CN109810647A - A kind of eyeshield computer screen membrane material - Google Patents
A kind of eyeshield computer screen membrane material Download PDFInfo
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- CN109810647A CN109810647A CN201910081796.0A CN201910081796A CN109810647A CN 109810647 A CN109810647 A CN 109810647A CN 201910081796 A CN201910081796 A CN 201910081796A CN 109810647 A CN109810647 A CN 109810647A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 121
- 238000010521 absorption reaction Methods 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 238000005342 ion exchange Methods 0.000 claims abstract description 32
- 230000001681 protective effect Effects 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 18
- RPTUSVTUFVMDQK-UHFFFAOYSA-N Hidralazin Chemical compound C1=CC=C2C(NN)=NN=CC2=C1 RPTUSVTUFVMDQK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960002877 dihydralazine Drugs 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
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000012790 adhesive layer Substances 0.000 claims abstract description 15
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004677 Nylon Substances 0.000 claims abstract description 11
- 229920001778 nylon Polymers 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 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
- JLXXLCJERIYMQG-UHFFFAOYSA-N phenylcyanamide Chemical compound N#CNC1=CC=CC=C1 JLXXLCJERIYMQG-UHFFFAOYSA-N 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 20
- 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
- 235000010290 biphenyl Nutrition 0.000 claims description 17
- 239000004305 biphenyl Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000004781 supercooling Methods 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
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- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 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
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 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 8
- 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 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
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- 238000003490 calendering Methods 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 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
- 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
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910052771 Terbium Inorganic materials 0.000 claims 1
- 238000012644 addition polymerization Methods 0.000 claims 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- JKRHDMPWBFBQDZ-UHFFFAOYSA-N n'-hexylmethanediimine Chemical compound CCCCCCN=C=N JKRHDMPWBFBQDZ-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
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- 239000000243 solution Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- CBDRQDHBLUNMDT-UHFFFAOYSA-N [Re+3] Chemical compound [Re+3] CBDRQDHBLUNMDT-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 3
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- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 210000001525 retina Anatomy 0.000 description 2
- OGZUGPOTBGMCLE-UHFFFAOYSA-N 4-(2-phenylethynyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC1=CC=CC=C1 OGZUGPOTBGMCLE-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
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- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of eyeshield computer screen membrane materials; including the wearing layer, blue absorption layer, release protective film layer set gradually from top to bottom; between the wearing layer and blue absorption layer, connected respectively by transparent adhesive layer independent between blue absorption layer and release protective film layer；The blue absorption layer is to polymerize the addition polymers to be formed as substrate using monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile, vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, ion exchange again is prepared after adding additive；The wearing layer is blended and is prepared with the polycondensation product of nepresol by transparent nylon, 1,3- adamantane acid.The invention also discloses the preparation methods of the eyeshield computer screen membrane material.Eyeshield computer screen membrane material eyeshield significant effect that the present invention is prepared, crocking resistance are good, and while guaranteeing beneficial to blue light high transmittance, the transmitance of harmful blue light can be effectively reduced.
Description
Technical field
The present invention relates to film field of display technology more particularly to a kind of applied to the optically thin of computer screen eyeshield anti-blue light
Film.
Background technique
With advances in technology and electronic digital product it is universal, electronic equipment has become people's daily life must not
The articles that can lack are typically equipped with liquid crystal display on these electronic equipments, and liquid crystal display utilizes the physical characteristic of liquid crystal,
Arrangement becomes orderly, light to be made to be easy to pass through when energization, and fall into disarray when no power prevents light from passing through.Computer is exactly this kind of
One of the most common type in electronic equipment, when in use, computer screen can issue a large amount of high energy shortwave blue light, these blue lights to computer
Our eyes of prolonged exposure, can cause the functional disturbance of eyes, these blue lights with very high energies can penetrate crystalline lens
Through retina, causes photochemistry to damage in retina, directly or indirectly leads to the damage of macular area cell.Therefore, how will
The blue light that these device screens issue filters out a part, will be very useful to the protection of skin and eyes.
The irradiation for a long time of barrier blue light is to reduce damage most effectual way, and can effectively solve this using film for eye
Point.However, the generally existing complex process of existing anti-blue light eyeshield protective film, at high cost, blue light and absorption of UV and thoroughly
The low disadvantage of luminosity leads to object in addition, it can also reflect while absorbing harmful blue light or sponge beneficial to blue light
The display distortion of color.
Application No. is 201410238605.4 Chinese patent literatures to report a kind of eyeglass anti-blue light film, including following heavy
Measure the component of ratio: tin oxide 30%-60%；Rubidium 10%-40%；Platinum 10%-40%.It, can be effective by adding metallic element
Isolation ultraviolet and also can filtration fraction harmful blue light, mitigate stimulation of the blue light to eyes, eliminate sour and astringent eyes, fever or
The malaise symptoms such as person's pain, relieving eye strain.But the eyeglass anti-blue light film is formed using vacuum vapour deposition, expensive process,
Adsorption capacity is not strong between metal and its oxide component and eyeglass, easy to fall off.
106366608 B of Chinese patent CN discloses a kind of anti-blue light polycarbonate membrane and preparation method thereof, Yi Zhongfang
Blue light polycarbonate membrane, includes: 75~90 parts of polycarbonate powder by weight, and 5~15 parts of anti-blue light nano particle, phase
Hold 2~5 parts of 2~5 parts of agent and other auxiliary agents；A kind of preparation method of anti-blue light polycarbonate membrane, comprises the following steps that:
A) mechanical premixing；B) melting mixing；C) cooling and dicing；D) extrusion molding, the final preparation for realizing product.The invention technique stream
Journey is simple, high production efficiency, at low cost, and film is good to the absorbent properties of blue light and ultraviolet light, and light transmittance is high, is used for electronic product
On, protection eyes can be played well to be avoided by the injury of high energy shortwave blue light, but anti-blue light nano particle therein and poly-
It is poor to close object matrix compatibility, dispersion is uneven, and exosmose, and blue light absorption effect can occur in the long-term use process
It is limited, and then influence eyeshield effect.
Therefore, it is good that a kind of eyeshield significant effect, crocking resistance are developed, while guaranteeing beneficial to blue light high transmittance,
The computer shielding protective film that the transmitance of harmful blue light can be effectively reduced accords with the demands of the market, and has extensive market value and answers
Use prospect.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of eyeshield computer screen membrane material, the eyeshield computer
Screen overcomes the generally existing complex process of traditional anti-blue light eyeshield protective film, at high cost, blue light and ultraviolet light with membrane material and inhales
Yield and light transmittance are low, can also reflect or sponged beneficial to blue light while absorbing harmful blue light, lead to object color
Display distortion the technical issues of, have eyeshield significant effect, crocking resistance good, guaranteeing beneficial to the same of blue light high transmittance
When, the advantages of transmitance of harmful blue light can be effectively reduced.
To achieve the above object of the invention, the technical solution adopted by the present invention is that,
A kind of eyeshield computer screen membrane material, including the wearing layer, blue absorption layer, release guarantor set gradually from top to bottom
Cuticular layer, between the wearing layer and blue absorption layer, respectively by respectively only between blue absorption layer and release protective film layer
Vertical transparent adhesive layer connection；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) it benzene, Tb-Eu-Re-O, is prepared after silane coupling agent KH560；The wearing layer is by transparent Buddhist nun
Dragon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
Further, the material for preparing of the transparent adhesive layer includes acrylate adhesive, adhesive for polyurethane, silicon
At least one of rubber adhesive.
Further, the material for preparing of the release protective film layer includes polymethyl methacrylate, polycarbonate, polyphenyl
At least one of ethylene, polyethylene terephthalate.
Preferably, the preparation method of the blue absorption layer, includes the following steps:
The preparation of I addition polymers: by four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile, vinylethylene carbonate, 1-
Allyl -3- vinyl imidazole villaumite is added in high boiling solvent, and initiator is added thereto, in nitrogen or inert gas
Be stirred to react at 75-85 DEG C of atmosphere 3-5 hours, after settle out in water, and be precipitated with ethanol washing again product 3-5 times, be placed on
It dries at 80-90 DEG C of vacuum oven to constant weight；
II ion exchange: the addition polymers being prepared by step I are immersed in the 2,9- bis- that mass fraction is 10-20%
In methyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid, carried out ion exchange 20-30 hours at 50-60 DEG C, after
It is washed with water 3-5 times, then is placed at 80-90 DEG C of vacuum oven and dries to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl of 1,3,5- tri-
Phenylene-ethynylene) benzene, cyano-aniline, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline are added in ethyl alcohol, in room
It is stirred to react under temperature 20-24 hours, rear filter removes solvent, and with ether washed product 3-5 times, then rotates removing residual second
Ether；
The preparation of IV Tb-Eu-Re-O: terbium nitrate, europium nitrate, chlorination rhenium (III), sodium hydroxide are added to deionized water
In, ultrasonic disperse 15-30 minutes, citric acid is added afterwards, obtains mixed solution within magnetic agitation 10-15 minutes, after by mixed solution
Be placed in micro-wave oven, microwave power be 300-500W under the conditions of sustained response 25-30 minute, after be cooled to room temperature, centrifugation divide
From, be washed with deionized water 3-5 times, it is dry, obtain Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers, by step III
What is be prepared is modified the Tb- that 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene, is prepared by step IV to cyano-aniline
Eu-Re-O, silane coupling agent KH560 are added in double screw extruder, solid by supercooling in 220-250 DEG C of melting extrusion
Change, obtain blue absorption layer after roll calendering.
Preferably, [4- (4'- carboxyl phenyl) phenyl] ethylene four described in step I, acrylonitrile, vinylethylene carbonate,
1- allyl -3- vinyl imidazole villaumite, high boiling solvent, initiator mass ratio be 0.5:1:1:0.3:(10-15):
0.01。
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is at least one；The initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile；The inert gas is selected from
One of helium, neon, argon gas.
Preferably, addition polymers described in step II, 2,9- dimethyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salt are molten
The mass ratio of liquid is 1:(20-30).
Preferably, (4- carboxyl phenyl acetenyl) benzene 1,3,5- tri- described in step III, to cyano-aniline, 2- ethyoxyl-
1- ethoxy carbonic acyl radical -1,2- dihydroquinoline, ethyl alcohol mass ratio be 1:1.44:(0.2-0.4): (10-12).
Preferably, terbium nitrate described in step IV, europium nitrate, chlorination rhenium (III), sodium hydroxide, deionized water, citric acid
Mass ratio be 1:1:1:0.5:(20-30): 0.25.
Preferably, the addition polymers after ion exchange described in step V, to modified 1,3,5- tri- (the 4- carboxyl benzene of cyano-aniline
Ethyl-acetylene base) benzene, Tb-Eu-Re-O, silane coupling agent KH560 mass ratio be 1:0.01:0.01:0.005.
Preferably, the preparation method of the wearing layer, includes the following steps:
Step S1: 1,3- adamantane acid, nepresol are added in N-Methyl pyrrolidone, then are added thereto
Dicyclohexylcarbodiimide, 4-dimethylaminopyridine are stirred to react 2-3 hours for 95-105 DEG C under nitrogen atmosphere, then in 125-
Be stirred to react at 135 DEG C 8-10 hours, after reaction, be precipitated in water, after with ethanol washing be precipitated product 4-6 times, then
It is placed at 85-95 DEG C of vacuum oven and dries to constant weight；
Step S2: transparent nylon, the condensation polymer being prepared by step S1, compatilizer are added to double screw extruder
In, in 220-250 DEG C of melting extrusion, wearing layer is obtained after rolling by supercooling solidification, roll.
Preferably, 1,3- adamantane acid, nepresol, N-Methyl pyrrolidone, dicyclohexyl described in step S1
Carbodiimide, 4-dimethylaminopyridine mass ratio be 1.18:1:(10-12): (0.2-0.4): 0.5.
Preferably, nylon described in step S2, condensation polymer, compatilizer mass ratio be 1:0.1:0.01；The compatilizer
Selected from one or more of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH.
The beneficial effects of adopting the technical scheme are that
1) eyeshield computer screen membrane material provided by the invention, raw material is easy to get, cheap, the membrane material gram being prepared
The generally existing complex process of traditional anti-blue light eyeshield protective film, at high cost, blue light and absorption of UV and light transmittance are taken
It is low, it can also reflect or sponged beneficial to blue light while absorbing harmful blue light, lead to the display distortion of object color
Technical problem has eyeshield significant effect, crocking resistance good, while guaranteeing beneficial to blue light high transmittance, can effectively drop
The advantages of transmitance of low harmful blue light.
2) eyeshield computer screen membrane material provided by the invention, including wearing layer, blue absorption layer, release protective film layer are more
Film structure to improve the comprehensive performance of membrane material, while reducing cost；Wearing layer uses transparent transparent nylon, 1,3-
Adamantane acid is blended with the polycondensation product of nepresol, under the premise of not influencing mist degree, improve film layer weatherability,
The performance of wearability, anti-fingerprint and dust；Blue absorption layer with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) benzene, Tb-Eu-Re-O, be prepared after silane coupling agent KH560, combine inorganic blue absorbent and
The advantages of organic absorbent, for synergistic effect so that anti-harmful blue light performance is stronger, especially first time is this with Tb-Eu-Re-O
Alloyed oxide obviously mentions together with modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of cyano-aniline with a conjugated structure
High anti-harmful blue light performance；Addition coupling agent makes Tb-Eu-Re-O dispersion more uniform, and compatibility is more preferable；Each tunic layer collaboration
Effect is so that membrane material light transmittance is high, other excellent combination properties good to the absorbent properties of blue light and ultraviolet light, service life compared with
It is long.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is purchased from shellfish (Shanghai) Biotechnology Co., Ltd that rubs.
Embodiment 1
A kind of eyeshield computer screen membrane material, including the wearing layer, blue absorption layer, release guarantor set gradually from top to bottom
Cuticular layer, between the wearing layer and blue absorption layer, respectively by respectively only between blue absorption layer and release protective film layer
Vertical transparent adhesive layer connection；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) it benzene, Tb-Eu-Re-O, is prepared after silane coupling agent KH560；The wearing layer is by transparent Buddhist nun
Dragon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
The material for preparing of the transparent adhesive layer is acrylate adhesive.
The material for preparing of the release protective film layer is polymethyl methacrylate.
The preparation method of the blue absorption layer, includes the following steps:
The preparation of I addition polymers: four [4- (4'- carboxyl phenyl) phenyl] ethylene 0.5kg, acrylonitrile 1kg, ethylene carbonate is sub-
Ethyl ester 1kg, 1- allyl -3- vinyl imidazole villaumite 0.3kg is added in dimethyl sulfoxide 10kg, and azo two is added thereto
Isobutyronitrile 0.01kg is stirred to react 3 hours at 75 DEG C of nitrogen atmosphere, after the production that settles out in water, and be precipitated with ethanol washing again
It object 3 times, is placed at 80 DEG C of vacuum oven and dries to constant weight；
II ion exchange: the addition polymers 1kg being prepared by step I is immersed in the 2,9- bis- that mass fraction is 10%
In methyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid 20kg, carried out ion exchange 20 hours at 50 DEG C, it is rear to use
Washing 3 times, then be placed at 80 DEG C of vacuum oven and dry to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl of 1,3,5- tri-
Phenylene-ethynylene) benzene 1kg, to cyano-aniline 1.44kg, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline 0.2kg be added
Into ethyl alcohol 10kg, reaction 20 hours is stirred at room temperature, rear filter removes solvent, and with ether washed product 3 times, then rotates
Remove residual ether；
The preparation of IV Tb-Eu-Re-O: by terbium nitrate 100g, europium nitrate 100g, chlorination rhenium (III) 100g, sodium hydroxide
50g is added in deionized water 2000g, ultrasonic disperse 15 minutes, rear that citric acid 25g is added, and is mixed within magnetic agitation 10 minutes
Close solution, after mixed solution is placed in micro-wave oven, microwave power be 300W under the conditions of sustained response 25 minutes, after be cooled to
Room temperature is centrifugated, is washed with deionized water 3 times, dry, obtains Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers 1kg, by step
III be prepared 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene 0.01kg modified to cyano-aniline, be prepared by step IV
To Tb-Eu-Re-O 0.01kg, silane coupling agent KH560 0.005kg be added in double screw extruder, 220 DEG C melt
It squeezes out, obtains blue absorption layer after rolling by supercooling solidification, roll.
The preparation method of the wearing layer, includes the following steps:
Step S1: 1,3- adamantane acid 1.18kg, nepresol 1kg are added to N-Methyl pyrrolidone 10kg
In, then dicyclohexylcarbodiimide 0.2kg, 4-dimethylaminopyridine 0.5kg are added thereto, 95 DEG C of stirrings under nitrogen atmosphere
Reaction 2 hours, then is stirred to react 8 hours at 125 DEG C, after reaction, is precipitated in water, after the production that is precipitated with ethanol washing
Object 4 times, then be placed at 85 DEG C of vacuum oven and dry to constant weight；
Step S2: by transparent nylon 1kg, the condensation polymer 0.1kg, the compatilizer PE-g-ST that are prepared by step S1
0.01kg is added in double screw extruder, wear-resisting by obtaining after supercooling solidification, roll calendering in 220 DEG C of melting extrusions
Layer.
Embodiment 2
A kind of eyeshield computer screen membrane material, including the wearing layer, blue absorption layer, release guarantor set gradually from top to bottom
Cuticular layer, between the wearing layer and blue absorption layer, respectively by respectively only between blue absorption layer and release protective film layer
Vertical transparent adhesive layer connection；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) it benzene, Tb-Eu-Re-O, is prepared after silane coupling agent KH560；The wearing layer is by transparent Buddhist nun
Dragon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
The material for preparing of the transparent adhesive layer is adhesive for polyurethane.
The material for preparing of the release protective film layer is polycarbonate.
The preparation method of the blue absorption layer, includes the following steps:
The preparation of I addition polymers: four [4- (4'- carboxyl phenyl) phenyl] ethylene 0.5kg, acrylonitrile 1kg, ethylene carbonate is sub-
Ethyl ester 1kg, 1- allyl -3- vinyl imidazole villaumite 0.3kg is added in n,N-Dimethylformamide 11kg, and is added thereto
Enter azobisisoheptonitrile 0.01kg, be stirred to react at 75-85 DEG C of helium atmosphere 3-5 hours, after settle out in water again, and use ethyl alcohol
Product 3-5 times of washing precipitation is placed at 80-90 DEG C of vacuum oven and dries to constant weight；
II ion exchange: the addition polymers 1kg being prepared by step I is immersed in the 2,9- bis- that mass fraction is 12%
In methyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid 22kg, carried out ion exchange 22 hours at 52 DEG C, it is rear to use
Washing 4 times, then be placed at 82 DEG C of vacuum oven and dry to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl of 1,3,5- tri-
Phenylene-ethynylene) benzene 1kg, cyano-aniline 1.44kg, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline 0.25kg is added
Entering into ethyl alcohol 10.5kg, reaction 21 hours is stirred at room temperature, rear filter removes solvent, and with ether washed product 4 times, then
Revolving removes residual ether；
The preparation of IV Tb-Eu-Re-O: by terbium nitrate 100g, europium nitrate 100g, chlorination rhenium (III) 100g, sodium hydroxide
50g is added in deionized water 2300g, ultrasonic disperse 18 minutes, rear that citric acid 25g is added, and is mixed within magnetic agitation 11 minutes
Close solution, after mixed solution is placed in micro-wave oven, microwave power be 350W under the conditions of sustained response 26 minutes, after be cooled to
Room temperature is centrifugated, is washed with deionized water 4 times, dry, obtains Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers 1kg, by step
III be prepared 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene 0.01kg modified to cyano-aniline, be prepared by step IV
To Tb-Eu-Re-O 0.01kg, silane coupling agent KH560 0.005kg be added in double screw extruder, 230 DEG C melt
It squeezes out, obtains blue absorption layer after rolling by supercooling solidification, roll.
The preparation method of the wearing layer, includes the following steps:
Step S1: 1,3- adamantane acid 1.18kg, nepresol 1kg are added to N-Methyl pyrrolidone 10.5kg
In, then dicyclohexylcarbodiimide 0.25kg, 4-dimethylaminopyridine 0.5kg are added thereto, it stirs for 97 DEG C under nitrogen atmosphere
Mix reaction 2.3 hours, then be stirred to react at 127 DEG C 8.5 hours, after reaction, is precipitated in water, after analysed with ethanol washing
Product out 5 times, then be placed at 87 DEG C of vacuum oven and dry to constant weight；
Step S2: by transparent nylon 1kg, the condensation polymer 0.1kg, the compatilizer PP-g-ST that are prepared by step S1
0.01kg is added in double screw extruder, wear-resisting by obtaining after supercooling solidification, roll calendering in 230 DEG C of melting extrusions
Layer.
Embodiment 3
A kind of eyeshield computer screen membrane material, including the wearing layer, blue absorption layer, release guarantor set gradually from top to bottom
Cuticular layer, between the wearing layer and blue absorption layer, respectively by respectively only between blue absorption layer and release protective film layer
Vertical transparent adhesive layer connection；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) it benzene, Tb-Eu-Re-O, is prepared after silane coupling agent KH560；The wearing layer is by transparent Buddhist nun
Dragon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
The material for preparing of the transparent adhesive layer is silicone rubber adhesive.
The material for preparing of the release protective film layer is polystyrene.
The preparation method of the blue absorption layer, includes the following steps:
The preparation of I addition polymers: four [4- (4'- carboxyl phenyl) phenyl] ethylene 0.5kg, acrylonitrile 1kg, ethylene carbonate is sub-
Ethyl ester 1kg, 1- allyl -3- vinyl imidazole villaumite 0.3kg is added in N-Methyl pyrrolidone 12kg, and is added thereto
Azodiisobutyronitrile 0.01kg is stirred to react 4 hours at 80 DEG C of neon atmosphere, after settle out in water again, and analysed with ethanol washing
Product out 4 times is placed at 85 DEG C of vacuum oven and dries to constant weight；
II ion exchange: the addition polymers 1kg being prepared by step I is immersed in the 2,9- bis- that mass fraction is 15%
In methyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid 25kg, carried out ion exchange 25 hours at 55 DEG C, it is rear to use
Washing 4 times, then be placed at 85 DEG C of vacuum oven and dry to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl of 1,3,5- tri-
Phenylene-ethynylene) benzene 1kg, to cyano-aniline 1.44kg, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline 0.3kg be added
Into ethyl alcohol 11kg, reaction 22 hours is stirred at room temperature, rear filter removes solvent, and with ether washed product 4 times, then rotates
Remove residual ether；
The preparation of IV Tb-Eu-Re-O: by terbium nitrate 100g, europium nitrate 100g, chlorination rhenium (III) 100g, sodium hydroxide
50g is added in deionized water 2700g, ultrasonic disperse 25 minutes, rear that citric acid 25g is added, and is mixed within magnetic agitation 13 minutes
Close solution, after mixed solution is placed in micro-wave oven, microwave power be 400W under the conditions of sustained response 28 minutes, after be cooled to
Room temperature is centrifugated, is washed with deionized water 4 times, dry, obtains Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers 1kg, by step
III be prepared 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene 0.01kg modified to cyano-aniline, be prepared by step IV
To Tb-Eu-Re-O 0.01kg, silane coupling agent KH560 0.005kg be added in double screw extruder, 240 DEG C melt
It squeezes out, obtains blue absorption layer after rolling by supercooling solidification, roll.
The preparation method of the wearing layer, includes the following steps:
Step S1: 1,3- adamantane acid 1.18kg, nepresol 1kg are added to N-Methyl pyrrolidone 11kg
In, then dicyclohexylcarbodiimide 0.3kg, 4-dimethylaminopyridine 0.5kg are added thereto, it stirs for 100 DEG C under nitrogen atmosphere
Mix reaction 2.6 hours, then be stirred to react at 130 DEG C 9 hours, after reaction, is precipitated in water, after be precipitated with ethanol washing
Product 5 times, then be placed at 90 DEG C of vacuum oven and dry to constant weight；
Step S2: by transparent nylon 1kg, the condensation polymer 0.1kg, the compatilizer ABS-g-MAH that are prepared by step S1
0.01kg is added in double screw extruder, wear-resisting by obtaining after supercooling solidification, roll calendering in 240 DEG C of melting extrusions
Layer.
Embodiment 4
A kind of eyeshield computer screen membrane material, including the wearing layer, blue absorption layer, release guarantor set gradually from top to bottom
Cuticular layer, between the wearing layer and blue absorption layer, respectively by respectively only between blue absorption layer and release protective film layer
Vertical transparent adhesive layer connection；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) it benzene, Tb-Eu-Re-O, is prepared after silane coupling agent KH560；The wearing layer is by transparent Buddhist nun
Dragon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
The material for preparing of the transparent adhesive layer is acrylate adhesive, adhesive for polyurethane, silicone rubber adhesive
The mixture that 1:2:3 in mass ratio is mixed.
The material for preparing of the release protective film layer is polymethyl methacrylate, polycarbonate, polystyrene, gathers to benzene
The mixture that dioctyl phthalate second diester 1:1:2:1 in mass ratio is mixed.
The preparation method of the blue absorption layer, includes the following steps:
The preparation of I addition polymers: four [4- (4'- carboxyl phenyl) phenyl] ethylene 0.5kg, acrylonitrile 1kg, ethylene carbonate is sub-
Ethyl ester 1kg, 1- allyl -3- vinyl imidazole villaumite 0.3kg is added in high boiling solvent 14kg, and is added causes thereto
Agent 0.01kg is stirred to react 4.5 hours at 83 DEG C of argon atmosphere, after the product 5 that settles out in water, and be precipitated with ethanol washing again
It is secondary, it is placed at 88 DEG C of vacuum oven and dries to constant weight；The high boiling solvent is dimethyl sulfoxide, N, N- dimethyl formyl
The mixture that amine, N-Methyl pyrrolidone 1:1:2 in mass ratio are mixed；The initiator is azodiisobutyronitrile, azo
The mixture that two different heptonitrile 3:5 in mass ratio are mixed；
II ion exchange: the addition polymers 1kg being prepared by step I is immersed in the 2,9- bis- that mass fraction is 18%
In methyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid 28kg, carried out ion exchange 28 hours at 58 DEG C, it is rear to use
Washing 5 times, then be placed at 80-90 DEG C of vacuum oven and dry to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl of 1,3,5- tri-
Phenylene-ethynylene) benzene 1kg, cyano-aniline 1.44kg, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline 0.35kg is added
Entering into ethyl alcohol 11.5kg, reaction 23 hours is stirred at room temperature, rear filter removes solvent, and with ether washed product 5 times, then
Revolving removes residual ether；
The preparation of IV Tb-Eu-Re-O: by terbium nitrate 100g, europium nitrate 100g, chlorination rhenium (III) 100g, sodium hydroxide
50g is added in deionized water 2900g, ultrasonic disperse 25 minutes, rear that citric acid 25g is added, and is mixed within magnetic agitation 14 minutes
Close solution, after mixed solution is placed in micro-wave oven, microwave power be 450W under the conditions of sustained response 29 minutes, after be cooled to
Room temperature is centrifugated, is washed with deionized water 5 times, dry, obtains Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers 1kg, by step
III be prepared 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene 0.01kg modified to cyano-aniline, be prepared by step IV
To Tb-Eu-Re-O 0.01kg, silane coupling agent KH560 0.005kg be added in double screw extruder, 245 DEG C melt
It squeezes out, obtains blue absorption layer after rolling by supercooling solidification, roll.
The preparation method of the wearing layer, includes the following steps:
Step S1: 1,3- adamantane acid 1.18kg, nepresol 1kg are added to N-Methyl pyrrolidone 11.5kg
In, then dicyclohexylcarbodiimide 0.35kg, 4-dimethylaminopyridine 0.5kg are added thereto, it stirs for 103 DEG C under nitrogen atmosphere
Mix reaction 2.9 hours, then be stirred to react at 133 DEG C 9.5 hours, after reaction, is precipitated in water, after analysed with ethanol washing
Product out 6 times, then be placed at 93 DEG C of vacuum oven and dry to constant weight；
Step S2: it is added by transparent Buddhist nun 1kg dragon, by condensation polymer 0.1kg, compatilizer 0.01kg that step S1 is prepared
Into double screw extruder, in 245 DEG C of melting extrusions, wearing layer is obtained after rolling by supercooling solidification, roll；It is described compatible
Agent is the mixture that PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH 1:2:1:1 in mass ratio are mixed.
Embodiment 5
A kind of eyeshield computer screen membrane material, including the wearing layer, blue absorption layer, release guarantor set gradually from top to bottom
Cuticular layer, between the wearing layer and blue absorption layer, respectively by respectively only between blue absorption layer and release protective film layer
Vertical transparent adhesive layer connection；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile,
It is substrate that vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9- dimethyl -
After 4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salts carry out ion exchange, then add 1,3,5- tri- (4-s modified to cyano-aniline
Carboxyl phenyl acetenyl) it benzene, Tb-Eu-Re-O, is prepared after silane coupling agent KH560；The wearing layer is by transparent Buddhist nun
Dragon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
The material for preparing of the transparent adhesive layer is acrylate adhesive.
The material for preparing of the release protective film layer is polyethylene terephthalate.
The preparation method of the blue absorption layer, includes the following steps:
The preparation of I addition polymers: four [4- (4'- carboxyl phenyl) phenyl] ethylene 0.5kg, acrylonitrile 1kg, ethylene carbonate is sub-
Ethyl ester 1kg, 1- allyl -3- vinyl imidazole villaumite 0.3kg is added in n,N-Dimethylformamide 15kg, and is added thereto
Enter azobisisoheptonitrile 0.01kg, be stirred to react at 85 DEG C of nitrogen atmosphere 5 hours, after settle out in water again, and use ethanol washing
The product of precipitation 5 times is placed at 90 DEG C of vacuum oven and dries to constant weight；
II ion exchange: the addition polymers 1kg being prepared by step I is immersed in the 2,9- bis- that mass fraction is 20%
In methyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid 30kg, carried out ion exchange 30 hours at 60 DEG C, it is rear to use
Washing 5 times, then be placed at 90 DEG C of vacuum oven and dry to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl of 1,3,5- tri-
Phenylene-ethynylene) benzene 1kg, to cyano-aniline 1.44kg, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline 0.4kg be added
Into ethyl alcohol 12kg, reaction 24 hours is stirred at room temperature, rear filter removes solvent, and with ether washed product 5 times, then rotates
Remove residual ether；
The preparation of IV Tb-Eu-Re-O: by terbium nitrate 100g, europium nitrate 100g, chlorination rhenium (III) 100g, sodium hydroxide
50g is added in deionized water 3000g, ultrasonic disperse 30 minutes, rear that citric acid 25g is added, and is mixed within magnetic agitation 15 minutes
Close solution, after mixed solution is placed in micro-wave oven, microwave power be 500W under the conditions of sustained response 30 minutes, after be cooled to
Room temperature is centrifugated, is washed with deionized water 5 times, dry, obtains Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers 1kg, by step
III be prepared 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene 0.01kg modified to cyano-aniline, be prepared by step IV
To Tb-Eu-Re-O 0.01kg, silane coupling agent KH560 0.005kg be added in double screw extruder, 250 DEG C melt
It squeezes out, obtains blue absorption layer after rolling by supercooling solidification, roll.
The preparation method of the wearing layer, includes the following steps:
Step S1: 1,3- adamantane acid 1.18kg, nepresol 1kg are added to N-Methyl pyrrolidone 12kg
In, then dicyclohexylcarbodiimide 0.4kg, 4-dimethylaminopyridine 0.5kg are added thereto, it stirs for 105 DEG C under nitrogen atmosphere
Mix reaction 3 hours, then be stirred to react at 135 DEG C 10 hours, after reaction, is precipitated in water, after be precipitated with ethanol washing
Product 6 times, then be placed at 95 DEG C of vacuum oven and dry to constant weight；
Step S2: by transparent nylon 1kg, the condensation polymer 0.1kg, the compatilizer PE-g-MAH that are prepared by step S1
0.01kg is added in double screw extruder, wear-resisting by obtaining after supercooling solidification, roll calendering in 250 DEG C of melting extrusions
Layer.
Comparative example
A kind of anti-blue light and the protective film for obstructing ultraviolet light, according to 105385376 B embodiment of Chinese invention patent CN.
The film described in above-described embodiment 1-5 and comparative example is tested for the property, and test result and test method are shown in Table 1.
Table 1
As seen from Table 1, eyeshield computer screen membrane material disclosed by the embodiments of the present invention, compared with the product of comparative example, tool
There are more excellent ultraviolet light and blue light absorption rate, bigger peel strength and hardness.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of eyeshield computer screen membrane material, which is characterized in that including set gradually from top to bottom wearing layer, blue light absorption
Layer, release protective film layer, between the wearing layer and blue absorption layer, lead to respectively between blue absorption layer and release protective film layer
Cross transparent adhesive layer connection independent；The blue absorption layer be with monomer four [4- (4'- carboxyl phenyl) phenyl] ethylene,
It is substrate that acrylonitrile, vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, which polymerize the addition polymers to be formed, with 2,9-
After dimethyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salt carries out ion exchange, then add to cyano-aniline modified 1,3,
It is prepared after 5- tri- (4- carboxyl phenyl acetenyl) benzene, Tb-Eu-Re-O, silane coupling agent KH560；The wearing layer be by
Transparent nylon, 1,3- adamantane acid are blended with the polycondensation product of nepresol and are prepared.
2. a kind of eyeshield computer screen membrane material according to claim 1, which is characterized in that the transparent adhesive layer
Preparing material includes at least one of acrylate adhesive, adhesive for polyurethane, silicone rubber adhesive；The release protection
Film layer prepare material include polymethyl methacrylate, polycarbonate, polystyrene, in polyethylene terephthalate extremely
Few one kind.
3. a kind of eyeshield computer screen membrane material according to claim 1, which is characterized in that the system of the blue absorption layer
Preparation Method includes the following steps:
The preparation of I addition polymers: by four [4- (4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile, vinylethylene carbonate, 1- allyl
Base -3- vinyl imidazole villaumite is added in high boiling solvent, and initiator is added thereto, in nitrogen or atmosphere of inert gases
Be stirred to react at 75-85 DEG C 3-5 hours, after settle out in water, and be precipitated with ethanol washing again product 3-5 times, be placed on vacuum
It dries at 80-90 DEG C of drying box to constant weight；
II ion exchange: the addition polymers being prepared by step I are immersed in the 2,9- diformazan that mass fraction is 10-20%
In base -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid, carried out ion exchange 20-30 hours at 50-60 DEG C, it is rear to use
Washing 3-5 times, then be placed at 80-90 DEG C of vacuum oven and dry to constant weight；
The preparation of modified 1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene of III pair of cyano-aniline: by (the 4- carboxyl phenyl of 1,3,5- tri-
Acetenyl) benzene, cyano-aniline, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline are added in ethyl alcohol, at room temperature
It is stirred to react 20-24 hours, rear filter removes solvent, and with ether washed product 3-5 times, then rotates removing residual ether；
The preparation of IV Tb-Eu-Re-O: terbium nitrate, europium nitrate, chlorination rhenium (III), sodium hydroxide are add to deionized water,
Ultrasonic disperse 15-30 minutes, citric acid is added afterwards, obtains mixed solution within magnetic agitation 10-15 minutes, after mixed solution is placed in
In micro-wave oven, microwave power be 300-500W under the conditions of sustained response 25-30 minutes, after be cooled to room temperature, be centrifugated, use
Deionization is washed 3-5 times, dry, obtains Tb-Eu-Re-O；
V blue light absorption formable layer: by after the ion exchange that step II is prepared addition polymers, prepare by step III
What is obtained is modified the Tb-Eu- that 1,3,5- tri- (4- carboxyl phenyl acetenyl) benzene, is prepared by step IV to cyano-aniline
Re-O, silane coupling agent KH560 are added in double screw extruder, in 220-250 DEG C of melting extrusion, solidify by supercooling,
Blue absorption layer is obtained after roll calendering.
4. a kind of eyeshield computer screen membrane material according to claim 3, which is characterized in that four [4- described in step I
(4'- carboxyl phenyl) phenyl] ethylene, acrylonitrile, vinylethylene carbonate, 1- allyl -3- vinyl imidazole villaumite, higher boiling
Solvent, initiator mass ratio be 0.5:1:1:0.3:(10-15): 0.01；The high boiling solvent is selected from dimethyl sulfoxide, N, N-
At least one of dimethylformamide, N-Methyl pyrrolidone；The initiator is selected from azodiisobutyronitrile, azo two different heptan
At least one of nitrile；The inert gas is selected from one of helium, neon, argon gas.
5. a kind of eyeshield computer screen membrane material according to claim 3, which is characterized in that addition polymerization described in step II
Object, 2,9- dimethyl -4,7- diphenyl -1,10- phenanthrene sulfonate moiety disodium salting liquid mass ratio be 1:(20-30)；In step III
1,3,5- tri- (the 4- carboxyl phenyl acetenyl) benzene, to cyano-aniline, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydro quinoline
Quinoline, ethyl alcohol mass ratio be 1:1.44:(0.2-0.4): (10-12).
6. a kind of eyeshield computer screen membrane material according to claim 3, which is characterized in that nitric acid described in step IV
Terbium, europium nitrate, chlorination rhenium (III), sodium hydroxide, deionized water, citric acid mass ratio be 1:1:1:0.5:(20-30):
0.25；It is addition polymers after ion exchange described in step V, modified 1,3,5- tri- (4- carboxyl phenyl acetenyl) to cyano-aniline
Benzene, Tb-Eu-Re-O, silane coupling agent KH560 mass ratio be 1:0.01:0.01:0.005.
7. a kind of eyeshield computer screen membrane material according to claim 1, which is characterized in that the preparation side of the wearing layer
Method includes the following steps:
Step S1: 1,3- adamantane acid, nepresol are added in N-Methyl pyrrolidone, then two rings are added thereto
Hexyl carbodiimide, 4-dimethylaminopyridine are stirred to react 2-3 hours for 95-105 DEG C under nitrogen atmosphere, then at 125-135 DEG C
Under be stirred to react 8-10 hours, after reaction, be precipitated in water, after with ethanol washing be precipitated product 4-6 time, then be placed in very
It dries at 85-95 DEG C of empty drying box to constant weight；
Step S2: transparent nylon, the condensation polymer being prepared by step S1, compatilizer are added in double screw extruder,
In 220-250 DEG C of melting extrusion, wearing layer is obtained after rolling by supercooling solidification, roll.
8. a kind of eyeshield computer screen membrane material according to claim 7, which is characterized in that the gold of 1,3- described in step S1
Rigid alkane dioctyl phthalate, nepresol, N-Methyl pyrrolidone, dicyclohexylcarbodiimide, 4-dimethylaminopyridine mass ratio be
1.18:1:(10-12):(0.2-0.4):0.5。
9. a kind of eyeshield computer screen membrane material according to claim 7, which is characterized in that nylon described in step S2,
Condensation polymer, compatilizer mass ratio be 1:0.1:0.01.
10. a kind of eyeshield computer screen membrane material according to claim 7, which is characterized in that the compatilizer is selected from PE-
One or more of g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040104377A1 (en) * | 2002-01-04 | 2004-06-03 | Phelps Andrew Wells | Non-toxic corrosion-protection pigments based on rare earth elements |
| 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 |
-
2019
- 2019-01-28 CN CN201910081796.0A patent/CN109810647B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040104377A1 (en) * | 2002-01-04 | 2004-06-03 | Phelps Andrew Wells | Non-toxic corrosion-protection pigments based on rare earth elements |
| 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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