CN106188429B - Quantum dot composition, quantum dot composite material, preparation method and application - Google Patents
Quantum dot composition, quantum dot composite material, preparation method and application Download PDFInfo
- Publication number
- CN106188429B CN106188429B CN201610632828.8A CN201610632828A CN106188429B CN 106188429 B CN106188429 B CN 106188429B CN 201610632828 A CN201610632828 A CN 201610632828A CN 106188429 B CN106188429 B CN 106188429B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- composite material
- curing agent
- epoxy
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002096 quantum dot Substances 0.000 title claims abstract description 236
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 70
- 239000011159 matrix material Substances 0.000 claims abstract description 53
- 229920002521 macromolecule Polymers 0.000 claims abstract description 51
- 229920001400 block copolymer Polymers 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 40
- -1 Phenolic Acrylates Chemical class 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 79
- 238000001723 curing Methods 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 47
- 239000003431 cross linking reagent Substances 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 28
- 238000000016 photochemical curing Methods 0.000 claims description 26
- 238000003848 UV Light-Curing Methods 0.000 claims description 24
- 238000007711 solidification Methods 0.000 claims description 22
- 230000008023 solidification Effects 0.000 claims description 22
- 150000001768 cations Chemical class 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 14
- 238000013007 heat curing Methods 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 238000001029 thermal curing Methods 0.000 claims description 10
- 238000009792 diffusion process Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003822 epoxy resin Substances 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 229920000647 polyepoxide Polymers 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 12
- 230000004888 barrier function Effects 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 7
- 235000003642 hunger Nutrition 0.000 abstract description 5
- 230000037351 starvation Effects 0.000 abstract description 5
- 239000004843 novolac epoxy resin Substances 0.000 description 30
- 150000003254 radicals Chemical group 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005191 phase separation Methods 0.000 description 12
- 230000009471 action Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 244000144992 flock Species 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 125000006188 2-phenyl benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 0 Cc1c(C)c(*)ccc1 Chemical compound Cc1c(C)c(*)ccc1 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- VWQMVURBILHJJF-UHFFFAOYSA-N O.OC(=O)C=C.OC(=O)C=C Chemical compound O.OC(=O)C=C.OC(=O)C=C VWQMVURBILHJJF-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000012663 cationic photopolymerization Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-(1,1-dimethylethyl)-phenol Natural products CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical class C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- HHZAHYUACNWGAQ-UHFFFAOYSA-N 3,4-diaminobutan-2-ol Chemical compound CC(O)C(N)CN HHZAHYUACNWGAQ-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- KDNYCTPSPZHJQF-UHFFFAOYSA-N 3-phenylbutan-2-ol Chemical compound CC(O)C(C)C1=CC=CC=C1 KDNYCTPSPZHJQF-UHFFFAOYSA-N 0.000 description 1
- UZNDHCZORMBARB-UHFFFAOYSA-N 4-hydroxylauric acid Chemical class CCCCCCCCC(O)CCC(O)=O UZNDHCZORMBARB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BKGYPYOTCMXDGV-UHFFFAOYSA-N Cc(c(C)ccc1)c1NC Chemical compound Cc(c(C)ccc1)c1NC BKGYPYOTCMXDGV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- GVETWXKNKJJNST-UHFFFAOYSA-N N-phenyl-2,3-bis(2,4,4-trimethylpentan-2-yl)aniline Chemical class CC(CC(C)(C)C)(C)C=1C(=C(C=CC1)NC1=CC=CC=C1)C(CC(C)(C)C)(C)C GVETWXKNKJJNST-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 229910008253 Zr2O3 Inorganic materials 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- QFJVRMQMEQYFIB-UHFFFAOYSA-N [SH3+].[Br-].C1(=CC=CC=C1)[PH+](C1=CC=CC=C1)C1=CC=CC=C1.[Br-] Chemical compound [SH3+].[Br-].C1(=CC=CC=C1)[PH+](C1=CC=CC=C1)C1=CC=CC=C1.[Br-] QFJVRMQMEQYFIB-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzenetetracarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ROMWNDGABOQKIW-UHFFFAOYSA-N phenyliodanuidylbenzene Chemical compound C=1C=CC=CC=1[I-]C1=CC=CC=C1 ROMWNDGABOQKIW-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of quantum dot composition, quantum dot composite material, preparation method and applications.Wherein, quantum dot composition includes quantum dot and macromolecule matrix solidfied material precursor, and macromolecule matrix solidfied material precursor includes Epoxy Phenolic Acrylates block copolymer.Above-mentioned quantum dot composition includes macromolecule matrix solidfied material precursor of the Epoxy Phenolic Acrylates block copolymer as dispersion quantum dot by selecting, since Epoxy Phenolic Acrylates block copolymer combines the advantages of acrylate and quantum dot compatibility are good and epoxy resin is to oxygen and aqueous vapor good barrier property, and epoxy block is linked with arylate blocks by chemical bond and effect, has extraordinary chemical stability.The application sets about in terms of macromolecule matrix solidfied material precursor material composition, solve the problems, such as with the compatibility of quantum dot and starvation and aqueous vapor, improve the luminous efficiency and stability of quantum dot composite material.
Description
Technical field
The present invention relates to quantum dot composite material fields, compound in particular to a kind of quantum dot composition, quantum dot
Material, preparation method and application.
Background technology
Quantum dot, and can be described as nanocrystalline, it is a kind of nano particle being made of II-VI group or iii-v element.Amount
The grain size of son point is typically in the range of between 1~10nm, and since electrons and holes are by quantum confinement, continuous band structure becomes to have
The discrete energy level structure of molecular characterization can emit fluorescence after being excited.Based on quantum effect, quantum dot is in solar cell, hair
The fields such as optical device and optical bio label are with a wide range of applications.
Quantum dot has exciting light spectrum width and continuously distributed, and emission spectrum is narrow and symmetrical, Color tunable, photochemical stable
Property high, the superior fluorescent characteristic such as fluorescence lifetime length.By the shape, structure and size that control quantum dot, so that it may with easily
Its energy gap width, exciton are adjusted (in semiconductor, if an electronics is gone on from full valence to empty conduction band, in valence
With one hole of interior generation, and an electronics is generated in conduction band, to form an electron-hole pair.Hole is positively charged, electricity
Subband negative electricity, the coulomb adelphotaxy between them can be spatially bound together under certain conditions, such shape
At complex be known as exciton) (bands of a spectrum of organic compound are often because of substituent group for the energy blue shift of the size of binding energy and exciton
Change with quantity of solvent makes maximum absorption wavelength and absorption intensity change.It is known as when maximum wavelength is moved to shortwave direction
Blue shift；Blue shift refers to the frequency of the electromagnetic wave that the object of positive observer's movement is scattered on spectrum line to the direction at blue end
It is mobile, it is meant that wavelength reduces.With the reduction of particle size color to blue light direction move) etc. electronic states.Therefore, can lead to
The size for crossing control quantum dot obtains the arbitrarily desired color in visible light region, and can be obtained by the size of control half-peak breadth
The monochromatic light of pure color can increase substantially colour gamut and color saturation for display field.
Between being typically in the range of 1~10nm due to the grain size of quantum dot, there is very big specific surface area, surface phase atomicity
Increase, the coordination for resulting in surface atom is insufficient, unsaturated bond and dangling bond (i.e. the unpaired electronics of crystalline surface) increase, and makes
These surface atoms have high activity, extremely unstable, it is easy to be combined with other atoms.Therefore, general quantum dot surface needs
Suitable ligand is selected to be coordinated with the metal of quantum dot surface, the type of ligand has certainly the efficiency and stability of quantum dot
Qualitatively influence.With the development and optimization of quantum dot synthetic technology, the efficiency and stability of quantum dot have reached industrialization
Level.But the unique skin effect of quantum dot also determines that its sensibility to aqueous vapor and oxygen, aqueous vapor and oxygen can be broken
The ligand of bad quantum dot surface reduces the efficiency of quantum dot.Quantum dot size is smaller, and specific surface area is bigger, to aqueous vapor and oxygen
Sensibility it is higher.
With the maturation of quanta point material, the application of quanta point material is more and more wider, especially in display field.But it measures
Son point material cannot be used alone, it is necessary to be dispersed in macromolecule matrix.In view of the characteristic of quantum dot itself, macromolecule matrix
There must be following characteristic：(1) there is preferable compatibility with quanta point material, the luminous efficiency of quantum dot can be kept well
(2) there is preferable barrier property to aqueous vapor and oxygen；It (3) can be by liquid curing at solid-state under the action of light or heat.
Macromolecule matrix about dispersion quantum dot has many reports, can be summarized as following a few classes：(1) to quantum dot surface
It carries out silicone-modified, selects organosilicon material as macromolecule matrix, be mainly used for the encapsulation in situ of LED chip.Organosilicon
Material has extraordinary thermal stability and optical stability, still, due to the high-flexibility of organosilicon material silicon oxygen bond and big
Bond angle, it is poor to the barrier property of aqueous vapor and oxygen.Under conditions of high temperature and blue light illumination, quanta point material be easy by
The destruction of aqueous vapor and oxygen and fail.(2) it is made using porous material absorption quantum dot or by quantum dot epoxy resin cladding
Microballoon.Epoxy resin is poor with the compatibility of quantum dot due to higher polarity, and hair is easy under conditions of high temperature illumination
Huang influences quantum dot luminous efficiency.(3) select acrylate monomer or polyacrylate as macromolecule matrix.Acrylate
There are preferable compatibility, quantum dot that can preferably be dispersed in acrylate with quantum dot.But acrylate is to aqueous vapor and oxygen
The barrier property of gas is poor.(4) phase separation structure is formed, disperses quantum dot using hydrophobic systems (acrylate), outer layer is used
Hydrophilic system (epoxy resin) starvation, is macroscopically forming phase separation structure.Nothing between acrylic resin and epoxy resin
Chemical bond and effect, there are certain defects for long-term chemical durability aspect.
Therefore, it is still necessary to the application of quantum dot in the prior art is improved, to improve the luminous efficiency of quantum dot
And stability.
Invention content
The main purpose of the present invention is to provide a kind of quantum dot composition, quantum dot composite material, preparation method and
Using, with solve the prior art due to aqueous vapor and oxygen barrier property difference or with dispersion quantum dot matrix poor compatibility and lead
The low problem of the luminous efficiency of the quantum dot composite material of cause.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of quantum dot composition, quantum dot group
It includes quantum dot and macromolecule matrix solidfied material precursor to close object, and macromolecule matrix solidfied material precursor includes epoxy novolac-acrylic acid
Ester block copolymer.
Further, epoxy novolac-acrylate block copolymer is that epoxy novolac-acrylate of following structural formula is embedding
Duan Gongju
Object：Wherein, x, y are integer, and x >=1, y >=1, and 3≤x+y≤7.
Further, further include crosslinking agent in quantum dot composition, preferably crosslinking agent is double/three-functionality-degree acrylic monomers
And/or double/three-functionality-degree epoxy monomer；More preferably double/three-functionality-degree acrylic monomers and/or double/three-functionality-degree epoxy monomer
Mass ratio with epoxy novolac-acrylate block copolymer is 1~3：10~20.
Further, in quantum dot composition further include curing agent, preferred consolidation agent is radical UV curing agent and thermosetting
Agent, or be radical UV curing agent and cation photocuring agent.
Further, quantum dot composition further includes additive, and preferable additives are light diffusion particle and/or antioxidant.
According to another aspect of the present invention, a kind of preparation method of quantum dot composite material is provided, preparation method includes：
Macromolecule matrix solidfied material precursor, crosslinking agent, curing agent quantum dot and optional additive are mixed to get the first mixture；
First mixture is cured, quantum dot composite material is obtained；Wherein, macromolecule matrix solidfied material precursor includes phenolic aldehyde ring
Oxygen-acrylate block copolymer.
Further, the structural formula of epoxy novolac-acrylate block copolymer is：
Wherein, x, y are integer, and x >=1, y >=1, and 3≤x+y
≤7。
Further, crosslinking agent is bifunctionality acrylic monomers, three-functionality-degree acrylic monomers, bifunctionality epoxy list
Body and/or three-functionality-degree epoxy monomer；The mass ratio of more preferable crosslinking agent and epoxy novolac-acrylate block copolymer is 1
~3：10~20.
Further, curing agent is radical UV curing agent and thermal curing agents, and the step of preferred consolidation includes：Using freedom
The first mixture of base light curing agent pair carries out photocuring, obtains solidification semi-finished product；Solidification semi-finished product are carried out using thermal curing agents
Heat cure obtains quantum dot composite material.
Further, curing agent is radical UV curing agent and cation photocuring agent, and the step of solidification includes：In freedom
The first mixture is cured under being acted on while base light curing agent and cation photocuring agent, obtains quantum dot composite wood
Material.
Further, additive is light diffusion particle and/or antioxidant.
According to an aspect of the present invention, a kind of quantum dot composite material is provided, quantum dot composite material uses above-mentioned
A kind of preparation method is prepared.
According to another aspect of the present invention, a kind of quantum dot composite material is provided, quantum dot composite material includes quantum
Point and the macromolecule matrix solidfied material being coated on around quantum dot, macromolecule matrix solidfied material are that epoxy novolac-acrylate is embedding
Cross-linking products between section copolymer, cross-linking products have the structural unit as shown in following formula (I)：
To achieve the goals above, according to a further aspect of the invention, a kind of quantum dot light emitting device is provided, including
Quantum dot composite material, quantum dot composite material are above-mentioned quantum dot composite material.
Further, the quantum dot in quantum dot composite material is red quantum dot and/or green quantum dot.
Further, quantum dot light emitting device is quantum dot film or quantum dot pipe.
It applies the technical scheme of the present invention, above-mentioned quantum dot composition is embedding comprising epoxy novolac-acrylate by selection
Macromolecule matrix solidfied material precursor of the section copolymer as dispersion quantum dot, due to epoxy novolac-acrylate block copolymer
The advantages of acrylate and quantum dot compatibility are good and epoxy resin is to oxygen and aqueous vapor good barrier property is combined, and epoxy is embedding
Section is linked with arylate blocks by chemical bond and effect, has extraordinary chemical stability.The application is from polymer-based
Set about in terms of body solidfied material precursor material composition, solve the problems, such as with the compatibility of quantum dot and starvation and aqueous vapor,
Improve the luminous efficiency and stability of quantum dot composite material.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c), which are shown in a kind of preferred embodiment according to the present invention, forms lamellar phase
The microcosmic chain form schematic diagram of epoxy novolac-acrylate block copolymer of separation：Before Fig. 1 (a) solidifications；Fig. 1 (b) photocurings
Afterwards；After Fig. 1 (c) heat or photocuring；
Fig. 2 (a), Fig. 2 (b) and Fig. 2 (c), which are shown in a kind of preferred embodiment according to the present invention, forms spherical phase
The microcosmic chain form schematic diagram of epoxy novolac-acrylate block copolymer of separation：Wherein, before Fig. 2 (a) solidifications；Fig. 2 (b)
After photocuring；After Fig. 2 (c) heat or photocuring；
In above-mentioned attached drawing 1 (a) to attached drawing 2 (b), individual pore represents green quantum dot, and individually big stain represents
Red quantum dot, the molecules present novolac epoxy resin block with pore on linear segment, the generation with double bond on linear segment
The monomer molecule of table arylate blocks, three double bonds represents acrylic monomers, and the monomer molecule of three pores represents epoxy
Monomer, the corresponding reference numeral of above compound are respectively：
10, green quantum dot；20, red quantum dot；30, novolac epoxy resin block；40, arylate blocks；50, third
Acrylic monomer；60, epoxy monomer；80, arylate blocks cured layer；90, novolac epoxy resin block cured layer；100, first
Shell；110, the second shell.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
In the application, epoxy novolac-acrylate block copolymer refers to that novolac epoxy resin is formed with acrylate
Block copolymer.
As background technology part is previously mentioned, due to the barrier property difference to aqueous vapor and oxygen or the matrix with dispersion quantum dot
Poor compatibility and cause quantum dot light emitting material in the prior art to there is a problem of that luminous efficiency is low and stability difference, in order to change
It is apt to this situation, in a kind of typical embodiment of the present invention, provides a kind of quantum dot composition, the quantum dot composition
Including quantum dot and macromolecule matrix solidfied material precursor, macromolecule matrix solidfied material precursor includes that epoxy novolac-acrylate is embedding
Section copolymer.
Above-mentioned quantum dot composition is by selecting comprising epoxy novolac-acrylate block copolymer as dispersion quantum dot
Macromolecule matrix solidfied material precursor, since epoxy novolac-acrylate block copolymer combines acrylate and quantum dot
The advantages of compatibility is good and epoxy resin is to oxygen and aqueous vapor good barrier property, and epoxy block and passing through of arylate blocks
It learns key and effect links, there is extraordinary chemical stability, in terms of macromolecule matrix solidfied material precursor material composition
Set about, solve the problems, such as with the compatibility of quantum dot and starvation and aqueous vapor, improve the hair of quantum dot composite material
Light efficiency and stability.
In above-mentioned quantum dot composition, epoxy novolac-acrylate block copolymer is novolac epoxy resin and acrylic acid
React the not only block copolymer containing epoxy group but also containing acrylic acid groups formed.Its reaction route is as follows：
Wherein, n=x+y, x, y are integer, and x >=1, y >=1, and 3≤n=x+y≤7.
The block copolymer of heterogeneity can be obtained in the ratio for adjusting above-mentioned novolac epoxy resin and acrylic acid.In this hair
In a kind of bright preferred embodiment, above-mentioned novolac epoxy resin-acrylic block copolymers are the epoxy novolac of following structural formula
Resin-propylene acid block copolymer：Wherein, x >=1,
Y >=1, and 3≤x+y≤7.Different phase separation structures can be formed according to the size of x and y.As x and y approximately equals, phenolic aldehyde ring
Oxygen-acrylate block copolymer formation stratiform phase separation structure, novolac epoxy resin block and arylate blocks rule
It is arranged in layer structure.As shown in Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c), novolac epoxy resin block 30 is arranged in side, propylene
Acid esters block 40 is arranged in the other side.And work as x=1, when y=5, epoxy novolac-acrylate block copolymer then forms spherical
Phase separation structure.Such as Fig. 2 (a) to Fig. 2 (c), arylate blocks 40 since segment is shorter, flock together to be formed it is spherical in
The heart, and novolac epoxy resin block 30 is then arranged in outside, is formed to arylate blocks 40 and surrounds shape.Quantum dot (including it is green
Color quantum dot 10 and red quantum dot 20) due to preferable with the compatibility of arylate blocks 40, preferentially it is dispersed in acrylate
In block 40.
In above-mentioned quantum dot composition, special want is had no to the amount ratio of quantum dot and macromolecule matrix solidfied material precursor
It asks, as long as macromolecule matrix solidfied material precursor can be evenly dispersed to quantum dot progress, and the luminous efficiency of quantum dot can be maintained
With stability.For example, a certain amount of macromolecule matrix solidfied material precursor can be to one or a group amount according to actual needs
Son point is disperseed.In a kind of preferred embodiment of the present invention, the mass ratio of quantum dot and macromolecule matrix solidfied material precursor
It is 0.1~1：10~100.Specific ratio need to be depending on objective optics parameter.
In above-mentioned quantum dot composition, according to actual needs, can will be prepared into it is required a kind of in product process or
Various other auxiliary elements are included, and can not also be included and are provided separately in specific preparation process.In this hair
Further include crosslinking agent in above-mentioned quantum dot composition, preferably crosslinking agent is more than for degree of functionality in bright another kind preferred embodiment
The acrylic monomers and/or difunctionality of acrylic monomers equal to 2 or epoxy monomer, more preferably bifunctionality or three-functionality-degree
The epoxy monomer of degree or three-functionality-degree.
Crosslinking agent herein is internal crosslinker, is entered in macromolecular structure chain in polymerization as a kind of monomer, Huo Zhezuo
Be added in macromolecule matrix solidfied material precursor for a component, can storage-stable, only be heated to certain temperature or
Radiation condition can just crosslink reaction.It is preferred that the acrylic monomers and epoxy monomer of three-functionality-degree are as crosslinking agent, activity
Group forms cross-linked structure with arylate blocks and novolac epoxy resin block reaction respectively, and cross-linking efficiency is high, and does not occur
Adverse reaction and cohesion.
It is highly preferred that the acrylic monomers of above-mentioned bifunctionality or three-functionality-degree be selected from 1,6- hexanediyl esters,
Triethylene-glycol dimethylacrylate, Tricyclodecane Dimethanol diacrylate, three (2- ethoxys) isocyanic acids, three propylene
Acid esters, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, 3- ethyoxyls-trimethylolpropane tris acrylic acid
Ester, 9- ethyoxyls-trimethylolpropane trimethacrylate, propoxyl group-trimethylolpropane trimethacrylate and trihydroxy methyl
It is one or more in propane trimethyl acrylic ester.The epoxy monomer of above-mentioned bifunctionality or three-functionality-degree is selected from ethylene glycol two
Glycidol ether, 1,6- hexanediol diglycidyl ethers, 1,4-butanediol diglycidyl ether, trimethylolpropane tris shrink sweet
It is one or more in oily ether and triglycidyl isocyanurate.These crosslinking agents are ensureing curing rate and the degree of cross linking
Under the premise of, there is preferable flexibility and intensity.
In above-mentioned quantum dot composition, according to actual production technique and the specific kind of difference of crosslinking agent, used in
The dosage of crosslinking agent can be by suitably adjusting to obtain.In another preferred embodiment of the invention, bifunctionality or three officials
The acrylic monomers and/or bifunctionality of energy degree or the epoxy monomer of three-functionality-degree and epoxy novolac-acrylic ester block
The mass ratio of object is 1~3：10~20.In the range by mass ratio control, it can be realized under the premise of relatively fewer dosage
The cross-linking effect that speed well and cross-linked structure are stablized.
It has been observed that according to actual needs, other required one or more auxiliary in product process can will be prepared into
Ingredient is included.Further include curing agent in above-mentioned quantum dot composition in another preferred embodiment of the invention, it is excellent
It is radical UV curing agent and thermal curing agents or radical UV curing agent and cation curing agent to select curing agent.Free radical light
The more preferable UV free radical curing agents of curing agent, the more preferable cation photocuring agent of cation curing agent.
The specific type of radical UV curing agent in above preferred embodiment includes but are not limited to 1- hydroxy-cyclohexyls
Phenyl ketone (photoinitiator 184), 2- methyl-1s-[4- methyl mercaptos phenyl] -2- morpholinyl -1- acetone (photoinitiator 907), 2- hydroxyls
Base-aminomethyl phenyl propane -1- ketone (photoinitiator 1173), 2,4,6- trimethylbenzoy-dipheny phosphine oxide (photoinitiators
TPO), bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides (photoinitiator 819) of phenyl, 2- phenyl benzyl -2- dimethyl amines -1-
[4- morpholine benzyls phenyl]-butanone (photoinitiator 369), α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone (photoinitiator 651), hexichol
Any one or a few in ketone (photoinitiator b P) and methyl benzoylformate (photoinitiator MBF).Cationic photopolymerization is solid
The specific type of agent includes but are not limited to 4,4'- dimethyl diphenyl salt compounded of iodine hexafluorophosphate, bis- (4- 2-methyl-2-phenylpropanes bases)
Iodine hexafluorophosphate, bis- (4- 2-methyl-2-phenylpropanes base) iodine fluoroform sulphonates, cyclopropyl diphenyl sulphur tetrafluoroborate, diphenyl
Iodine hexafluorophosphate, diphenyl iodine arsenate, diphenyl iodine trifluoro-methanyl sulfonate, triphenyl sulphur tetrafluoroborate,
Any one or a few in triphenyl phosphonium bromide sulfonium and tri-p-tolylsulfonium hexafluorophosphate.The specific type packet of thermal curing agents
Include but lose be limited to ethylenediamine, diethylenetriamine, polyethylene polyamine, dipropylenetriamine, m-phenylene diamine (MPD), two amido diphenyl sulfones,
Hydroxyethyl ethylenediamine, benzophenone tetracarboxylic dianhydride, tetrabydrophthalic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride,
Any one or a few in benzene tetracarboxylic acid acid anhydride, 2-methylimidazole and 2- ethyl imidazol(e)s.These curing agent have applicability wide,
The advantages that curing rate is fast, and curing efficiency is high, being used in combination has certain synergistic effect, obtains solidfied material of good performance.
In actual production, according to the difference of the performance requirement for the luminescent device to be prepared, above-mentioned quantum dot composition
In can also include improving or the ingredient comprising its performance, to further increase the luminous efficiency of quantum dot in luminescent device
And stability of photoluminescence.Further include additive in above-mentioned quantum dot composition, this adds in another preferred embodiment of the invention
It is light diffusion particle and/or antioxidant to add agent.
In above preferred embodiment, the conventional photodiffusion material of light diffusion particle selection, in the present invention include but
It is not limited only to TiO2、Zr2O3、ZnO、Al2O3、BaSO4、CaCO3、SiO2And any one or a few in organic silicon.Antioxygen
Agent includes but are not limited to 4- hydroxy-dodecanoic acids anilid, N, double -3 (3, the 5- di-t-butyl -4- hydroxyls of six methines of N'-
Phenyl) propionamide, 4,4-, bis- t-octyl diphenylamines, 2,6-di-tert-butyl p-cresol (BHT), β (3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid octadecyl (antioxidant 1076), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
(antioxidant 1010), three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168), bis- (2,4- DI-tert-butylphenol compounds) seasons penta
Any one in tetrol diphosphites (antioxidant 626) and the double octadecyl esters (antioxidant 618) of pentaerythrite diphosphorous acid
Or it is several.Light diffusion particle can effectively improve the luminous efficiency of quantum dot, and antioxidant helps to extend quantum dot composite material
Stability.On the one hand, the light diffusion particle of mentioned kind has preferable light diffusion effect, can effectively improve quantum dot effect
Rate, and cost is relatively low, preferably dissolves each other with physical efficiency before macromolecule matrix solidfied material.On the other hand, the antioxidant tool of mentioned kind
Phenomena such as having preferable antioxidant effect, xanthochromia and the degradation of macromolecule matrix solidfied material precursor can be effectively inhibited.Moreover, being obstructed
Phenols and phosphite ester kind antioxidant are used in compounding the synergistic effect that can reach certain, have more good antioxidant effect.
In another typical embodiment of the invention, a kind of preparation method of quantum dot composite material is provided, it should
Preparation method includes：Macromolecule matrix solidfied material precursor, crosslinking agent, curing agent, quantum dot and optional additive are carried out
Mixing, obtains the first mixture；First mixture is cured, quantum dot composite material is obtained；Wherein, macromolecule matrix is solid
Compound precursor includes epoxy novolac-acrylate block copolymer.
The preparation method of above-mentioned quantum dot composite material, by using having both insulating of the epoxy resin to aqueous vapor and oxygen
Epoxy novolac-acrylate block copolymer of the good advantage of the compatibility of the good and acrylate of energy and quantum dot is as amount
The macromolecule matrix solidfied material precursor of son point, the solidification caused by the crosslinking of crosslinking agent and curing agent successfully solve with
The compatibility of quantum dot and barrier sex chromosome mosaicism, and the presence of additive also contributes to improve the efficiency of quantum dot and steady in a long-term
Property.
In above-mentioned preparation method, the ratio of two blocks can be according to reality in epoxy novolac-acrylate block copolymer
The difference that border needs rationally is adjusted.Different phase separation structures can be formed according to the adjustment of the size of x and y.When x is approximate with y
When equal, epoxy novolac-acrylate block copolymer forms stratiform phase separation structure, novolac epoxy resin block and acrylic acid
Ester block rule is arranged in layer structure.As shown in Fig. 1 (a), Fig. 1 (b) and Fig. 1 (c), novolac epoxy resin block 30 arranges
In side, arylate blocks 40 are arranged in the other side, and arylate blocks 40 first form acrylic acid under the action of photocuring
Ester block cured layer 80；Then novolac epoxy resin block 30 forms novolac epoxy resin under the action of heat cure or photocuring
Block cured layer 90.And work as x=1, when y=5, epoxy novolac-acrylate block copolymer then forms spherical phase separation structure.
As shown in Fig. 2 (a), Fig. 2 (b) and Fig. 2 (c), arylate blocks 40 since segment is shorter, flock together to be formed it is spherical in
The heart, and novolac epoxy resin block 30 is then arranged in outside, is formed to arylate blocks 40 and surrounds shape.Quantum dot (including it is green
Color quantum dot 10 and red quantum dot 20) due to preferable with the compatibility of arylate blocks 40, preferentially it is dispersed in acrylate
In block 40.After radical UV curing, arylate blocks 40 are first cured to be formed around green quantum dot 10 and amount of red
First shell 100 of son point 20, then under the action of heat cure or photocuring, novolac epoxy resin block 30 is formed by curing
The periphery of first shell 100 forms the second shell 110.
In the above preparation method, the mass ratio of quantum dot and macromolecule matrix solidfied material precursor can be according to being intended to prepare
Requirement of the luminous product to luminescent properties reasonably select.Quantum dot can be single quantum dot, or numerous
Quantum dot.In a kind of preferred embodiment of the present invention, the mass ratio of above-mentioned quantum dot and macromolecule matrix solidfied material precursor
It is 0.1~1：10~100.It within the above range by the control of the mass ratio of quantum dot and macromolecule matrix solidfied material precursor, can base
This meets requirement of the current luminous product to luminescent properties.
Crosslinking agent used in above-mentioned preparation method is the crosslinking agent of routine, and dosage can be according to specific crosslinking agent kind
The difference of class and it is different.In a kind of preferred embodiment of the present invention, above-mentioned crosslinking agent is the acrylic acid that degree of functionality is more than or equal to 2
Monomer and epoxy monomer；More preferable crosslinking agent is three-functionality-degree acrylic monomers and epoxy monomer；More preferable three-functionality-degree propylene
The mass ratio of acid monomers and epoxy monomer and epoxy novolac-acrylate block copolymer is 1~3：10~20.Degree of functionality is more than
Acrylic monomers and epoxy monomer equal to 2 have curing rate fast and the advantages such as degree of cross linking height.And by bifunctionality or three officials
The mass ratio of energy degree acrylic monomers and epoxy monomer and epoxy novolac-acrylate block copolymer is controlled 1~3：10~
In the range of 20, under the premise of ensureing fast curing rate and degree of cross linking height, the flexibility demand of solidfied material is balanced.
Particular/special requirement is had no to the specific type of used curing agent in above-mentioned preparation method, as long as can be formed by curing
Quantum dot composite material.In a kind of preferred embodiment of the present invention, above-mentioned curing agent include radical UV curing agent and
The step of thermal curing agents, above-mentioned solidification includes：Pair the first progress photocuring, is cured under the action of radical UV curing agent
Semi-finished product；Heat cure is carried out to solidification semi-finished product under the action of thermal curing agents, obtains quantum dot composite material.
Above preferred embodiment by using radical UV curing agent and thermal curing agents to contain quantum dot and crosslinking agent with
And the first mixture of additive carries out step curing, obtains quantum dot composite material.Above-mentioned radical UV curing agent is selected from 1-
Hydroxycyclohexylphenylketone (photoinitiator 184), 2- methyl-1s-[4- methyl mercaptos phenyl] -2- morpholinyl -1- acetone are (light-initiated
Agent 907), 2- hydroxy-methyl phenyl-propane -1- ketone (photoinitiator 1173), 2,4,6- trimethylbenzoy-diphenies oxidation
Bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides (photoinitiator 819) of phosphine (photoinitiator TPO), phenyl, 2- phenyl benzyls -2- two
Methyl amine -1- [4- morpholine benzyls phenyl]-butanone (photoinitiator 369), α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone (photoinitiator
651), any one or a few in benzophenone (photoinitiator b P) and methyl benzoylformate (photoinitiator MBF).Heat
Curing agent is selected from ethylenediamine, diethylenetriamine, polyethylene polyamine, dipropylenetriamine, m-phenylene diamine (MPD), two amido diphenyl sulfones, hydroxyl
Ethylethylenediamine, benzophenone tetracarboxylic dianhydride, tetrabydrophthalic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, equal benzene
Any one or a few in tetracarboxylic acid anhydride, 2-methylimidazole and 2- ethyl imidazol(e)s.Work of the esters of acrylic acid in light curing agent
Semi-solid preparation product are formed with lower cross-linking reaction, then, cures after being carried out to epoxy resin by thermal curing agents, system can be effectively improved
The degree of cross linking.Different curing agent, which are used in compounding, can realize curing rate soon and curing efficiency height and condensate performance is excellent consolidates
Change effect.
The solidification process of above-mentioned quantum dot composite material such as Fig. 1 (a)-Fig. 1 (b)-Fig. 1 (c) and Fig. 2 (a)-Fig. 2 (b)-Fig. 2
(c) shown in.Wherein, Fig. 1 (a) to Fig. 1 (c) respectively illustrates epoxy novolac-acrylate block copolymer and forms lamellar phase point
Before curing when from structure after (a), photocuring after (b) and heat or photocuring (c) microcosmic chain form schematic diagram.
As shown in Fig. 1 (a), before solidification, novolac epoxy resin block 30 is arranged in side, and arylate blocks 40 are arranged in
The other side；Under the action of photocuring, as shown in Fig. 1 (b), using acrylic monomers 50 as crosslinking agent, arylate blocks 40
It is first cured to form arylate blocks cured layer 80；Then as shown in Fig. 1 (c), using epoxy monomer 60 as crosslinking agent, phenol
Formaldehyde epoxy resin block 30 forms novolac epoxy resin block cured layer 90 under the action of heat cure or photocuring.And work as x=
When 1, y=5, epoxy novolac-acrylate block copolymer then forms spherical phase separation structure.As shown in Fig. 2 (a), acrylic acid
Ester block 40 flocks together to form spherical center since segment is shorter, and novolac epoxy resin block 30 is then arranged in outside,
Arylate blocks 40 are formed and surround shape.Quantum dot (including green quantum dot 10 and red quantum dot 20) due to acrylic acid
The compatibility of ester block 40 is preferable, is preferentially dispersed in arylate blocks 40.After radical UV curing, as shown in Fig. 2 (b),
Arylate blocks 40 are first cured to be formed around green quantum dot 10 and amount of red using acrylic monomers 50 as crosslinking agent
First shell 100 of son point 20, then under the action of heat cure or photocuring, as shown in Fig. 2 (c), novolac epoxy resin is embedding
Section 30 is formed by curing in the periphery of the first shell 100 using epoxy monomer 60 as crosslinking agent, is formed the second shell 110.
In another preferred embodiment of the invention, above-mentioned curing agent includes that radical UV curing agent and cationic photopolymerization are solid
The step of agent, above-mentioned solidification includes：It is mixed to first under being acted on while radical UV curing agent and cation photocuring agent
It closes object to be cured, obtains quantum dot composite material.The preferred embodiment uses free radical and cation photocuring agent, by same
When pair the first mixture carry out a UV irradiations solidification process can be completed, obtain quantum dot composite material.
In above-mentioned curing schedule, the solidification of novolac epoxy resin block 30 is to realize that light is solid by cation photocuring agent
Change.It is added radical UV curing agent and cation photocuring agent in epoxy novolac-acrylate block copolymer, when solidification is selected
365nm UV lamps (and 450nm blue-ray lights are simultaneously) irradiation is selected, can ensure that the free radical of acrylic acid causes (365nm) and ring in this way
The cation of oxygen groups causes (ultraviolet 365nm and blue light 450nm can) and is carried out at the same time.Moreover, because free radical causes speed
Degree is more faster than cationic curing, and the state initially formed is equally as shown in Fig. 1 (b) and Fig. 2 (b), and only double bond is partial cross-linked,
Epoxy group is still in free state；And after curing after the cation of certain time, what end-state and heat cure were formed
Fig. 1 (c) is consistent with Fig. 2 (c), and epoxy group is successfully crosslinked.The advantages of radical UV curing is quick solidifying, the disadvantage is that volume contraction
Rate is big；And the advantages of cation photocuring is that cubical contraction is small, the disadvantage is that slow curing is (all than heat cure, radical UV curing
Slowly), but above-mentioned curing not only takes full advantage of its advantage, but also has adapted to successively cured demand using its disadvantage,
Save irradiation time simultaneously.
In a kind of more specifical embodiment, in the different solidification process of above two, the light source of UV irradiations is 365nm
LED cold light sources or it is metal halogen lamp source centered on 365nm or mercury lamp light source or is centered on 450nm
Visible light source.
In another typical embodiment of the invention, a kind of quantum dot composite material is additionally provided, the quantum dot is multiple
Condensation material is prepared using any of the above-described kind of preparation method.Had using the quantum dot composite material that the above method is prepared
Compatibility and barrier property are superior, and luminous efficiency is high, the good advantageous effect of stability of photoluminescence.
In another typical embodiment of the invention, a kind of quantum dot composite material is additionally provided, the quantum dot is multiple
Condensation material includes quantum dot and the macromolecule matrix solidfied material being coated on around quantum dot, which is phenolic aldehyde
Cross-linking products between epoxy-acrylic ester block copolymer, the cross-linking products have the structural unit as shown in following formula (I)：
Quantum dot composite material with above structure unit can be embedding according to novolac epoxy resin block and acrylate
The length of section can form different phase separation structures.When novolac epoxy resin block and arylate blocks approximately equal, phenol
Aldehyde epoxy-acrylic ester block copolymer forming layer shape phase separation structure, as shown in Fig. 1 (a) to Fig. 1 (c), novolac epoxy resin
40 rule of block 30 and arylate blocks is arranged in layer structure, and novolac epoxy resin block 30 is arranged in side, propylene
Acid esters block 40 is arranged in the other side, and novolac epoxy resin block cured layer 90 is respectively formed after solidification and arylate blocks are solid
Change layer 80.And when arylate blocks 40 are much smaller than novolac epoxy resin block 30, epoxy novolac-acrylic ester block
Object then forms spherical phase separation structure, and as shown in Fig. 2 (a) to Fig. 2 (c), arylate blocks 40 are gathered in since segment is shorter
Spherical center is formed together, and novolac epoxy resin block 30 is then arranged in outside, is formed to arylate blocks 40 and surrounds shape.
Quantum dot is preferentially dispersed in arylate blocks 40 due to preferable with the compatibility of arylate blocks 40.Acrylate is embedding
Section 40 is solidificated in internal layer and forms the first shell 100 around green quantum dot 10 and red quantum dot 20, and novolac epoxy resin is embedding
Section 30 is then formed by curing the second shell 110 around green quantum dot 10 and red quantum dot 20 in outer layer, to be formed to measure
Nucleocapsid centered on son point.
Structural unit in above-mentioned quantum dot composite material refers to constituting macromolecular chain and determining macromolecular structure with certain
The atom combination that mode connects.Multiple "-" of above structure cell end represent half after double bond or epoxy bond are opened
Chemical bond, arbitrary half in the structural unit that arbitrary half of chemical bond in each above structure unit can be adjacent thereto
Chemical bond is attached to form complete chemical bond.Arbitrary half of chemical bond of every half of chemical bond and another structural unit connects
It connects, just forms the macromolecule matrix solidfied material of reticular structure in this way.The macromolecule matrix solidfied material of reticular structure surrounds center
Quantum dot just form above-mentioned quantum dot composite material.
In another typical embodiment of the invention, a kind of quantum dot light emitting device, quantum dot hair are additionally provided
Optical device includes quantum dot composite material, and quantum dot composite material is above-mentioned quantum dot composite material.Including above-mentioned quantum dot is multiple
The quantum dot light emitting device of condensation material has the advantages that luminous efficiency is high and stability is good.
In quantum dot composite material contained by above-mentioned quantum dot light emitting device, the specific luminescent color of quantum dot can basis
Practical luminescent device is reasonably selected.In a kind of preferred embodiment of the present invention, quantum dot be red quantum dot and
Green quantum dot.Red quantum dot and green quantum dot can be used in display field, red under the irradiation of blue led backlight
Blue light can be absorbed with green quantum dot and converts thereof into red and green light, and it is white to form RGB with unabsorbed blue light
Light field.Due to the half-peak width of red and green quantum dot, compared with traditional liquid crystal display, quantum dot shows that colour gamut is high, face
Color saturation is high.
Above-mentioned quantum dot light emitting device can be quantum dot film or quantum dot pipe according to actual needs.Quantum dot composition exists
Film-forming can form quantum dot film on carrier.In concrete application environment, the upper layer of quantum dot film or lower layer can be with
There are the Obstruct membrane or protective film that polymer film is formed, or there can also be other among quantum dot film and polymer film
Layer.Quantum dot composition cures in the cavity of pipeline forms quantum dot pipe, and quantum dot pipe is to place quantum dot composition
It is then sealed to solidification in tubular container, is used for the light-switching device of display backlight system.
Advantageous effect to further illustrate the present invention below in conjunction with specific embodiments.
Embodiment 1
Using epoxy novolac-acrylate block copolymer as macromolecule matrix solidfied material precursor, by macromolecule matrix
Solidfied material precursor, crosslinking agent and curing agent obtain the first mixture；First mixture is cured, it is multiple to obtain quantum dot
Condensation material, each specific reactant of step is raw materials used to be shown in Table 1, and when specific reaction condition is shown in Table 2 to the dosage between each raw material.
Embodiment 2
Embodiment 2 uses epoxy novolac-acrylate block copolymer as macromolecule matrix solidfied material precursor, by high score
Subbase body solidfied material precursor, crosslinking agent, curing agent and additive, obtain the first mixture；First mixture is consolidated
Change, obtains quantum dot composite material, each specific reactant of step is raw materials used to be shown in Table 1, and the dosage between each raw material is when specific
Reaction condition is shown in Table 2.
Embodiment 3-10
Embodiment 3-10 uses the step identical as embodiment 1 or 2, using preparation parameter shown in Tables 1 and 2 and condition
It is prepared.
Comparative example 1
Using polyacrylate as macromolecule matrix solidfied material precursor, other parameters condition is shown in Tables 1 and 2.
Comparative example 2
Using bisphenol A epoxide resin as macromolecule matrix solidfied material precursor, other parameters condition is shown in Tables 1 and 2.
Comparative example 3
Using the mixture of acrylate and epoxy resin as macromolecule matrix solidfied material precursor, other parameters condition is shown in
Tables 1 and 2.
Table 1：Each raw materials used type of embodiment and comparative example
Table 2：The preparation condition of each embodiment and comparative example
Detection：The performance of quantum dot composite material prepared by the various embodiments described above and comparative example is detected, is detected
It the results are shown in Table 3 and table 4.
The detection method of quantum dot light emitting efficiency is：Using 450nm blue LED lamps as backlight spectra, integrating sphere is utilized
Blue backlight spectrum and the spectrum through quantum dot composite material are tested respectively, and calculating quantum dot using the integral area of spectrogram sends out
Light efficiency.
Quantum dot light emitting efficiency=(red quantum dot absorbs peak area+green quantum dot peak absorption area)/(Blue backlight
Peak area-is through the unabsorbed blue peak area of quantum dot composite material) * 100%.
The test method of stability of photoluminescence includes mainly：The illumination of high temperature blue light (70 DEG C, 0.5W/cm2), high temperature and humidity
(65 DEG C/95%RH) under the aging conditions such as high-temperature storage (85 DEG C), detect the efficiency change and invalid edges of quantum dot composite material
Size.
Table 3：
Note：The above efficiency is relative efficiency, the efficiency of comparative example 1 is set to 100%, other efficiency correspond in proportion.
Table 4：
Note：The above invalid edges are after making quantum dot film, by determining the size of edge invalid edges, quantum dot under microscope
The size of film is 6cm*6cm.
From table 3 and table 4 as can be seen that arylate blocks are more, start efficiency is higher, and aging attenuation amplitude is bigger, black
Bian Yue great；Conversely, epoxy block is more, start efficiency is lower, and aging attenuation amplitude is smaller, and black surround is smaller.Embodiment 1-10 with
Comparative example 1 is compared, and initial light emission efficiency is not much different with comparative example 1, but luminous efficiency attenuation amplitude (passes through formula：Decaying width
Degree=(aging behind efficiency-starting efficiency)/starting efficiency x 100% is calculated) it is substantially reduced compared with comparative example 1, stable luminescence
Property greatly enhances.For embodiment 1-10 compared with comparative example 2, initial light emission efficiency is far above comparative example 2, and luminous efficiency decaying width
Degree is not much different with comparative example 2.Compared with comparative example 3, embodiment 1-10, which is used, contains novolac epoxy resin block and acrylic acid
The block copolymer of ester block, the macromolecule matrix solidfied material precursor formed in a manner of being keyed by chemistry surround quantum
The luminescent material that point is formed, compared with the quanta point material that acrylate and epoxy resin using physical blending are formed,
Not only have higher luminous efficiency, and after aging luminous efficiency attenuation amplitude it is small, the size of invalid edges is also relatively small,
The stability of luminous efficiency is stronger.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：Pass through selection
Include macromolecule matrix solidfied material precursor of the novolac epoxy resin-acrylic block copolymers as dispersion quantum dot, due to phenol
Formaldehyde epoxy resin-acrylic block copolymers combine that acrylate and quantum dot compatibility be good and epoxy resin to oxygen and
The advantages of aqueous vapor good barrier property, have it is amphipathic, to setting about from macromolecule matrix solidfied material precursor material composition in terms of, solution
The problem of compatibility and starvation and aqueous vapor with quantum dot, improves the luminous efficiency of quantum dot composite material and steady
It is qualitative.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (20)
1. a kind of quantum dot composition, which is characterized in that the quantum dot composition includes quantum dot and macromolecule matrix solidification
Object precursor further includes crosslinking agent and curing agent in the quantum dot composition, and the macromolecule matrix solidfied material precursor includes phenol
Aldehyde epoxy-acrylic ester block copolymer.
2. quantum dot composition according to claim 1, which is characterized in that the epoxy novolac-arylate blocks are total
Polymers is epoxy novolac-acrylate block copolymer of following structural formula：
Wherein, x, y are integer, and x >=1, y >=1, and 3≤x+y≤7.
3. quantum dot composition according to claim 1, which is characterized in that the crosslinking agent is double/three-functionality-degree propylene
Acid monomers and/or double/three-functionality-degree epoxy monomer.
4. quantum dot composition according to claim 3, which is characterized in that described double/three-functionality-degree acrylic monomers and/
Or the mass ratio of double/three-functionality-degree epoxy monomer and the epoxy novolac-acrylate block copolymer is 1~3：10~20.
5. quantum dot composition according to claim 1, which is characterized in that the curing agent be radical UV curing agent and
Thermal curing agents, or be radical UV curing agent and cation photocuring agent.
6. quantum dot composition according to claim 1, which is characterized in that the quantum dot composition further includes addition
Agent.
7. quantum dot composition according to claim 6, which is characterized in that the additive be light diffusion particle and/or
Antioxidant.
8. a kind of preparation method of quantum dot composite material, which is characterized in that the preparation method includes：
Macromolecule matrix solidfied material precursor, crosslinking agent, curing agent, quantum dot and optional additive are mixed to get first to mix
Close object；
First mixture is cured, the quantum dot composite material is obtained；
Wherein, the macromolecule matrix solidfied material precursor includes epoxy novolac-acrylate block copolymer.
9. preparation method according to claim 8, which is characterized in that the epoxy novolac-acrylate block copolymer
Structural formula be：Wherein, x, y are integer, and
X >=1, y >=1, and 3≤x+y≤7.
10. preparation method according to claim 8, which is characterized in that the crosslinking agent be bifunctionality acrylic monomers,
Three-functionality-degree acrylic monomers, bifunctionality epoxy monomer and/or three-functionality-degree epoxy monomer.
11. preparation method according to claim 8, which is characterized in that the crosslinking agent and the epoxy novolac-acrylic acid
The mass ratio of ester block copolymer is 1~3：10~20.
12. preparation method according to claim 8, which is characterized in that the curing agent is radical UV curing agent and heat
Curing agent.
13. preparation method according to claim 12, which is characterized in that the step of solidification includes：
Photocuring is carried out to first mixture using the radical UV curing agent, obtains solidification semi-finished product；
Heat cure is carried out to the solidification semi-finished product using thermal curing agents, obtains the quantum dot composite material.
14. preparation method according to claim 8, which is characterized in that the curing agent is radical UV curing agent and sun
The step of ion light curing agent, the solidification includes：
First mixture is cured under being acted on while radical UV curing agent and cation photocuring agent, is obtained
The quantum dot composite material.
15. preparation method according to claim 8, which is characterized in that the additive is light diffusion particle and/or antioxygen
Agent.
16. a kind of quantum dot composite material, which is characterized in that the quantum dot composite material, which uses in claim 8 to 15, appoints
Preparation method described in one is prepared.
17. a kind of quantum dot composite material, which is characterized in that the quantum dot composite material includes quantum dot and is coated on described
Macromolecule matrix solidfied material around quantum dot, the macromolecule matrix solidfied material are epoxy novolac-acrylic ester block
Cross-linking products between object, the cross-linking products have the structural unit as shown in following formula (I)：
18. a kind of quantum dot light emitting device, including quantum dot composite material, which is characterized in that the quantum dot composite material is
Quantum dot composite material described in claim 17.
19. quantum dot light emitting device according to claim 18, which is characterized in that the amount in the quantum dot composite material
Son point is red quantum dot and/or green quantum dot.
20. quantum dot light emitting device according to claim 18, which is characterized in that the quantum dot light emitting device is quantum
Point film or quantum dot pipe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610632828.8A CN106188429B (en) | 2016-08-02 | 2016-08-02 | Quantum dot composition, quantum dot composite material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610632828.8A CN106188429B (en) | 2016-08-02 | 2016-08-02 | Quantum dot composition, quantum dot composite material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106188429A CN106188429A (en) | 2016-12-07 |
| CN106188429B true CN106188429B (en) | 2018-10-12 |
Family
ID=57498650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610632828.8A Active CN106188429B (en) | 2016-08-02 | 2016-08-02 | Quantum dot composition, quantum dot composite material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106188429B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359264B (en) * | 2017-08-03 | 2019-12-31 | 青岛海信电器股份有限公司 | QLED, preparation method and display device |
| CN109423275B (en) | 2017-08-29 | 2020-03-31 | 纳晶科技股份有限公司 | Quantum dot composition, quantum dot luminescent material, preparation method thereof and luminescent device containing quantum dot luminescent material |
| CN117687243A (en) * | 2017-10-17 | 2024-03-12 | 科迪华公司 | Ink composition with high quantum dot concentration for display device |
| CN112375497B (en) * | 2020-11-16 | 2022-09-27 | 京东方科技集团股份有限公司 | Light-emitting film, light-emitting device, manufacturing method of light-emitting device and display substrate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280565A (en) * | 2010-06-14 | 2011-12-14 | 三星Led株式会社 | Light Emitting Device Package Using Quantum Dot, Illumination Apparatus and Display Apparatus |
| CN102916116A (en) * | 2012-08-14 | 2013-02-06 | 杭州纳晶科技有限公司 | LED (light-emitting diode) optical accessory, LED lamp and LED optical accessory preparation method |
| CN103069331A (en) * | 2010-08-16 | 2013-04-24 | Lg伊诺特有限公司 | Member for backlight unit using quantum dots and method of manufacturing the same |
| CN103146262A (en) * | 2012-12-12 | 2013-06-12 | 京东方科技集团股份有限公司 | Use of quantum dot in pigment dispersion liquid, and pigment dispersion liquid and preparation method thereof |
| CN103430337A (en) * | 2011-03-28 | 2013-12-04 | 奥斯兰姆施尔凡尼亚公司 | LED device utilizing quantum dots |
| CN103937158A (en) * | 2014-03-24 | 2014-07-23 | 北京化工大学 | Quantum dot with high transparency and high fluorescence efficiency/epoxy resin nano composite material, preparation and applications thereof |
| CN104501043A (en) * | 2014-12-19 | 2015-04-08 | 广东普加福光电科技有限公司 | Long-service-life quantum dot fluorescent composite thin film and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100466297C (en) * | 2002-09-05 | 2009-03-04 | 奈米系统股份有限公司 | Nanostructures,nano coompositon and photovolaitic device |
| KR100789559B1 (en) * | 2006-12-20 | 2007-12-28 | 삼성전자주식회사 | Inorganic eletroluminescent device comprising the insulating layer, method for preparing the same and electronic device comprising the same |
-
2016
- 2016-08-02 CN CN201610632828.8A patent/CN106188429B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280565A (en) * | 2010-06-14 | 2011-12-14 | 三星Led株式会社 | Light Emitting Device Package Using Quantum Dot, Illumination Apparatus and Display Apparatus |
| CN103069331A (en) * | 2010-08-16 | 2013-04-24 | Lg伊诺特有限公司 | Member for backlight unit using quantum dots and method of manufacturing the same |
| CN103430337A (en) * | 2011-03-28 | 2013-12-04 | 奥斯兰姆施尔凡尼亚公司 | LED device utilizing quantum dots |
| CN102916116A (en) * | 2012-08-14 | 2013-02-06 | 杭州纳晶科技有限公司 | LED (light-emitting diode) optical accessory, LED lamp and LED optical accessory preparation method |
| CN103146262A (en) * | 2012-12-12 | 2013-06-12 | 京东方科技集团股份有限公司 | Use of quantum dot in pigment dispersion liquid, and pigment dispersion liquid and preparation method thereof |
| CN103937158A (en) * | 2014-03-24 | 2014-07-23 | 北京化工大学 | Quantum dot with high transparency and high fluorescence efficiency/epoxy resin nano composite material, preparation and applications thereof |
| CN104501043A (en) * | 2014-12-19 | 2015-04-08 | 广东普加福光电科技有限公司 | Long-service-life quantum dot fluorescent composite thin film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Entropic Ligands for Nanocrystals: From Unexpected Solution Properties to Outstanding Processability;Yu Yang, et al.;《Nano Letters》;20160228;第16卷(第4期);第2133-2138页 * |
| PGMA-g-EDA梳状聚合物的制备及其对量子点修饰的研究;王玉珍 等;《高分子学报》;20130820(第8期);第1039-1046页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106188429A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106381140B (en) | Quantum dot composition, quantum dot composite material, preparation method and application | |
| CN106188429B (en) | Quantum dot composition, quantum dot composite material, preparation method and application | |
| JP6832898B2 (en) | Quantum dot film using polyphase resin | |
| EP3122840B1 (en) | Quantum dot compositions | |
| CN105778887B (en) | A kind of method, quantum dot complex particle and the application of sealing quantum dot | |
| US11091691B2 (en) | Quantum dot composition, quantum dot luminescent material, preparation method thereof and light-emitting device containing the same | |
| TWI547541B (en) | Transformative wavelength conversion medium | |
| JP6158905B2 (en) | Light emitting device or phosphor-containing sheet for light emitting device | |
| CN103937158B (en) | A kind of high transparent, the quantum dot/epoxy resin nano composites of high fluorescence efficiency, preparation and application | |
| KR102087270B1 (en) | Wavelength conversion member and light-emitting device | |
| CN106967412A (en) | Containing phosphor particle and using it light-emitting device, containing phosphor plates | |
| CN107828416A (en) | A kind of quantum dot fluorescence composite and its preparation method and application | |
| CN106098905B (en) | The method of the emission spectrum of the continuous flow synthetic method and correction light emitting device of the quantum dot-doped polymer pad of core-shell structure copolymer | |
| KR20150140720A (en) | Organic phosphor-functionalized nanoparticles and compositions comprising the same | |
| WO2020254236A1 (en) | Luminescent component | |
| KR20060000313A (en) | White led comprising photo-luminescent powder with large mean particle size and manufacturing method thereof and transparent resin composition used therein | |
| Galeotti et al. | Tailorable perylene-loaded fluorescent nanostructures: a multifaceted approach enabling their application in white hybrid LEDs | |
| CN107534075A (en) | With the quantum dot of metal mercaptide polymer stabilising | |
| CN109233804B (en) | Quantum dot powder and preparation method thereof, light-emitting device, quantum dot composition, quantum dot film and preparation method thereof | |
| WO2023065535A1 (en) | Preparation method for cyanuric acid coated halogen perovskite nano mixed crystal and use thereof | |
| CN108864384A (en) | Quantum dot dispersion resin formed body, quantum dot dispersion colloid and luminescent device | |
| JP2014520924A (en) | High-efficiency light-converting plastic parts incorporating a phosphor in the polymer by adding to the monomer before polymerization | |
| JP2008159756A (en) | Manufacturing method of white light-emitting diode, and photo-curing phosphor containing composition | |
| TW201035197A (en) | Phosphor-containing resin composition and phosphor sheet | |
| CN106590622A (en) | Modified rare earth light conversion material high-molecular polymer agricultural film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |