CN101426883B - 无机荧光增白剂 - Google Patents
无机荧光增白剂 Download PDFInfo
- Publication number
- CN101426883B CN101426883B CN200780014234XA CN200780014234A CN101426883B CN 101426883 B CN101426883 B CN 101426883B CN 200780014234X A CN200780014234X A CN 200780014234XA CN 200780014234 A CN200780014234 A CN 200780014234A CN 101426883 B CN101426883 B CN 101426883B
- Authority
- CN
- China
- Prior art keywords
- phosphor
- purposes
- sulfide
- white
- halogenide
- 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.)
- Expired - Fee Related
Links
- 230000003287 optical effect Effects 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 238000006862 quantum yield reaction Methods 0.000 claims abstract description 5
- 230000007423 decrease Effects 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 34
- 239000000975 dye Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 230000002087 whitening effect Effects 0.000 claims description 16
- 239000008199 coating composition Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 halogen ion Chemical class 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012463 white pigment Substances 0.000 claims description 5
- BKQMNPVDJIHLPD-UHFFFAOYSA-N OS(=O)(=O)[Se]S(O)(=O)=O Chemical compound OS(=O)(=O)[Se]S(O)(=O)=O BKQMNPVDJIHLPD-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 150000003346 selenoethers Chemical class 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical group 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical group 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 238000005282 brightening Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 11
- 239000004753 textile Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 235000021286 stilbenes Nutrition 0.000 description 6
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000037072 sun protection Effects 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 241000669298 Pseudaulacaspis pentagona Species 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 235000012211 aluminium silicate Nutrition 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
- 239000007844 bleaching agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- PLOYJEGLPVCRAJ-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid;styrene Chemical compound C=CC=C.OC(=O)C=C.C=CC1=CC=CC=C1 PLOYJEGLPVCRAJ-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YJHDFAAFYNRKQE-YHPRVSEPSA-L disodium;5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S([O-])(=O)=O)=CC=2)S([O-])(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 YJHDFAAFYNRKQE-YHPRVSEPSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000005539 phosphorimetry Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011155 quantitative monitoring Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- 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
- C08K3/32—Phosphorus-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/919—Paper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Luminescent Compositions (AREA)
- Detergent Compositions (AREA)
- Glass Compositions (AREA)
- Paints Or Removers (AREA)
Abstract
本发明涉及新颖的无机增白剂、它们的制备方法和它们用于增白基底的用途。更特别地，该新颖的无机增白剂是无机发光材料，其特征在于它们具有：(i)在350-375nm范围内的最大吸收；(ii)接近400nm的吸收带的急剧下降；(iii)至少0.8的磷光量子产率；和(iv)在415-445nm的最大磷光。
Description
本发明涉及新颖的无机增白剂、它们的制备方法和它们的用于增白基底的用途。
通常，荧光增白剂是无色到微弱着色的有机化合物，其在溶液中或者被施用到基底上，吸收紫外光(例如从在大约300-430nm的日光中)并将大部分所吸收的能量作为在大约400-500nm的蓝色荧光而再发出。在日光中，荧光增白剂因此可以补偿在白色工业基底例如纺织品、纸张或塑料上所发现的审美上不期望的微黄色脱落物(cast)。此外，因为一部分眼睛不能察觉的日光光谱被转化为可见光，因此增强了材料的亮度，产生了耀眼的白色。
一种补偿微黄色脱落物的方法是使用蓝色染料例如群青或靛蓝。蓝变降低了样品在可见光光谱的长波长部分的反射比。作为结果，该样品呈现出中性白色外观，但是同时它损失了亮度以使它看起来更灰白。相反，荧光增白剂通过吸收主要降低了UV和近可见光的反射比；在可见光波长(主要在435-440nm具有最大值)，它们通过荧光非常大的提高了反射比。该增白剂充当了辅助的发射源。
典型的荧光增白剂的特征在于π-电子发色团，其中存在着π-π*跃迁。发色团必须是刚性的，并且在电子基态和第一激发态中它们的构造应当仅仅有轻微的差别。最好的已知荧光增白剂包括碳环例如二苯乙烯基苯，二苯乙烯基联苯，二乙烯基芪；三嗪基氨基芪；芪基-2H-三唑例如芪基-2H-萘并[1，2-d]三唑和双(1，2，3-三唑-2-基)芪；苯并噁唑例如芪基苯并噁唑和双(苯并噁唑)；呋喃，苯并[b]呋喃，和苯并咪唑例如双(苯并[b]呋喃-2-基)联苯和阳离子苯并咪唑；1，3-二苯基-2-吡唑啉；香豆素；萘亚胺；和1，3，5-三嗪-2-基衍生物。
商业荧光增白剂是具体根据结构、基底和使用模式而配制的。无粉尘的、易于计量的形式是优选的：具有高粉碎强度的自由流动粒子、溶液或者浓缩的分散体。非离子化的荧光增白剂必须被尽可能的细微分散，目的是它们可以快速的和最佳的分散在非极性基底中。它们是通常以粉末(例如用于塑料或者纺纱物)或者作为低粘度分散体(例如用于纺织品工业)来销售的。用添加剂使配方最佳化来控制颗粒强度、溶解、化学稳定性、粘度、储存稳定性或真菌生长。它们还可以包含调色染料和辅助剂来提高它们在给定的应用中的效率。
几千种具有大于100个商标名的荧光增白剂产品在世界范围的市场上销售例如BlankophorTM(Bayer)，HakkolTM(Showa Kayaku)，HostaluxTM(Clariant)，KayaphorTM(Nippon Kayaku)，LeukophorTM(Clariant)，OptiblancTM(3V)，PhotineTM(Hickson&Welch)，TinopalTM(Ciba SpecialtyChemicals)，UltraphorTM(BASF)，UvitexTM(Ciba Specialty Chemicals)，WhitexTM(Sumitomo)，BeloforTM，Calcofluor WhiteTM，EastobrightTM，EnkantineTM，HeliophorTM，MikephorTM，RanipalTM，RyluxTM，ViophosTM，和WobitalTM。
但是，在全部上述的例子中，尽可能大的UV光吸收与尽可能少的固有颜色的结合、强烈的荧光来产生最大的白度和增白剂在基底中的可分散性仍然不能满足全部的日益增长的需求。另外，这里还存在着对于用来在不同应用中更好满足对于荧光增白剂特定的需要的新化学种类的荧光增白剂的持续的需求。
根据本发明，现在已经令人惊讶的发现当所选择的无机发光材料被用作荧光增白剂时，能够更令人满意的满足上述需求。
本发明因此涉及一种用作荧光增白剂的无机发光材料，其中所述的无机发光材料特征在于：
(i)在350-375nm范围内的最大吸收；
(ii)接近400nm的吸收带的急剧下降；
(iii)至少0.8，优选0.95的磷光量子产率；和
(iv)在415-445nm的最大磷光。
术语“无机发光材料”涉及合成产生的结晶化合物，其吸收作用于它们上的能量，并随后立即或者在更长的时期内将该所吸收的能量作为光进行发射，该光发射超过了热辐射。这种光发射也被称作发光，与热辐射相比，对该光发射来说，所激发的能量首先不变成该化合物的热能。它起于原子或分子中的激发态，该激发态具有至少10-9s的寿命。这意味着在激发和光发射之间有10-9s的时间间隔。在激发过程中和随后高到大约10-8s中发生的光发射称作荧光，而持续长于10-8s的发光被称作后余辉(afterglow)或者磷光。对于双曲线衰减和指数式衰减来说，衰变时间分别是其中亮度降低到初始强度的1/10或者1/e的时间。
合适的无机发光材料包括但不限于硫化物和硒化物例如硫化镉和硫硒化物，碱土金属硫化物和硫硒化物；氧硫化物；氧占优的无机发光材料例如铝酸盐，镓酸盐，硅酸盐，锗酸盐，卤代磷酸盐和磷酸盐，氧化物，砷酸盐，钒酸盐，铌酸盐和钽酸盐，硫酸盐，钨酸盐和钼酸盐；卤化物无机发光材料例如金属卤化物和锰活化的卤化物无机发光材料。
此外，本发明的无机发光材料优选具有0.01-20μm的粒度分布。粒度分布的测量可以用粒子计数仪器(Coulter计数器)来进行或者通过激光或者光束散射(Cilas)来进行。费氏(Fisher)数被广泛的用作平均粒径(费氏亚筛分粒度)的度量。特别优选的是至少一种维数尺寸低于100nm的纳米粒子。
本发明的无机发光材料粒子的形状优选是球状，但是具有立方体或薄片形状的粒子同样是合适的。无机发光材料的晶体形式可以通过扫描电子显微镜来评价。
对于相对粗糙的无机发光材料，例如D50>5μm，粒度分布是从筛渣曲线来确定的。
同样的，本发明无机发光材料用沉降速度、沉降密度或者其它沉降特性来表征。沉降流体中的沉降速度可以根据Stokes定律，通过粒子的尺寸、形状、密度和表面电荷来确定。无机发光材料和它们的共混物的沉降特性是除了发光亮度和发光颜色之外，为它们的适用性的一种重要的评价标准。沉降密度能够对于沉降流体的单个晶体在恒定的极性和电解质浓度的凝聚程度进行结论性判断。低密度表示形成了广泛的凝聚形成。本发明的无机发光材料甚至在高浓度也提供单分子增白剂分布。由于没有增白剂分子的聚集，因此不降低量子产率，并且光谱基本上不变。
优选的荧光增白剂是符合下式(I)的这些
AxBy:Eu (I)
其中
A是至少一种碱土金属和/或锌；
B是至少一种阴离子，其选自硅铝酸盐，氧化铝，氧化硅，磷酸盐和卤素；
x是1-10的整数，y是1-5的整数，并且x和y的目的是使得电荷平衡；和
其中铕的含量是0.01-1mol％。
特别优选的增白剂符合式(I)，其中
A是至少一种碱土金属，其选自钡，镁，钙和/或锶；
B是至少一种阴离子，其选自Al10O17 4-、Al16O27 6-、PO4 3-和卤素；并且其中铕的含量是0.1-0.5mol％。
优选的式(I)的增白剂是BaMgAl10O17:Eu、BaMg2Al16O27:Eu和Sr3Ca2(PO4)3Cl:Eu或者(SrBaCa)5(PO4)3Cl:Eu。
本发明进一步提供一种制备式(I)的增白剂的方法，其特征在于：反应是在l100-1600℃的温度，优选在N2和/或H2，例如90％N2和10％H2，或者可选择的95％N2和5％H2存在下完成的。
本发明还提供增白剂制剂，其含有根据本发明式(I)的增白剂和非离子或者离子表面活性剂。优选的是聚乙二醇醚。
非发光的盐也可以另外的存在。
本发明无机发光材料可以用作纺织品、洗涤剂和造纸工业中的荧光增白剂并且还可以加入到塑料中。应用方式和所需性能二者对于一种基底到另外一种基底来说非常不同，但是这里有五个共同的基本原则：
(1)如果基底在它们的激发和磷光范围内没有太强的吸收，则本发明荧光增白剂可以仅仅有效的提高白度。具有弱的“基础白色”的物体例如未漂白的纺织品或者弱清洗的制品不可能被增白到高度的白度，甚至用高浓度的本发明荧光增白剂也不行。
(2)如果它们单分子分散于基底中，则该增白剂仅仅有效的起作用。这不仅取决于无机发光材料的沉降特性，而且取决于基底类型和应用方式。
(3)变白效果随着无机发光材料浓度高到饱和限度而增加。因为这个原因，无机发光材料的施用浓度必须保持低：相对于基底大约0.002-0.2wt％，或者是通常的染料浓度的大约十分之一。
根据本发明通式(I)的无机发光材料是用于不同基底的荧光增白剂。特别优选的基底是那些由细微分散的天然纤维素例如棉花、纸张和木材的基底构成，或者是由羊毛或合成聚酰胺的再生纤维素构成的材料。待荧光增白的材料可以存在于广泛的多个加工阶段例如原料、中间制品、或者最终制品以及存在于广泛的多种加工形式中例如诸如纤维、细丝、机织织物、成环编织、网以及膜等。
根据本发明的化合物还可以具有加入其中的洗衣粉。所用的固体和液体洗衣粉可以包含相应于现有技术的常规的成分。
本发明的化合物可以进一步在纤维材料的树脂整理以及相联系的合成树脂和合成树脂预缩合过程中应用。合成树脂的交联可以在宽的pH范围，特别是从pH1-pH10中以常规的方式来进行。
本发明的化合物可以进一步用来提高纺织品材料的防晒系数。使用二胺芪二磺酸衍生物来提高纺织品材料的防晒系数是已知的并描述于例如EP-A728749中。
为了提高纺织品材料的防晒系数，该纺织品材料可以用本发明的化合物直接进行处理，或者当所用的洗衣粉包含根据本发明的化合物时，该效果是作为通常的家庭洗衣过程的一部分而实现的。
根据本发明式(I)的增白剂适于增白造纸中的纸张材料，例如纤维素、化学品和机械纸浆，并用于增白通常用于造纸工业中的涂料组合物，特别是用于增白未着色的但是尤其是用于增白着色的纸张材料和涂料组合物。特别优选的是将根据本发明式(I)的无机发光材料用作微孔喷墨介质中的荧光增白剂。
根据本发明式(I)的增白剂优选被包含于印刷油墨(溶剂基的、水基的、可能量固化的(UV&EB)油墨和调色剂)，该油墨用于平版印刷、柔版、凹版、丝网、凹雕、数字(喷墨/电子摄影法)和移印加工。
在已知的涂料组合物中的粘合剂包括聚合物分散体，其基于共聚物：丁二烯-苯乙烯，丙烯腈-丁二烯-苯乙烯，丙烯酸酯，乙烯-氯乙烯或者乙烯-醋酸乙烯酯，或者基于均聚物例如聚氯乙烯，聚偏1，1-氯乙烯，聚乙烯，聚乙酸乙烯酯或者聚氨酯。一种优选的粘合剂由苯乙烯-丙烯酸丁酯或者苯乙烯丁二烯-丙烯酸互聚物。另外的聚合物胶乳描述在例如美国专利No.3265654中。
涂料组合物通常是使用硅酸铝着色的，例如陶土和高岭土，还有硫酸钡，缎光白，二氧化钛或碳酸钙(白垩)。
根据本发明的涂料组合物优选包含5-70重量％的白色颜料。粘合剂优选是以这样的量使用：即，聚合化合物的固含量包含1-30重量％，优选5-25重量％的白色颜料。本发明增白剂的量是以这样的方式确定的：即，增白剂是以基于白色颜料的0.005-1重量％，特别是0.01-0.55重量％的量而存在的。
根据本发明的涂料组合物可以通过以任意的顺序在10-100℃，优选20-80℃的温度混合所述的组分来制备。所述的组分还包括常规的辅助剂，其可以用来调节涂料组合物的流变性能，例如粘度或者水保持能力。这样的辅助剂是例如天然粘合剂，例如淀粉，酪蛋白，蛋白质或者凝胶，纤维素醚，例如羧烷基纤维素或者羟烷基纤维素，褐藻酸，藻酸盐，聚氧化乙烯或者聚氧化乙烯烷基醚，环氧乙烷和环氧丙烷的互聚物，聚乙烯醇，聚乙烯吡咯烷酮，甲醛和尿素或者蜜胺的水溶性缩合产物，聚磷酸盐或者聚丙烯酸盐。
根据本发明式(I)的增白剂被混入到最终的涂料组合物中，或者被混入到涂料组合物的一种组分中。
根据本发明的涂料组合物可以用来涂覆纸张、木头、薄膜例如诸如纤维素，纤维素三醋酸酯，纺织品材料等等。特别优选给出的是应用到纸张和纸板以及像纸上。
所述的涂料组合物可以通过任何常规的方法施涂到基底上，例如使用气刀、涂覆刀、刷子、辊子、刮刀或者棒子，然后例如使用红外干燥器和/或热空气干燥器来干燥涂层，使得残余水分量为3-6重量％，所述的干燥是在基底表面温度处于70-200℃，优选90-130℃的范围进行的。
根据本发明的涂料组合物提供了涂层，该涂层显著的具有沿着整个表面的荧光增白剂的最佳分布和白度伴随的提高以及高的耐晒度。
实施例
分析方法
色谱法(在薄层色谱中磷光点的解释或者在HPLC中UV吸收峰的解释)能够客观快速和明确的识别荧光增白剂。相同的方法可以用于定性和定量表征荧光增白剂在磷光或者非磷光副产物方面的纯度。活性物质的含量是通过在溶液中的消光(吸光率)的光度测量来确定的(E11)。波长和最大吸收高度取决于溶剂。
荧光增白剂在使用的浴液中的浓度可以通过与校准标准物的磷光测量比较来定量监控。基底上的荧光增白剂可以直接通过测量反射比来确定。可选择的，荧光增白剂可以用适当的溶剂萃取并在溶液中确定；在塑料的情况中，这包括了溶解该基底。
变白效果评价
变白可以用肉眼或仪器(比色法)来评价。评价的量是白度和色调。特别的注意力应当放在处于UV和可见光范围内的入射光的光谱分布上面，因为这控制着增白剂对于白度的磷光贡献。肉眼评价通过与漫射的日光中的参考相比较来进行的。可以使用由带有明确定义的白度值的分段所组成的白色标尺(例如Ciba-Geigy棉花或者塑料白色标尺)。对于仪器评价，分光光度计是优选的；但是，也是用三滤光器仪器。所获得的色度值取决于所述的仪器和它的瞬时状态(首要的是样品照明条件)，并且必须通过合适的方法进行控制。仪器的影响可以通过转化为标准照明D65(其代表具有6504K相关色温的日光)来消除。白度和色调值然后可以从这些色度数据用适当的式子来计算。通常使用的白度公式可以在G.Wyszecki，W.S.Stiles：Color Science，Concepts and Methods，Quantitative Data and Formulas，J.Wiley & Sons，纽约-伦敦-悉尼1967中找到。
Claims (12)
1.一种无机发光材料作为荧光增白剂的用途，其中所述的无机发光材料特征在于：
(i)在350-375nm范围内的最大吸收；
(ii)接近400nm的吸收带的急剧下降；
(iii)至少为0.8的磷光量子产率；和
(iv)在415-445nm的最大磷光。
2.权利要求1的用途，其中所述的无机发光材料选自硫化物和硒化物；氧硫化物；氧占优的无机发光材料；和卤化物无机发光材料。
3.权利要求1的用途，其中磷光量子产率至少为0.95。
4.权利要求2的用途，其中所述硫化物和硒化物为硫化镉和硫硒化物、碱土金属硫化物和硫硒化物。
5.权利要求2的用途，其中所述氧占优的无机发光材料为铝酸盐、镓酸盐、硅酸盐、锗酸盐、卤代磷酸盐和磷酸盐、氧化物、砷酸盐、钒酸盐、铌酸盐和钽酸盐、硫酸盐、钨酸盐和钼酸盐。
6.权利要求2的用途，其中所述卤化物无机发光材料为金属卤化物和锰活化的卤化物无机发光材料。
7.权利要求1或者2的用途，其中所述的无机发光材料符合式(I)
AxBy:Eu (I)
其中
A是至少一种碱土金属和/或锌；
B是至少一种阴离子，其选自硅铝酸根、Al10O17 4-、Al16O27 6-、磷酸根和卤离子；
x是1-10的整数，y是1-5的整数，并且x和y的目的是使得电荷平衡；和
其中铕的含量是0.01-1mol％。
8.权利要求7的用途，其中
A是至少一种碱土金属，其选自钡、镁、钙和/或锶；
B是至少一种阴离子，其选自Al10O17 4-、Al16O27 6-、PO4 3-和卤素；和
其中铕的含量是0.1-0.5mol％。
9.权利要求7的用途，其中所述的无机发光材料选自BaMgAl10O17:Eu、BaMg2Al16O27:Eu 和Sr3Ca2(PO4)3Cl:Eu 或者(SrBaCa)5(PO4)3Cl:Eu。
10.一种增白剂制剂，其包含至少一种权利要求1-9任何一项中所定义的无机发光材料和至少一种非离子或者离子表面活性剂。
11.一种涂料组合物，其包含(i)5-70重量％的白色颜料，和(ii)基于该白色颜料0.005-1重量％的权利要求1-9任何一项中所定义的无机发光材料。
12.一种方法，其包括使用权利要求1-9任何一项中所定义的无机发光材料来增白聚酰胺、纤维素、纸张或者洗衣粉。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06112757.7 | 2006-04-19 | ||
| EP06112757 | 2006-04-19 | ||
| PCT/EP2007/053439 WO2007118813A1 (en) | 2006-04-19 | 2007-04-10 | Inorganic optical brightener |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101426883A CN101426883A (zh) | 2009-05-06 |
| CN101426883B true CN101426883B (zh) | 2013-01-02 |
Family
ID=37022980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780014234XA Expired - Fee Related CN101426883B (zh) | 2006-04-19 | 2007-04-10 | 无机荧光增白剂 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US8945239B2 (zh) |
| EP (1) | EP2007848B1 (zh) |
| JP (1) | JP2009534490A (zh) |
| KR (1) | KR20080110916A (zh) |
| CN (1) | CN101426883B (zh) |
| AT (1) | ATE440929T1 (zh) |
| DE (1) | DE602007002183D1 (zh) |
| TW (1) | TW200804566A (zh) |
| WO (1) | WO2007118813A1 (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011504520A (ja) * | 2007-10-26 | 2011-02-10 | ビーエーエスエフ ソシエタス・ヨーロピア | 機密保護要素 |
| EP2231815A1 (en) * | 2007-12-14 | 2010-09-29 | Basf Se | Inorganic phosphor, obtainable by wet milling |
| EP2743080B1 (en) * | 2012-12-13 | 2016-10-05 | AIRBUS HELICOPTERS DEUTSCHLAND GmbH | Multi-layered transparency and method of producing such a multi-layered transparency |
| EP3240858A4 (en) * | 2015-01-02 | 2018-07-11 | Imerys USA, Inc. | Compositions and methods for providing high whiteness and/or brightness |
| JP2017186488A (ja) * | 2016-04-08 | 2017-10-12 | 山陽色素株式会社 | 蛍光顔料分散体および白色積層体 |
| EP3584089A1 (en) | 2018-06-19 | 2019-12-25 | Borealis AG | Polyolefin composition providing improved contrast of laser marks |
| EP3584088B1 (en) | 2018-06-19 | 2020-09-30 | Borealis AG | Polyolefin composition providing marking by fluorescence |
| JP7174238B2 (ja) * | 2018-11-29 | 2022-11-17 | 日亜化学工業株式会社 | ハロリン酸塩蛍光体及び発光装置 |
| US20230407121A1 (en) * | 2022-06-17 | 2023-12-21 | The Boeing Company | Phosphor-containing inks for disinfection and improving photostability of synthetic polymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148729A (zh) * | 1995-05-29 | 1997-04-30 | 日亚化学工业株式会社 | 余辉性灯泡 |
| CN1386306A (zh) * | 2000-05-15 | 2002-12-18 | 通用电气公司 | 一种用于led装置的白光发射荧光材料共混物 |
| CN1483663A (zh) * | 2002-08-07 | 2004-03-24 | ���ٻ�ѧ��ҵ��ʽ���� | 高结晶性氧化物粉末的制造方法 |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0212197B2 (zh) * | 1980-05-30 | 1990-03-19 | Gee Aa Oo G Fuyuuru Automatsuioon Unto Oruganizatsuioon Mbh | |
| JPS59225400A (ja) * | 1983-06-07 | 1984-12-18 | 富士写真フイルム株式会社 | 放射線増感スクリ−ン |
| US5308824A (en) * | 1990-09-28 | 1994-05-03 | Mitsubishi Paper Mills Limited | Recording material |
| JP2543825B2 (ja) * | 1993-04-28 | 1996-10-16 | 根本特殊化学株式会社 | 蓄光性蛍光体 |
| JP3456553B2 (ja) * | 1994-11-01 | 2003-10-14 | 根本特殊化学株式会社 | 蓄光性蛍光体 |
| JP3457435B2 (ja) | 1995-08-04 | 2003-10-20 | 特種製紙株式会社 | 蛍光増白紙の製造方法 |
| US6652967B2 (en) * | 2001-08-08 | 2003-11-25 | Nanoproducts Corporation | Nano-dispersed powders and methods for their manufacture |
| JPH1116503A (ja) * | 1997-06-24 | 1999-01-22 | Okuno Chem Ind Co Ltd | プラズマディスプレイパネルの隔壁及び蛍光体形成用積層シート |
| US6692660B2 (en) * | 2001-04-26 | 2004-02-17 | Nanogram Corporation | High luminescence phosphor particles and related particle compositions |
| JPH1161115A (ja) | 1997-08-25 | 1999-03-05 | Lonseal Corp | 蛍光体組成物 |
| US20030143426A1 (en) * | 1998-10-07 | 2003-07-31 | Akira Haneda | Forgery prevention sheet |
| US6375864B1 (en) * | 1998-11-10 | 2002-04-23 | M.A. Hannacolor, A Division Of M.A. Hanna Company | Daylight/nightglow colored phosphorescent plastic compositions and articles |
| DE19934473A1 (de) | 1999-07-27 | 2001-02-01 | Thomson Brandt Gmbh | Gerät zum Beschreiben optischer Aufzeichnungsträger |
| PT1255893E (pt) | 1999-12-29 | 2004-06-30 | Minerals Tech Inc | Agentes fluorescentes |
| CN1267946C (zh) * | 2000-08-10 | 2006-08-02 | 奥斯兰姆施尔凡尼亚公司 | 在使用期限内具有降低的色移的显示器件 |
| DE10130330A1 (de) * | 2001-06-22 | 2003-01-02 | Philips Corp Intellectual Pty | Gasentladungslampe für dielektrisch behinderte Entladungen mit blauen Leuchtstoff |
| DE10158273A1 (de) * | 2001-11-28 | 2003-06-18 | Philips Intellectual Property | Plasmafarbbildschirm mit grünem Leuchtstoff |
| US6869753B2 (en) * | 2002-10-11 | 2005-03-22 | Agilent Technologies, Inc. | Screen printing process for light emitting base layer |
| ATE454718T1 (de) * | 2002-11-08 | 2010-01-15 | Nichia Corp | Lichtemissionsbauelement, leuchtstoff und verfahren zur herstellung eines leuchtstoffs |
| US6982523B2 (en) * | 2003-01-28 | 2006-01-03 | Kabushiki Kaisha Fine Rubber Kenkyuusho | Red light emitting phosphor, its production and light emitting device |
| US7229600B2 (en) * | 2003-01-31 | 2007-06-12 | Nanoproducts Corporation | Nanoparticles of rare earth oxides |
| US20060180792A1 (en) * | 2003-06-26 | 2006-08-17 | Prime Technology Llc | Security marker having overt and covert security features |
| US7723740B2 (en) * | 2003-09-18 | 2010-05-25 | Nichia Corporation | Light emitting device |
| JP3792704B2 (ja) | 2004-08-11 | 2006-07-05 | 株式会社神戸製鋼所 | 光反射性塗装金属板 |
| JP4790256B2 (ja) | 2004-11-19 | 2011-10-12 | 根本特殊化学株式会社 | 蛍光増白用蛍光体 |
| JP2006186182A (ja) * | 2004-12-28 | 2006-07-13 | Okaya Electric Ind Co Ltd | 発光ダイオード及びその製造方法 |
-
2007
- 2007-04-10 CN CN200780014234XA patent/CN101426883B/zh not_active Expired - Fee Related
- 2007-04-10 DE DE602007002183T patent/DE602007002183D1/de active Active
- 2007-04-10 WO PCT/EP2007/053439 patent/WO2007118813A1/en active Application Filing
- 2007-04-10 US US12/226,296 patent/US8945239B2/en not_active Expired - Fee Related
- 2007-04-10 EP EP07727907A patent/EP2007848B1/en not_active Not-in-force
- 2007-04-10 AT AT07727907T patent/ATE440929T1/de not_active IP Right Cessation
- 2007-04-10 JP JP2009505844A patent/JP2009534490A/ja active Pending
- 2007-04-10 KR KR1020087028185A patent/KR20080110916A/ko not_active Application Discontinuation
- 2007-04-18 TW TW096113606A patent/TW200804566A/zh unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148729A (zh) * | 1995-05-29 | 1997-04-30 | 日亚化学工业株式会社 | 余辉性灯泡 |
| CN1386306A (zh) * | 2000-05-15 | 2002-12-18 | 通用电气公司 | 一种用于led装置的白光发射荧光材料共混物 |
| CN1483663A (zh) * | 2002-08-07 | 2004-03-24 | ���ٻ�ѧ��ҵ��ʽ���� | 高结晶性氧化物粉末的制造方法 |
Non-Patent Citations (2)
| Title |
|---|
| 滕玉洁等.Sr3Ca2(PO4)3X:Eu2+（X=F，Cl，Br）的光激励发光与F色心.《中国稀土学报》.1992,第10卷(第4期),331-334. * |
| 韩万书.稀土卤磷酸盐的发光.《中国固体无机化学十年进展(第一版)》.1998,44. * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080110916A (ko) | 2008-12-19 |
| WO2007118813A1 (en) | 2007-10-25 |
| US20090137445A1 (en) | 2009-05-28 |
| JP2009534490A (ja) | 2009-09-24 |
| US8945239B2 (en) | 2015-02-03 |
| EP2007848B1 (en) | 2009-08-26 |
| EP2007848A1 (en) | 2008-12-31 |
| CN101426883A (zh) | 2009-05-06 |
| ATE440929T1 (de) | 2009-09-15 |
| DE602007002183D1 (de) | 2009-10-08 |
| TW200804566A (en) | 2008-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101426883B (zh) | 无机荧光增白剂 | |
| EP1074599B1 (en) | Fluorescent granules, method for preparing the same and paper for preventing forgery using the fluorescent granules | |
| US6302999B1 (en) | Method for optically brightening paper | |
| JP4550419B2 (ja) | 蛍光増白剤に関する改良 | |
| US5135568A (en) | Method for improving fluorescent coatings | |
| AU665110B2 (en) | Process for enhancing the whiteness, brightness and chromaticity of fillers and pigments | |
| CN101999020A (zh) | 改良的荧光增白组合物 | |
| CN1279242C (zh) | 控制纸类产品亮度的方法 | |
| US20110008637A1 (en) | Method for improving the performance of optical brightening agents | |
| EP0905317B1 (en) | A method for optically brightening paper | |
| US8894815B2 (en) | Storage stable solutions of optical brighteners | |
| EP1255893B1 (en) | Fluorescent agents | |
| Weaver | Surface brightening of paper | |
| Aman | Efficiency of fluorescent whitening agents in pigment coatings | |
| Shakespeare | Colorant modelling for on-line paper coloring: Evaluations of models and an extension to Kubelka-Munk model | |
| JP5941856B2 (ja) | 印刷用塗工紙 | |
| CN107501195A (zh) | 一种二苯基‑二嘧啶基荧光增白剂及其制备方法与应用 | |
| AU4769700A (en) | Kaolin products and their preparation and use in paper making and coating | |
| RU2214433C1 (ru) | Выпускная форма оптического отбеливателя | |
| WO2004050994A1 (en) | A method for increasing the stability of fluorescent whitening agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20180410 |