CN117594735A - Laminated board and preparation method thereof - Google Patents
Laminated board and preparation method thereof Download PDFInfo
- Publication number
- CN117594735A CN117594735A CN202311549168.3A CN202311549168A CN117594735A CN 117594735 A CN117594735 A CN 117594735A CN 202311549168 A CN202311549168 A CN 202311549168A CN 117594735 A CN117594735 A CN 117594735A
- Authority
- CN
- China
- Prior art keywords
- modified
- nanotube array
- titanium dioxide
- acrylic plate
- acrylic
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- Granted
Links
- 238000002360 preparation method Methods 0.000 title abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000002071 nanotube Substances 0.000 claims abstract description 81
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 54
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 25
- 239000002096 quantum dot Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 239000004408 titanium dioxide Substances 0.000 claims description 28
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 26
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 20
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 20
- 229910021389 graphene Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002826 coolant Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 37
- 230000032683 aging Effects 0.000 abstract description 30
- 230000006750 UV protection Effects 0.000 abstract description 24
- 230000000052 comparative effect Effects 0.000 description 44
- 230000000903 blocking effect Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 230000002195 synergetic effect Effects 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000003491 array Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/552—Protection against radiation, e.g. light or electromagnetic waves
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/58—Structural electrical arrangements for semiconductor devices not otherwise provided for, e.g. in combination with batteries
- H01L23/60—Protection against electrostatic charges or discharges, e.g. Faraday shields
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/64—Heat extraction or cooling elements
- H01L33/641—Heat extraction or cooling elements characterized by the materials
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of display, in particular to a laminated board and a preparation method thereof. The laminated board comprises a quantum dot film, an acrylic board and an LED light source assembly, wherein the acrylic board comprises the following components in parts by weight: 100-200 parts of modified prepolymer and 20-50 parts of heat radiating agent, wherein the modified prepolymer comprises methyl methacrylate and modified cage-type silsesquioxane, and the heat radiating agent comprises anhydride grafted ethylene propylene diene monomer rubber and a modified titanium dioxide nanotube array. The acrylic plate has excellent ultraviolet resistance and ageing resistance and high light transmittance, and the luminous performance of the laminated plate is greatly improved.
Description
Technical Field
The invention relates to the technical field of display, in particular to a laminated board and a preparation method thereof.
Background
Light emitting diodes, abbreviated as LEDs, are a commonly used light emitting device that emits light by energy released by electron and hole recombination, and have a wide range of applications in modern society, such as lighting, flat panel display, and medical devices. Individual LEDs are not capable of meeting the needs of practical applications and need to be made into laminates with other components to function. The laminated board consists of a quantum dot film, an acrylic plate and an LED light source assembly, and the light source emitted by the LED is processed through the acrylic plate and the quantum dot film to obtain light meeting various requirements. The acrylic plate makes light scattered to each light guide point, and the LED uniformly emits light through the light guide points with different densities and sizes.
Currently, energy of a large specific gravity is converted into heat energy because photoelectric conversion efficiency is low. The acrylic plate in the laminated board is exposed to high temperature and light for a long time, is easy to age and yellow, and affects the luminous performance of the laminated board, so the luminous performance of the laminated board needs to be improved.
Disclosure of Invention
The laminated board and the preparation method thereof adopt the following technical scheme:
in a first aspect, the present application provides a laminated board, which adopts the following technical scheme:
a laminate, characterized in that: the laminated board comprises a quantum dot film, an acrylic board and an LED light source assembly, wherein the acrylic board comprises the following components in parts by mass:
100-200 parts of modified prepolymer
20-50 parts of heat radiating agent
The modified prepolymer comprises methyl methacrylate and modified cage-type silsesquioxane;
the heat-radiating agent comprises anhydride grafted ethylene propylene diene monomer rubber and a modified titanium dioxide nanotube array.
The modified cage type silsesquioxane has a porous structure, and the methyl methacrylate is modified by using the modified cage type silsesquioxane, so that the mechanical, heat-resistant and flame-retardant properties of the acrylic plate can be effectively improved; the anhydride grafted ethylene propylene diene monomer rubber in the heat-radiating agent has good elasticity, chemical corrosion resistance and ageing resistance, has lower surface energy and certain hydrophobicity, and the heat-radiating agent obtained by compounding the modified titanium dioxide nanotube array has a structure with high porosity, so that the hydrophobicity of an acrylic plate is improved, and the acrylic plate has the functions of radiation self-cooling and self-cleaning; under the synergistic effect of the modified cage-type silsesquioxane and the heat-resistant agent, the acrylic plate can disperse and absorb external ultraviolet rays in a high-temperature illumination environment, and the self-cooling function is realized, so that the influence of the overheat environment and the ultraviolet rays on the chemical component properties in the acrylic plate is reduced, and the ageing is delayed.
Preferably, the modified titanium dioxide nanotube array comprises: titanium flakes, graphene oxide, sodium borohydride, silver nitrate and a modifier.
The graphene has high light transmittance, and the surface is rich in a large number of active groups, so that the graphene can be easily combined with oxide nano materials to form a compound, and the nano silver can be uniformly attached to the surface of the titanium dioxide nanotube array; the nano silver and the graphene oxide have synergistic effect on the titanium dioxide nanotube array, can expand the light response range of the modified titanium dioxide nanotube array, better shield and reflect ultraviolet rays, quench active substances which can cause performance degradation on the surface of the acrylic plate and in the system, enable the acrylic plate to have self-cleaning capability and improve the ageing resistance of the acrylic plate. The modifier carries out covalent surface modification on the titanium dioxide nanotube array, provides reaction sites with other organic phases for the titanium dioxide nanotube array, improves the compatibility of the titanium dioxide nanotube array in a high polymer system, thereby improving the overall stability of the acrylic plate and delaying the aging of the acrylic plate.
Preferably, the modifier comprises sodium methoxide and phenylacetylene.
Sodium methoxide helps phenylacetylene to react, phenylacetylene reacts with hydroxyl on the surface of the titanium dioxide nanotube array to form alkenyl, covalent surface modification is carried out, nano metal ions are deposited on the surface of the titanium dioxide nanotube array, alkenyl can react with other organic phases, the organic phases and the inorganic phases form a whole, and the stability of an acrylic plate is improved, so that the mechanical property and the ageing resistance of the acrylic plate are improved.
Preferably, the modified titanium dioxide nanotube array is prepared by the following steps:
pretreating a titanium sheet to obtain a titanium dioxide sheet, calcining the titanium dioxide sheet to obtain an anatase type titanium dioxide nanotube array, and calcining the anatase type titanium dioxide nanotube array in ammonia gas to obtain a nitrogen doped-nanotube array;
dispersing graphene oxide in water to obtain graphene dispersion liquid, soaking a nitrogen doped-nanotube array in the graphene dispersion liquid to obtain a soaked matter, cleaning the soaked matter, and drying to obtain a graphene-nanotube array;
dispersing sodium borohydride and silver nitrate into an ethylene glycol aqueous solution to obtain a mixed solution, soaking a graphene-nanotube array in the mixed solution, cleaning and drying to obtain a silver-graphene-nanotube array;
dispersing phenylacetylene and sodium methoxide into alcohol to obtain a modified solution, soaking the silver-graphene-nanotube array in the modified solution, washing and drying to obtain the modified titanium dioxide nanotube array.
The modified titanium dioxide nanotube array reduces the influence of high temperature and illumination on the acrylic plate, and improves the ultraviolet resistance and ageing resistance of the acrylic plate; the porous structure enables the acrylic plate to have better light transmission performance and higher reflectivity, and can improve the fluorescence quantum yield of the laminated plate, thereby improving the luminous performance of the laminated plate.
Preferably, the anhydride grafted ethylene propylene diene monomer comprises ethylene propylene diene monomer, maleic anhydride and an initiator.
Ethylene propylene diene monomer is a good flexible toughening material and has good impact resistance and heat resistance; because the ethylene propylene diene monomer only contains C-C bonds and C-H bonds, the ethylene propylene diene monomer has the characteristic of infrared transparency, so that the energy absorption is less, and the reflectivity is higher; the anhydride group in the maleic anhydride can react with the hydroxyl on the surface of the ethylene propylene diene monomer molecule, and the maleic anhydride is used for grafting the ethylene propylene diene monomer, so that the thermal stability of the ethylene propylene diene monomer can be improved; the maleic anhydride can also perform addition reaction with alkenyl on the surface of the modified titanium dioxide nanotube array, so that the organic phase and the inorganic phase form a whole with good compatibility, the dispersibility of the coolant in the system is improved, the overall stability of the acrylic plate under high temperature and illumination conditions is improved, and the ageing resistance of the acrylic plate is improved.
Preferably, the mass ratio of the ethylene propylene diene monomer to the maleic anhydride to the initiator is 1: (0.05-0.15): 0.05.
the ethylene propylene diene monomer obtained according to the mass ratio has better heat resistance and compatibility.
Preferably, the initiator comprises benzoyl peroxide.
Benzoyl peroxide can be used as an initiator to initiate the grafting reaction of maleic anhydride and ethylene propylene diene monomer; the benzoyl peroxide can enhance the compatibility between the anhydride grafted ethylene propylene diene monomer and methyl methacrylate, promote the crosslinking between the two, and enhance the mechanical property of the acrylic plate.
Preferably, the modified cage silsesquioxane includes KH-550 and hexachlorocyclotriphosphazene.
KH-550 and hexachlorocyclotriphosphazene react to obtain modified cage-type silsesquioxane, so that the modified cage-type silsesquioxane realizes the synergistic promotion of the flame retardant effect of N, P, si elements, and simultaneously improves the thermal, mechanical and other properties of an acrylic plate; hexachlorocyclotriphosphazene can also cooperate with benzoyl peroxide to improve the compatibility of modified cage-type silsesquioxane and anhydride grafted ethylene propylene diene monomer rubber, so that the mechanical property and ageing resistance of an acrylic plate are improved.
Preferably, the mass ratio of KH-550 to hexachlorocyclotriphosphazene is 1: (0.15-0.25).
The acrylic plate obtained according to the mass ratio has excellent mechanical property and ageing resistance.
In a second aspect, the present application provides a laminated board, which adopts the following technical scheme: the laminated board is prepared by the following steps:
blending modified cage-type silsesquioxane and methyl methacrylate to obtain a modified prepolymer, blending the modified prepolymer and a cooling agent, and performing mold filling sealing, polymerization and post-treatment procedures to obtain an acrylic plate;
coating the quantum dot film on an acrylic plate, heating, vacuumizing, and cooling to obtain the acrylic plate with the quantum dot film; and bonding one surface of the acrylic plate, which is far away from the quantum dot film, with the LED light source assembly, and standing to obtain the laminated board.
The modified cage-type silsesquioxane and the coolant both have porous structures, and the porous structures are added into an acrylic plate system to promote the formation of a more porous structure, so that the acrylic plate is endowed with lower dielectric constant by the porous structures, the antistatic performance of the acrylic plate is improved, the deposition of dust can be reduced, and the safety performance of the laminated plate is improved; under the synergistic effect of the modified cage-type silsesquioxane and the coolant, the stability and the light transmittance of an acrylic plate system are improved, so that the acrylic plate can uniformly guide out light, the fluorescence quantum yield of the laminated board is increased, and the light-emitting effect is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the modified cage-type silsesquioxane can effectively improve the mechanical, heat-resistant and flame-retardant properties of an acrylic plate; the heat-dissipating agent and the modified cage-type silsesquioxane have high-porosity structures, and under the synergistic effect, the acrylic plate has the functions of self-cooling and self-cleaning by radiation, and external ultraviolet rays can be scattered and absorbed in a high-temperature illumination environment, so that the influence of overheat environment and ultraviolet rays on chemical components in the acrylic plate is reduced, and the ultraviolet resistance and ageing resistance of the acrylic plate are improved.
2. The porous structure generated by phase separation of the anhydride grafted ethylene propylene diene monomer and the modified titanium dioxide nanotube array in the heat-radiating agent improves the reflectivity of light, combines the high infrared transmission characteristic of the ethylene propylene diene monomer and the high emission characteristic of the modified titanium dioxide nanotube array, improves the light transmission performance of the acrylic plate, ensures that the acrylic plate can realize uniform light guide by the excellent dispersibility of the heat-radiating agent, and improves the fluorescence quantum yield of the laminated plate, thereby improving the light-emitting performance of the laminated plate.
3. The porous structure of the modified cage-type silsesquioxane and the coolant endows the acrylic plate with lower dielectric constant, improves the antistatic performance of the acrylic plate, can reduce dust deposition, and improves the safety performance of the laminated plate.
Drawings
FIG. 1 is a cross-sectional view of a laminate in an embodiment of the present application.
Reference numerals illustrate: 1. a quantum dot film; 2. an acrylic plate; 3. an LED light source assembly.
Detailed Description
The present application discloses a laminate and a method for preparing the same, and the present application is further described in detail with reference to the following examples:
examples
Example 1
Preparation of modified titanium dioxide nanotube arrays
Polishing a titanium sheet (CAS number: 7440-32-6) with a size of 3cm x 3cm by using sand paper, then ultrasonically cleaning the titanium sheet by using deionized water for 10min, ultrasonically cleaning the titanium sheet by using absolute ethyl alcohol for 10min, then polishing the titanium sheet by using hydrofluoric acid solution with a volume ratio of 1% for 5min, finally ultrasonically cleaning the surface by using deionized water for 10min, and drying to obtain a pretreated titanium sheet; connecting a graphite electrode with a negative electrode of a direct current power supply, connecting a pretreated titanium sheet with a positive electrode of the direct current power supply, setting the output voltage of the direct current power supply to be 40V, then placing the whole device into a heat collection type constant temperature heating magnetic stirrer, setting the temperature to be 30 ℃, turning on the direct current power supply, and reacting for 2 hours to obtain a reacted titanium sheet; washing the reacted titanium sheet with distilled water, and drying with a blower to obtain the titanium dioxide sheet.
Placing the titanium dioxide sheet prepared by the steps into an integrated program-controlled high-temperature furnace, and calcining for 2 hours at 450 ℃ to obtain an anatase type titanium dioxide nanotube array; placing the anatase type titanium dioxide nanotube array into a tube furnace, and calcining for 2 hours at 550 ℃ in an ammonia atmosphere to obtain a nitrogen doped nanotube array; adding 0.5g of graphene oxide (CAS number: 1034343-98-0) into 50mL of deionized water, and performing ultrasonic dispersion for 1h to obtain graphene dispersion; soaking the nitrogen doped-nanotube array in graphene dispersion liquid for 3 hours to obtain a soaked matter, washing the soaked matter with deionized water, and drying in vacuum to obtain a graphene-nanotube array; adding 0.16g of sodium borohydride and 0.5g of silver nitrate into 50mL of solution with the volume ratio of water to glycol of 1:1 under the magnetic stirring condition, and uniformly stirring to obtain a mixed solution; soaking 10g of graphene-nanotube array in a mixed solution for 3 hours, washing the soaked graphene-nanotube array with deionized water, and drying in vacuum to obtain a silver-graphene-nanotube array; the silver-graphene-nanotube array is immersed in 50mL of methanol solution containing 100 mu L of phenylacetylene and 5mg of sodium methoxide, soaked for 2 hours at 50 ℃, washed with ethanol, and dried in nitrogen atmosphere to obtain the modified titanium dioxide nanotube array.
Preparation of anhydride grafted ethylene propylene diene monomer
Ethylene propylene diene monomer (CAS number: 23627-24-9) is dried in a vacuum drying oven at 80 ℃ for 2 hours to obtain dried ethylene propylene diene monomer, 15.4g of dried ethylene propylene diene monomer, 0.8g of maleic anhydride (CAS number: 108-31-6) and 0.8g of benzoyl peroxide (CAS number: 94-36-0) are weighed and put into a torque rheometer for melt blending for 10 minutes, and the temperature of 1-3 sections of an internal mixer is 190 ℃ and the rotating speed is 40r/min to obtain the anhydride grafted ethylene propylene diene monomer.
Preparation of a Heat-dissipating agent
16.1g of anhydride grafted ethylene propylene diene monomer, 3.1g of modified titanium dioxide nanotube array and 1.1g of xylene are mixed to obtain a mixture, and the mixture is heated in an oil bath at 60 ℃ for reaction to obtain the heat-dissipating agent.
Preparation of modified cage-type silsesquioxane
Sequentially adding 40mL of tetrahydrofuran, 8.75-gKH-550 and 4.4g of triethylamine into a 250mL three-neck flask, fully stirring to uniformly mix the materials, then introducing chlorine as a protective gas for the reaction, and slowly heating to 60 ℃; dissolving 1.35g of hexachlorocyclotriphosphazene in 20mL of tetrahydrofuran, fully dissolving the hexachlorocyclotriphosphazene by magnetic stirring to obtain a hexachlorocyclotriphosphazene solution, dropwise adding the hexachlorocyclotriphosphazene solution into a three-neck flask, and reacting for 2 hours at 70 ℃ after the dropwise adding is finished to obtain a product; filtering the product to obtain filtrate, and carrying out vacuum rotary evaporation on the filtrate to obtain an intermediate product; sequentially adding the intermediate product, 150mL of acetone, 25mL of distilled water and 25mL of concentrated hydrochloric acid into a jacketed three-neck flask with a reflux condenser, a thermometer and magnetic stirring, fully stirring to uniformly mix the mixture, reacting at 40 ℃ for 4 hours to obtain a crude product, washing the crude product with acetone for 3 times, filtering, and drying at 60 ℃ for 2 hours to obtain the modified cage-type silsesquioxane.
Preparation of laminates
Blending 10g of modified cage-type silsesquioxane and 90g of methyl methacrylate to obtain a modified prepolymer, blending the modified prepolymer and 20g of a heat-dissipating agent, pouring the mixture into a mold, standing for 20min, sealing after discharging bubbles, polymerizing in a water bath at 60 ℃ for 4 hours, performing post-treatment in an oven at 120 ℃ for 2 hours, cooling, and demolding to obtain an acrylic plate;
coating a quantum dot film on an acrylic plate, and placing the acrylic plate in a vacuum oven at 60 ℃ for 2 hours, and cooling to obtain the acrylic plate with the quantum dot film;
and bonding one surface of the acrylic plate, which is far away from the quantum dot film, with the LED light source assembly, and standing to obtain the laminated board.
Example 2
Preparation of modified titanium dioxide nanotube arrays
Polishing a titanium sheet (CAS number: 7440-32-6) with a size of 3cm x 3cm by using sand paper, then ultrasonically cleaning the titanium sheet by using deionized water for 10min, ultrasonically cleaning the titanium sheet by using absolute ethyl alcohol for 10min, then polishing the titanium sheet by using hydrofluoric acid solution with a volume ratio of 1% for 5min, finally ultrasonically cleaning the surface by using deionized water for 10min, and drying to obtain a pretreated titanium sheet; connecting a graphite electrode with a negative electrode of a direct current power supply, connecting a pretreated titanium sheet with a positive electrode of the direct current power supply, setting the output voltage of the direct current power supply to be 40V, then placing the whole device into a heat collection type constant temperature heating magnetic stirrer, setting the temperature to be 30 ℃, turning on the direct current power supply, and reacting for 2 hours to obtain a reacted titanium sheet; washing the reacted titanium sheet with distilled water, and drying with a blower to obtain the titanium dioxide sheet.
Placing the titanium dioxide sheet prepared by the steps into an integrated program-controlled high-temperature furnace, and calcining for 2 hours at 450 ℃ to obtain an anatase type titanium dioxide nanotube array; placing the anatase type titanium dioxide nanotube array into a tube furnace, and calcining for 2 hours at 550 ℃ in an ammonia atmosphere to obtain a nitrogen doped nanotube array; adding 0.5g of graphene oxide (CAS number: 1034343-98-0) into 50mL of deionized water, and performing ultrasonic dispersion for 1h to obtain graphene dispersion; soaking the nitrogen doped-nanotube array in graphene dispersion liquid for 3 hours to obtain a soaked matter, washing the soaked matter with deionized water, and drying in vacuum to obtain a graphene-nanotube array; adding 0.16g of sodium borohydride and 0.5g of silver nitrate into 50mL of solution with the volume ratio of water to glycol of 1:1 under the magnetic stirring condition, and uniformly stirring to obtain a mixed solution; soaking 10g of graphene-nanotube array in a mixed solution for 3 hours, washing the soaked graphene-nanotube array with deionized water, and drying in vacuum to obtain a silver-graphene-nanotube array; the silver-graphene-nanotube array is immersed in 50mL of methanol solution containing 100 mu L of phenylacetylene and 5mg of sodium methoxide, soaked for 2 hours at 50 ℃, washed with ethanol, and dried in nitrogen atmosphere to obtain the modified titanium dioxide nanotube array. Preparation of an anhydride grafted ethylene propylene diene monomer (CAS number: 23627-24-9) the ethylene propylene diene monomer (CAS number: 23627-24-9) was dried at 80 ℃ for 2 hours in a vacuum drying oven to obtain dried ethylene propylene diene monomer, 34.9g of dried ethylene propylene diene monomer, 5.3g of maleic anhydride (CAS number: 108-31-6) and 1.75g of benzoyl peroxide (CAS number: 94-36-0) were weighed and put into a torque rheometer to be melt-blended for 10 minutes, and the temperature of the 1-3 sections of an internal mixer was 190 ℃ at a rotating speed of 40r/min to obtain the anhydride grafted ethylene propylene diene monomer.
Preparation of a Heat-dissipating agent
40.1g of anhydride grafted ethylene propylene diene monomer, 7.6g of modified titanium dioxide nanotube array and 2.6g of xylene are mixed to obtain a mixture, and the mixture is heated in an oil bath at 60 ℃ for reaction to obtain the heat-dissipating agent.
Preparation of modified cage-type silsesquioxane
Sequentially adding 40mL of tetrahydrofuran, 16.1g of gKH-550 and 8.1g of triethylamine into a 250mL three-neck flask, fully stirring to uniformly mix the materials, then introducing chlorine as a protective gas for the reaction, and slowly heating to 60 ℃; dissolving 1.35g of hexachlorocyclotriphosphazene in 20mL of tetrahydrofuran, fully dissolving the hexachlorocyclotriphosphazene by magnetic stirring to obtain a hexachlorocyclotriphosphazene solution, dropwise adding the hexachlorocyclotriphosphazene solution into a three-neck flask, and reacting for 2 hours at 70 ℃ after the dropwise adding is finished to obtain a product; filtering the product to obtain filtrate, and carrying out vacuum rotary evaporation on the filtrate to obtain an intermediate product; sequentially adding the intermediate product, 150mL of acetone, 25mL of distilled water and 25mL of concentrated hydrochloric acid into a jacketed three-neck flask with a reflux condenser, a thermometer and magnetic stirring, fully stirring to uniformly mix the mixture, reacting at 40 ℃ for 4 hours to obtain a crude product, washing the crude product with acetone for 3 times, filtering, and drying at 60 ℃ for 2 hours to obtain the modified cage-type silsesquioxane.
Preparation of laminates
Blending 20g of modified cage-type silsesquioxane and 180g of methyl methacrylate to obtain a modified prepolymer, blending the modified prepolymer and 50g of a heat-dissipating agent, pouring the mixture into a mold, standing for 20min, discharging bubbles, sealing, polymerizing in a water bath at 60 ℃ for 4 hours, performing aftertreatment in an oven at 120 ℃ for 2 hours, cooling, and demolding to obtain an acrylic plate;
coating a quantum dot film on an acrylic plate, and placing the acrylic plate in a vacuum oven at 60 ℃ for 2 hours, and cooling to obtain the acrylic plate with the quantum dot film;
and bonding one surface of the acrylic plate, which is far away from the quantum dot film, with the LED light source assembly, and standing to obtain the laminated board.
Example 3
Preparation of modified titanium dioxide nanotube arrays
Polishing a titanium sheet (CAS number: 7440-32-6) with a size of 3cm x 3cm by using sand paper, then ultrasonically cleaning the titanium sheet by using deionized water for 10min, ultrasonically cleaning the titanium sheet by using absolute ethyl alcohol for 10min, then polishing the titanium sheet by using hydrofluoric acid solution with a volume ratio of 1% for 5min, finally ultrasonically cleaning the surface by using deionized water for 10min, and drying to obtain a pretreated titanium sheet; connecting a graphite electrode with a negative electrode of a direct current power supply, connecting a pretreated titanium sheet with a positive electrode of the direct current power supply, setting the output voltage of the direct current power supply to be 40V, then placing the whole device into a heat collection type constant temperature heating magnetic stirrer, setting the temperature to be 30 ℃, turning on the direct current power supply, and reacting for 2 hours to obtain a reacted titanium sheet; washing the reacted titanium sheet with distilled water, and drying with a blower to obtain the titanium dioxide sheet.
Placing the titanium dioxide sheet prepared by the steps into an integrated program-controlled high-temperature furnace, and calcining for 2 hours at 450 ℃ to obtain an anatase type titanium dioxide nanotube array; placing the anatase type titanium dioxide nanotube array into a tube furnace, and calcining for 2 hours at 550 ℃ in an ammonia atmosphere to obtain a nitrogen doped nanotube array; adding 0.5g of graphene oxide (CAS number: 1034343-98-0) into 50mL of deionized water, and performing ultrasonic dispersion for 1h to obtain graphene dispersion; soaking the nitrogen doped-nanotube array in graphene dispersion liquid for 3 hours to obtain a soaked matter, washing the soaked matter with deionized water, and drying in vacuum to obtain a graphene-nanotube array; adding 0.16g of sodium borohydride and 0.5g of silver nitrate into 50mL of solution with the volume ratio of water to glycol of 1:1 under the magnetic stirring condition, and uniformly stirring to obtain a mixed solution; soaking 10g of graphene-nanotube array in a mixed solution for 3 hours, washing the soaked graphene-nanotube array with deionized water, and drying in vacuum to obtain a silver-graphene-nanotube array; the silver-graphene-nanotube array is immersed in 50mL of methanol solution containing 100 mu L of phenylacetylene and 5mg of sodium methoxide, soaked for 2 hours at 50 ℃, washed with ethanol, and dried in nitrogen atmosphere to obtain the modified titanium dioxide nanotube array.
Preparation of anhydride grafted ethylene propylene diene monomer
Ethylene propylene diene monomer (CAS number: 23627-24-9) is dried in a vacuum drying oven at 80 ℃ for 2 hours to obtain dried ethylene propylene diene monomer, 25.6g of dried ethylene propylene diene monomer, 2.6g of maleic anhydride (CAS number: 108-31-6) and 1.28g of benzoyl peroxide (CAS number: 94-36-0) are weighed and put into a torque rheometer for melt blending for 10 minutes, and the temperature of 1-3 sections of an internal mixer is 190 ℃ and the rotating speed is 40r/min to obtain the anhydride grafted ethylene propylene diene monomer.
Preparation of a Heat-dissipating agent
28.1g of anhydride grafted ethylene propylene diene monomer, 5.4g of modified titanium dioxide nanotube array and 1.8g of xylene are mixed to obtain a mixture, and the mixture is heated in an oil bath at 60 ℃ for reaction to obtain the heat-dissipating agent.
Preparation of modified cage-type silsesquioxane
Sequentially adding 40mL of tetrahydrofuran, 12.6-gKH-550 and 6.3g of triethylamine into a 250mL three-neck flask, fully stirring to uniformly mix the materials, then introducing chlorine as a protective gas for the reaction, and slowly heating to 60 ℃; dissolving 2.6g of hexachlorocyclotriphosphazene in 20mL of tetrahydrofuran, fully dissolving the hexachlorocyclotriphosphazene by magnetic stirring to obtain a hexachlorocyclotriphosphazene solution, dropwise adding the hexachlorocyclotriphosphazene solution into a three-neck flask, and reacting for 2 hours at 70 ℃ after the dropwise adding is finished to obtain a product; filtering the product to obtain filtrate, and carrying out vacuum rotary evaporation on the filtrate to obtain an intermediate product; sequentially adding the intermediate product, 150mL of acetone, 25mL of distilled water and 25mL of concentrated hydrochloric acid into a jacketed three-neck flask with a reflux condenser, a thermometer and magnetic stirring, fully stirring to uniformly mix the mixture, reacting at 40 ℃ for 4 hours to obtain a crude product, washing the crude product with acetone for 3 times, filtering, and drying at 60 ℃ for 2 hours to obtain the modified cage-type silsesquioxane.
Preparation of laminates
Blending 15g of modified cage-type silsesquioxane and 135g of methyl methacrylate to obtain a modified prepolymer, blending the modified prepolymer and 35g of a cooling agent, pouring the mixture into a mold, standing for 20min, sealing after discharging bubbles, polymerizing in a water bath at 60 ℃ for 4 hours, performing post-treatment in an oven at 120 ℃ for 2 hours, cooling, and demolding to obtain an acrylic plate;
coating a quantum dot film on an acrylic plate, and placing the acrylic plate in a vacuum oven at 60 ℃ for 2 hours, and cooling to obtain the acrylic plate with the quantum dot film;
and bonding one surface of the acrylic plate, which is far away from the quantum dot film, with the LED light source assembly, and standing to obtain the laminated board.
Example 4
Example 4 based on example 3, example 4 differs from example 3 only in that the ethylene propylene diene monomer of example 4 is used in an amount of 27.6g, maleic anhydride is used in an amount of 0.56g, and benzoyl peroxide is used in an amount of 1.38g.
Example 5
Example 5 based on example 3, the only difference between example 5 and example 3 is that in example 5 the ethylene propylene diene monomer is used in an amount of 23.5g, maleic anhydride is used in an amount of 4.7g, and benzoyl peroxide is used in an amount of 1.2g.
Example 6
Example 6 based on example 3, example 6 differs from example 3 only in that in example 6 the amount of KH-550 used is 13.7g and in that the amount of hexachlorocyclotriphosphazene used is 1.4g.
Example 7
Example 7 based on example 3, example 7 differs from example 3 only in that in example 7 the amount of KH-550 used is 11.6g and in that the amount of hexachlorocyclotriphosphazene used is 3.5g.
Comparative example 1
Comparative example 1 based on example 3, comparative example 1 differs from example 3 only in that comparative example 1 replaces maleic anhydride with glycidyl methacrylate.
Comparative example 2
Comparative example 2 based on example 3, comparative example 2 differs from example 3 only in that comparative example 2 replaces the modified titanium dioxide nanotube array with nano titanium dioxide.
Comparative example 3
Comparative example 3 based on example 3, comparative example 3 differs from example 3 only in that comparative example 3 replaces the modified cage silsesquioxane with a cage silsesquioxane.
Comparative example 4
Comparative example 4 based on example 3, comparative example 4 differs from example 3 only in that comparative example 4 replaces phenylacetylene with styrene.
Comparative example 5
Comparative example 5 based on example 3, comparative example 5 differs from example 3 only in that comparative example 5 replaces benzoyl peroxide with potassium persulfate.
Performance test
(1) The method is characterized in that a light source exposure test method of GB/T16422.2-2022 plastic laboratory is adopted as a standard, an acrylic plate is cut into a sample with the length of 3cm, the sample is placed in a xenon arc exposure photo-aging test box and irradiated for 2000 hours, then the yellow index of a test sample is tested by adopting the measurement of the yellow index of GB/T39822-2021 plastic and the change value thereof as the standard, and the average value is obtained after measurement and recorded in a table 1.
(2) The method of light source exposure test in GB/T16422.3-2022 plastic laboratory is selected as a standard, an acrylic plate is cut into 3 cm-3 cm samples, the UV resistance of the samples is detected, each sample is tested three times, and the average value is taken after the measurement to obtain the ultraviolet blocking rate, and the ultraviolet blocking rate is recorded in Table 1.
(3) The method is characterized in that a standard test method for light transmittance of GB/T2410-2008 plastic materials is selected as a standard, an acrylic plate is cut into 3 cm-3 cm samples, the light transmittance of each sample is detected, each sample is tested three times, and the average value is taken after the measurement to obtain the light transmittance, and the light transmittance is recorded in a table 1.
(4) The method for absolute measurement of photoluminescence quantum efficiency of fluorescent material is selected as a standard, a laminated board is placed at a proper position of an integrating sphere, each sample is tested three times, and the measured sample is calculated and averaged to obtain brightness, and the brightness is recorded in table 1.
TABLE 1 detection results of acrylic plate aging resistance, UV resistance, light transmittance and laminate brightness
| Detection result | Yellow index | Uv blocking rate/% | Transmittance/% | Brightness cd/m 2 |
| Example 1 | 0.42 | 98.7 | 99.2 | 1121 |
| Example 2 | 0.46 | 98.2 | 98.9 | 1089 |
| Example 3 | 0.33 | 99.3 | 99.7 | 1190 |
| Example 4 | 0.78 | 97.6 | 98.1 | 1055 |
| Example 5 | 0.69 | 97.9 | 98.3 | 1061 |
| Example 6 | 0.97 | 96.1 | 97.8 | 1043 |
| Example 7 | 0.91 | 96.5 | 97.9 | 1057 |
| Comparative example 1 | 2.1 | 90.5 | 89.7 | 747 |
| Comparative example 2 | 3.5 | 89.3 | 87.2 | 696 |
| Comparative example 3 | 5.4 | 92.2 | 73.4 | 582 |
| Comparative example 4 | 4.7 | 90.1 | 85.2 | 669 |
| Comparative example 5 | 4.2 | 90.5 | 86.7 | 682 |
As is clear from Table 1, examples 1 to 3 all have a yellow index of less than 0.46, an ultraviolet blocking rate of 98.2% or more, a light transmittance of 98.9% or more, and a luminance of 1089cd/m 2 Above, it is seen that the laminate prepared by the present application has good anti-aging performance, ultraviolet resistance and light transmittance.
As can be seen from table 1, example 4 differs from example 3 only in that: in the example 4, the mass ratio of ethylene propylene diene monomer, maleic anhydride and benzoyl peroxide is 1:0.02:0.05, the mass ratio of ethylene propylene diene monomer, maleic anhydride and benzoyl peroxide in example 3 is 1:0.1:0.05, yellow index of 0.78 in example 4, UV blockingThe light transmittance was 97.6%, the light transmittance was 98.1%, and the luminance was 1055cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the method is characterized in that the consumption of maleic anhydride is reduced, the consumption of benzoyl peroxide is increased, the grafting rate of ethylene propylene diene monomer is reduced, the morphology of the anhydride grafted ethylene propylene diene monomer is changed due to the acceleration of grafting reaction, the compatibility of the anhydride grafted ethylene propylene diene monomer in an acrylic plate system is reduced, the overall stability of the acrylic plate system is poor, the ultraviolet resistance, the ageing resistance and the light transmittance of an acrylic plate are reduced, and the luminous performance of a laminated plate is reduced.
As can be seen from table 1, example 5 differs from example 3 only in that: in example 5, the mass ratio of ethylene propylene diene monomer, maleic anhydride and benzoyl peroxide is 1:0.2:0.05, the mass ratio of ethylene propylene diene monomer, maleic anhydride and benzoyl peroxide in example 3 is 1:0.1:0.05, yellow index of 0.69, UV blocking ratio of 97.9%, light transmittance of 98.3%, luminance of 1061cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the method is characterized in that the dosage of maleic anhydride is increased, the dosage of benzoyl peroxide is reduced, the grafting rate of ethylene propylene diene monomer is improved, and the synergistic effect of each component in an acrylic plate is influenced due to excessive anhydride; meanwhile, the reduced benzoyl peroxide causes the compatibility between the anhydride grafted ethylene propylene diene monomer and methyl methacrylate to be reduced, the stability of the acrylic plate is reduced, and the ultraviolet resistance, ageing resistance and light transmittance of the acrylic plate are reduced, so that the brightness of the laminated board is reduced, and the light-emitting performance is reduced.
From Table 1As is known, example 6 differs from example 3 only in that: the mass ratio of hexachlorocyclotriphosphazene to KH-550 in example 6 was 0.1:1, the mass ratio of hexachlorocyclotriphosphazene to KH-550 in example 3 is 0.2:1, the yellow index in example 6 was 0.97, the ultraviolet ray blocking ratio was 96.1%, the light transmittance was 97.8%, and the luminance was 1043cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the method is characterized in that the consumption of hexachlorocyclotriphosphazene is reduced, the synergistic effect of N, P, si elements in the modified cage-type silsesquioxane is weakened, the thermal and mechanical properties of an acrylic plate are reduced, meanwhile, the synergistic effect of hexachlorocyclotriphosphazene and benzoyl peroxide is weakened, the system compatibility of the acrylic plate is reduced, the stability of the acrylic plate is reduced, the ultraviolet resistance and ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, the brightness of a laminated plate is weakened, and the light-emitting performance is reduced.
As can be seen from table 1, example 7 differs from example 3 only in that: the mass ratio of hexachlorocyclotriphosphazene to KH-550 in example 7 was 0.3:1, the mass ratio of hexachlorocyclotriphosphazene to KH-550 in example 3 is 0.2:1, the yellow index in example 7 was 0.91, the ultraviolet ray blocking ratio was 96.5%, the light transmittance was 97.9%, and the luminance was 1057cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the example 7 and the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the method is characterized in that the consumption of hexachlorocyclotriphosphazene is increased, phosphorus-chlorine bonds in the hexachlorocyclotriphosphazene are active, substitution reaction is easy to occur, the excessive hexachlorocyclotriphosphazene leads to the reduction of system stability in an acrylic plate system, the synergistic effect is weakened, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced to some extent, and therefore the brightness of the laminated plate is weakened, and the light emitting performance is reduced.
As can be seen from Table 1Comparative example 1 differs from example 3 only in that: comparative example 1 in which maleic anhydride was replaced with glycidyl methacrylate, the yellow index in comparative example 1 was 2.1, the ultraviolet ray blocking ratio was 90.5%, the light transmittance was 89.7%, and the luminance was 747cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the comparative example 1 and the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the modified titanium dioxide nanotube array is characterized in that maleic anhydride is replaced by glycidyl methacrylate, the glycidyl methacrylate cannot react with alkenyl groups on the modified titanium dioxide nanotube array, the compatibility of each component in the coolant is reduced, the synergistic effect of each component in the acrylic plate is weakened, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, the brightness of the laminated plate is weakened, and the light emitting performance is reduced.
As can be seen from table 1, comparative example 2 differs from example 3 only in that: in comparative example 2, the modified titanium dioxide nanotube array was replaced with nano titanium dioxide, the yellow index in comparative example 2 was 3.5, the ultraviolet blocking rate was 89.3%, the light transmittance was 87.2%, and the brightness was 696cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the comparative example 2 and the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the modified titanium dioxide nanotube array is replaced by the nano titanium dioxide, the nano titanium dioxide has no pore structure, the light response range is narrow, the nano titanium dioxide has no reaction sites with other organic phases, the compatibility of the nano titanium dioxide and the anhydride grafted ethylene propylene diene monomer rubber is poor, the synergistic effect between the heat radiator and other components in the acrylic plate is weakened, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, the brightness of the laminated plate is weakened, and the light emitting performance is reduced.
As can be seen from table 1, comparative example 3 differs from example 3 only in that: comparative example 3The modified cage type silsesquioxane was replaced with cage type silsesquioxane, the yellow index in comparative example 3 was 5.4, the ultraviolet blocking rate was 92.2%, the light transmittance was 73.4%, and the brightness was 582cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the comparative example 3 and the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are reduced, the light transmission performance is reduced, and the luminous performance of the laminated board is reduced; the modified cage-type silsesquioxane is replaced by cage-type silsesquioxane, the transparency of the acrylic plate is greatly reduced by the cage-type silsesquioxane, the light transmittance is further influenced, the cage-type silsesquioxane also lacks the synergistic effect with components in the coolant, the stability of the acrylic plate is also reduced, the ultraviolet resistance and the ageing resistance of the acrylic plate are obviously reduced, the light transmittance is poorer, and therefore the brightness of the laminated plate is weakened, and the luminous performance is reduced.
As can be seen from table 1, comparative example 4 differs from example 3 only in that: in comparative example 4 in which phenylacetylene was replaced with styrene, the yellow index in comparative example 4 was 4.7, the ultraviolet ray blocking rate was 90.1%, the light transmittance was 85.2%, and the luminance was 669cd/m 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the comparative example 4 and the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are obviously reduced, the light transmission performance is obviously reduced, and the light-emitting performance of the laminated board is greatly reduced; the method is characterized in that phenylacetylene is replaced by styrene, unsaturated double bonds are converted into saturated bonds after the reaction of the styrene and the groups on the surface of the titanium dioxide nanotube array, the groups on the surface of the modified titanium dioxide nanotube array cannot react with maleic anhydride, and the system compatibility and stability of the acrylic plate are reduced, so that the ultraviolet resistance and ageing resistance of the acrylic plate are obviously reduced, the light transmittance is poor, the brightness of the laminated board is weakened, and the light emitting performance is reduced.
As can be seen from table 1, comparative example 5 differs from example 3 only in that: comparative example 5 where phenylacetylene was replaced with styrene, the yellow index in comparative example 5 was 4.2, and uv resistanceThe light transmittance was 86.7% and the brightness was 682cd/m, with a light transmittance of 90.5% 2 The yellowness index in example 3 was 0.33, the ultraviolet ray blocking ratio was 99.3%, the light transmittance was 99.7%, and the luminance was 1190cd/m 2 Compared with the comparative example 5 and the example 3, the ultraviolet resistance and the ageing resistance of the acrylic plate are obviously reduced, the light transmission performance is obviously reduced, and the light-emitting performance of the laminated board is greatly reduced; the method is characterized in that benzoyl peroxide is replaced by potassium persulfate, and the grafting reaction of maleic anhydride and ethylene propylene diene monomer is initiated by using the potassium persulfate as an initiator, but the compatibility between the anhydride grafted ethylene propylene diene monomer and other components in an acrylic plate system is improved limited, the dispersibility and stability of the system are reduced, the ageing resistance and ultraviolet resistance of the acrylic plate are obviously reduced, and the light transmittance is reduced, so that the luminous performance of the laminated plate is reduced.
The present embodiment is merely illustrative of the present application, and the present application is not limited thereto, and a worker can make various changes and modifications without departing from the scope of the technical idea of the present application. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of claims.
Claims (10)
1. A laminate, characterized in that: the laminated board comprises a quantum dot film, an acrylic board and an LED light source assembly, wherein the acrylic board comprises the following components in parts by mass:
100-200 parts of modified prepolymer
20-50 parts of heat radiating agent
The modified prepolymer comprises methyl methacrylate and modified cage-type silsesquioxane;
the heat-radiating agent comprises anhydride grafted ethylene propylene diene monomer rubber and a modified titanium dioxide nanotube array.
2. An acrylic sheet according to claim 1, wherein: the modified titanium dioxide nanotube array comprises: titanium flakes, graphene oxide, sodium borohydride, silver nitrate and a modifier.
3. An acrylic sheet according to claim 2, wherein: the modifier comprises sodium methoxide and phenylacetylene.
4. An acrylic sheet according to claim 2, wherein: the modified titanium dioxide nanotube array is prepared by the following steps:
pretreating a titanium sheet to obtain a titanium dioxide sheet, calcining the titanium dioxide sheet to obtain an anatase type titanium dioxide nanotube array, and calcining the anatase type titanium dioxide nanotube array in ammonia gas to obtain a nitrogen doped-nanotube array;
dispersing graphene oxide in water to obtain graphene dispersion liquid, soaking a nitrogen doped-nanotube array in the graphene dispersion liquid to obtain a soaked matter, cleaning the soaked matter, and drying to obtain a graphene-nanotube array;
dispersing sodium borohydride and silver nitrate into an ethylene glycol aqueous solution to obtain a mixed solution, soaking a graphene-nanotube array in the mixed solution, cleaning and drying to obtain a silver-graphene-nanotube array;
dispersing phenylacetylene and sodium methoxide into alcohol to obtain a modified solution, soaking the silver-graphene-nanotube array in the modified solution, washing and drying to obtain the modified titanium dioxide nanotube array.
5. An acrylic sheet according to claim 1, wherein: the anhydride grafted ethylene propylene diene monomer comprises ethylene propylene diene monomer, maleic anhydride and an initiator.
6. An acrylic sheet according to claim 5, wherein: the mass ratio of the ethylene propylene diene monomer to the maleic anhydride to the initiator is 1: (0.05-0.15): 0.05.
7. an acrylic sheet according to claim 5, wherein: the initiator comprises benzoyl peroxide.
8. An acrylic sheet according to claim 1, wherein: the modified cage type silsesquioxane comprises KH-550 and hexachlorocyclotriphosphazene.
9. An acrylic sheet according to claim 8, wherein: the mass ratio of KH-550 to hexachlorocyclotriphosphazene is 1: (0.15-0.25).
10. A method of manufacturing a laminate for use in accordance with claim 1, comprising: the laminated board is prepared by the following steps:
blending modified cage-type silsesquioxane and methyl methacrylate to obtain a modified prepolymer, blending the modified prepolymer and a cooling agent, and performing mold filling sealing, polymerization and post-treatment procedures to obtain an acrylic plate;
coating the quantum dot film on an acrylic plate, heating, vacuumizing, and cooling to obtain the acrylic plate with the quantum dot film;
and bonding one surface of the acrylic plate, which is far away from the quantum dot film, with the LED light source assembly, and standing to obtain the laminated board.
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