of citric acid, magnetically stirring for 13 minutes to obtain a mixed solution, then placing the mixed solution into a microwave oven, continuously reacting for 28 minutes under the condition that the microwave power is 400W, then cooling to room temperature, centrifugally separating, washing for 4 times by using deionized water, and drying to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: adding 1kg of the ion-exchanged addition polymer prepared in the step II, 0.01kg of the paracyanoaniline-modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step III, 0.01kg of Tb-Eu-Re-O prepared in the step IV and 0.005kg of silane coupling agent into a double-screw extruder, carrying out melt extrusion at 240 ℃, cooling and solidifying, and rolling by using a roller to obtain the blue light absorption layer.
The preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1.18kg of 1, 3-adamantanedicarboxylic acid and 1kg of dihydralazine into 11kg of N-methylpyrrolidone, adding 0.3kg of dicyclohexylcarbodiimide and 0.5kg of 4-dimethylaminopyridine into the mixture, stirring the mixture to react for 2.6 hours at 100 ℃ under the nitrogen atmosphere, stirring the mixture to react for 9 hours at 130 ℃, separating out the product in water after the reaction is finished, washing the separated product for 5 times by using ethanol, and drying the product in a vacuum drying oven at 90 ℃ to constant weight;
step S2: adding 1kg of transparent nylon, 0.1kg of polycondensate prepared in the step S1 and 0.01kg of compatilizer ABS-g-MAH into a double-screw extruder, carrying out melt extrusion at 240 ℃, cooling and solidifying, and rolling by using a roller to obtain the wear-resistant layer.
Example 4
A film material for an eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
The transparent adhesive layer is prepared from a mixture of an acrylate adhesive, a polyurethane adhesive and a silicone rubber adhesive in a mass ratio of 1:2: 3.
The release protective film layer is prepared from a mixture of polymethyl methacrylate, polycarbonate, polystyrene and polyethylene terephthalate in a mass ratio of 1:1:2: 1.
The preparation method of the blue light absorption layer comprises the following steps:
i preparation of addition polymer: adding 0.5kg of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, 1kg of acrylonitrile, 1kg of ethylene carbonate and 0.3kg of 1-allyl-3-vinyl imidazole chloride salt into 14kg of high boiling point solvent, adding 0.01kg of initiator, stirring and reacting for 4.5 hours at 83 ℃ under argon atmosphere, then precipitating in water, washing the precipitated product with ethanol for 5 times, and then placing in a vacuum drying oven for drying at 88 ℃ to constant weight; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 1:1: 2; the initiator is a mixture formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5;
II, ion exchange: soaking 1kg of the addition polymer prepared in the step I in 28kg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline disodium sulfonate salt solution with the mass fraction of 18%, performing ion exchange for 28 hours at the temperature of 58 ℃, washing for 5 times, and then placing in a vacuum drying oven for drying at the temperature of 80-90 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: 1kg of 1,3, 5-tri (4-carboxyphenylethynyl) benzene, 1.44kg of p-cyanoaniline and 0.35kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline are added into 11.5kg of ethanol, stirred and reacted for 23 hours at room temperature, then the solvent is removed by suction filtration, the product is washed for 5 times by diethyl ether, and the residual diethyl ether is removed by rotary evaporation;
IV Tb-Eu-Re-O preparation: adding 100g of terbium nitrate, 100g of europium nitrate, 100g of rhenium (III) chloride and 50g of sodium hydroxide into 2900g of deionized water, ultrasonically dispersing for 25 minutes, then adding 25g of citric acid, magnetically stirring for 14 minutes to obtain a mixed solution, then placing the mixed solution into a microwave oven, continuously reacting for 29 minutes under the condition that the microwave power is 450W, then cooling to room temperature, centrifugally separating, washing for 5 times by using deionized water, and drying to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: adding 1kg of the ion-exchanged addition polymer prepared in the step II, 0.01kg of the paracyanoaniline-modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step III, 0.01kg of Tb-Eu-Re-O prepared in the step IV and 0.005kg of silane coupling agent into a double-screw extruder, carrying out melt extrusion at 245 ℃, cooling and solidifying, and rolling by using a roller to obtain the blue light absorption layer.
The preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1.18kg of 1, 3-adamantanedicarboxylic acid and 1kg of dihydralazine into 11.5kg of N-methylpyrrolidone, adding 0.35kg of dicyclohexylcarbodiimide and 0.5kg of 4-dimethylaminopyridine into the mixture, stirring the mixture to react for 2.9 hours at 103 ℃ under a nitrogen atmosphere, stirring the mixture to react for 9.5 hours at 133 ℃, separating out the product in water after the reaction is finished, washing the separated product for 6 times by using ethanol, and drying the product in a vacuum drying oven at 93 ℃ to constant weight;
step S2: adding 1kg of transparent nylon, 0.1kg of polycondensate prepared in the step S1 and 0.01kg of compatilizer into a double-screw extruder, carrying out melt extrusion at 245 ℃, cooling and solidifying, and rolling by using a roller to obtain a wear-resistant layer; the compatilizer is a mixture formed by mixing PE-g-ST, PP-g-ST, ABS-g-MAH and PE-g-MAH according to the mass ratio of 1:2:1: 1.
Example 5
A film material for an eye-protecting computer screen comprises a wear-resistant layer, a blue light absorption layer and a release protection film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protection film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
The transparent adhesive layer is prepared from an acrylate adhesive.
The release protective film layer is made of polyethylene terephthalate.
The preparation method of the blue light absorption layer comprises the following steps:
i preparation of addition polymer: adding 0.5kg of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, 1kg of acrylonitrile, 1kg of ethylene carbonate and 0.3kg of 1-allyl-3-vinyl imidazole chloride salt into 15kg of N, N-dimethylformamide, adding 0.01kg of azobisisoheptonitrile into the mixture, stirring the mixture for reaction for 5 hours at 85 ℃ under the nitrogen atmosphere, then precipitating the mixture in water, washing the precipitated product for 5 times by using ethanol, and then placing the product in a vacuum drying oven for drying at 90 ℃ to constant weight;
II, ion exchange: soaking 1kg of the addition polymer prepared in the step I in 30kg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt solution with the mass fraction of 20%, performing ion exchange for 30 hours at the temperature of 60 ℃, washing with water for 5 times, and then placing in a vacuum drying oven for drying at the temperature of 90 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: adding 1kg of 1,3, 5-tri (4-carboxyphenylethynyl) benzene, 1.44kg of p-cyanoaniline and 0.4kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline into 12kg of ethanol, stirring and reacting for 24 hours at room temperature, then removing the solvent by suction filtration, washing the product for 5 times by using diethyl ether, and then removing the residual diethyl ether by rotary evaporation;
IV Tb-Eu-Re-O preparation: adding 100g of terbium nitrate, 100g of europium nitrate, 100g of rhenium (III) chloride and 50g of sodium hydroxide into 3000g of deionized water, ultrasonically dispersing for 30 minutes, then adding 25g of citric acid, magnetically stirring for 15 minutes to obtain a mixed solution, then placing the mixed solution into a microwave oven, continuously reacting for 30 minutes under the condition that the microwave power is 500W, then cooling to room temperature, centrifugally separating, washing for 5 times by using deionized water, and drying to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: adding 1kg of the ion-exchanged addition polymer prepared in the step II, 0.01kg of the paracyanoaniline-modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step III, 0.01kg of Tb-Eu-Re-O prepared in the step IV and 0.005kg of silane coupling agent into a double-screw extruder, carrying out melt extrusion at 250 ℃, cooling and solidifying, and rolling by using a roller to obtain the blue light absorption layer.
The preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1.18kg of 1, 3-adamantanedicarboxylic acid and 1kg of dihydralazine into 12kg of N-methylpyrrolidone, adding 0.4kg of dicyclohexylcarbodiimide and 0.5kg of 4-dimethylaminopyridine into the mixture, stirring the mixture to react for 3 hours at 105 ℃ under the nitrogen atmosphere, stirring the mixture to react for 10 hours at 135 ℃, separating out the product in water after the reaction is finished, washing the separated product for 6 times by using ethanol, and drying the product in a vacuum drying oven at 95 ℃ to constant weight;
step S2: adding 1kg of transparent nylon, 0.1kg of polycondensate prepared in the step S1 and 0.01kg of compatilizer PE-g-MAH into a double-screw extruder, carrying out melt extrusion at 250 ℃, cooling and solidifying, and rolling by using a roller to obtain the wear-resistant layer.
Comparative example
A protective film for preventing blue light and blocking ultraviolet rays is disclosed according to the embodiment of the Chinese invention patent CN 105385376B.
The membranes described in examples 1-5 and comparative examples above were tested for performance, the results and methods are shown in Table 1.
TABLE 1
As can be seen from table 1, the film material for an eye-protecting computer screen disclosed in the embodiments of the present invention has more excellent uv and blue light absorption rates, and greater peel strength and hardness than the comparative products.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A film material for an eye-protecting computer screen is characterized by comprising a wear-resistant layer, a blue light absorption layer and a release protective film layer which are sequentially arranged from top to bottom, wherein the wear-resistant layer is connected with the blue light absorption layer, and the blue light absorption layer is connected with the release protective film layer through respective independent transparent adhesive layers; the blue light absorption layer is prepared by taking an addition polymer formed by polymerizing monomers of tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt as a base material, carrying out ion exchange on the addition polymer and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt, and then adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and a silane coupling agent KH560 modified by cyananiline; the wear-resistant layer is prepared by blending transparent nylon, 1, 3-adamantanedicarboxylic acid and a polycondensation product of dihydralazine.
2. The film material for an eye-protecting computer screen of claim 1, wherein the transparent adhesive layer is prepared from a material comprising at least one of an acrylate adhesive, a polyurethane adhesive, and a silicone rubber adhesive; the preparation material of the release protective film layer comprises at least one of polymethyl methacrylate, polycarbonate, polystyrene and polyethylene terephthalate.
3. The film material for an eye-protecting computer screen of claim 1, wherein the preparation method of the blue light absorption layer comprises the following steps:
i preparation of addition polymer: adding tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, acrylonitrile, ethylene carbonate and 1-allyl-3-vinyl imidazole chloride salt into a high boiling point solvent, adding an initiator into the solvent, stirring the mixture for reaction for 3 to 5 hours at 75 to 85 ℃ under the atmosphere of nitrogen or inert gas, then precipitating the mixture in water, washing the precipitated product for 3 to 5 times by using ethanol, and then drying the product in a vacuum drying oven at 80 to 90 ℃ to constant weight;
II, ion exchange: soaking the addition polymer prepared in the step I in 10-20% by mass of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline disodium sulfonate salt solution, performing ion exchange for 20-30 hours at 50-60 ℃, washing for 3-5 times, and drying in a vacuum drying oven at 80-90 ℃ to constant weight;
III preparation of p-cyanoaniline modified 1,3, 5-tris (4-carboxyphenylethynyl) benzene: adding 1,3, 5-tri (4-carboxyphenylethynyl) benzene, p-cyananiline, 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline into ethanol, stirring and reacting at room temperature for 20-24 hours, then carrying out suction filtration to remove the solvent, washing the product with diethyl ether for 3-5 times, and then carrying out rotary evaporation to remove residual diethyl ether;
IV Tb-Eu-Re-O preparation: terbium nitrate, europium nitrate, rhenium (III) chloride and sodium hydroxide are added into deionized water, ultrasonic dispersion is carried out for 15-30 minutes, then citric acid is added, magnetic stirring is carried out for 10-15 minutes to obtain a mixed solution, then the mixed solution is placed into a microwave oven, continuous reaction is carried out for 25-30 minutes under the condition that the microwave power is 300-500W, then cooling is carried out to room temperature, centrifugal separation is carried out, deionized water is used for washing for 3-5 times, and drying is carried out to obtain Tb-Eu-Re-O;
v blue light absorption layer forming: and (3) adding the addition polymer after ion exchange prepared in the step (II), the paracyanoaniline modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene prepared in the step (III), Tb-Eu-Re-O prepared in the step (IV) and a silane coupling agent KH560 into a double-screw extruder, melting and extruding at the temperature of 220-250 ℃, cooling and solidifying, and rolling by using a roller to obtain the blue light absorption layer.
4. The membrane material for an eye-protecting computer screen as claimed in claim 3, wherein the mass ratio of the tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, the acrylonitrile, the ethylene carbonate, the 1-allyl-3-vinyl imidazole chloride salt, the high boiling point solvent and the initiator in the step I is 0.5:1:1:0.3 (10-15: 0.01); the high boiling point solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile; the inert gas is selected from helium, neon and argon.
5. The film material for an eye-protecting computer screen as claimed in claim 3, wherein the mass ratio of the addition polymer to the 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline disodium sulfonate salt solution in the step II is 1 (20-30); in the step III, the mass ratio of the 1,3, 5-tri (4-carboxyphenylethynyl) benzene, the p-cyananiline, the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline and the ethanol is 1:1.44 (0.2-0.4) to (10-12).
6. The film material for an eye-protecting computer screen according to claim 3, wherein the mass ratio of terbium nitrate, europium nitrate, rhenium (III) chloride, sodium hydroxide, deionized water and citric acid in the step IV is 1:1:1:0.5 (20-30) to 0.25; and the mass ratio of the addition polymer subjected to ion exchange, the cyanoaniline modified 1,3, 5-tri (4-carboxyphenylethynyl) benzene, Tb-Eu-Re-O and the silane coupling agent KH560 in the step V is 1:0.01:0.01: 0.005.
7. The film material for an eye-protecting computer screen of claim 1, wherein the preparation method of the wear-resistant layer comprises the following steps:
step S1: adding 1, 3-adamantanedicarboxylic acid and dihydrazino phthalazine into N-methylpyrrolidone, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine into the N-methylpyrrolidone, stirring and reacting for 2-3 hours at 95-105 ℃ in a nitrogen atmosphere, stirring and reacting for 8-10 hours at 125-135 ℃, separating out the product in water after the reaction is finished, washing the separated product with ethanol for 4-6 times, and drying the product in a vacuum drying oven at 85-95 ℃ to constant weight;
step S2: adding the transparent nylon, the polycondensate prepared in the step S1 and the compatilizer into a double-screw extruder, performing melt extrusion at the temperature of 220-250 ℃, cooling and solidifying, and performing roller calendering to obtain the wear-resistant layer.
8. The film material for an eye-protecting computer screen as claimed in claim 7, wherein the mass ratio of the 1, 3-adamantanedicarboxylic acid, dihydralazine, N-methylpyrrolidone, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in step S1 is 1.18:1 (10-12): 0.2-0.4: 0.5.
9. The film material for an eye-protecting computer screen of claim 7, wherein the mass ratio of the nylon, the condensation polymer and the compatilizer in the step S2 is 1:0.1: 0.01.
10. The film material for an eye-protecting computer screen as claimed in claim 7, wherein the compatilizer is one or more selected from PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN203625298U (en) * | 2013-12-04 | 2014-06-04 | 东莞市纳利光学材料有限公司 | Blue light resisting protective film |
| CN205130536U (en) * | 2015-10-28 | 2016-04-06 | 东莞市纳利光学材料有限公司 | Anti electromagnetic wave of anti blue light has substrate AB glue membrane |
| CN107283981A (en) * | 2017-07-05 | 2017-10-24 | 杨建� | A kind of blue light Obstruct membrane and preparation method thereof |
| CN108997949A (en) * | 2018-08-03 | 2018-12-14 | 深圳市翰博士科技有限公司 | A kind of touch screen screen protection glass of anti-blue light and preparation method thereof |
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| EP1472319A1 (en) * | 2002-01-04 | 2004-11-03 | University Of Dayton | Non-toxic corrosion protection pigments based on cobalt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203625298U (en) * | 2013-12-04 | 2014-06-04 | 东莞市纳利光学材料有限公司 | Blue light resisting protective film |
| CN205130536U (en) * | 2015-10-28 | 2016-04-06 | 东莞市纳利光学材料有限公司 | Anti electromagnetic wave of anti blue light has substrate AB glue membrane |
| CN107283981A (en) * | 2017-07-05 | 2017-10-24 | 杨建� | A kind of blue light Obstruct membrane and preparation method thereof |
| CN108997949A (en) * | 2018-08-03 | 2018-12-14 | 深圳市翰博士科技有限公司 | A kind of touch screen screen protection glass of anti-blue light and preparation method thereof |
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