WO2020066426A1 - 赤外線吸収材料微粒子分散液とその製造方法 - Google Patents
赤外線吸収材料微粒子分散液とその製造方法 Download PDFInfo
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- WO2020066426A1 WO2020066426A1 PCT/JP2019/033534 JP2019033534W WO2020066426A1 WO 2020066426 A1 WO2020066426 A1 WO 2020066426A1 JP 2019033534 W JP2019033534 W JP 2019033534W WO 2020066426 A1 WO2020066426 A1 WO 2020066426A1
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- WIPO (PCT)
- Prior art keywords
- absorbing material
- infrared absorbing
- material fine
- particle dispersion
- fine particles
- Prior art date
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 205
- 239000011358 absorbing material Substances 0.000 title claims abstract description 166
- 239000006185 dispersion Substances 0.000 title claims abstract description 133
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title description 16
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 47
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims description 39
- 239000002270 dispersing agent Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052716 thallium Inorganic materials 0.000 claims description 10
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- 229910052701 rubidium Inorganic materials 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000004715 keto acids Chemical class 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000003574 free electron Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- 238000012790 confirmation Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 150000003658 tungsten compounds Chemical class 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AAWZNWVCESLFTD-UHFFFAOYSA-N tungsten;hydrate Chemical compound O.[W] AAWZNWVCESLFTD-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
Definitions
- the present invention relates to an infrared absorbing material fine particle dispersion containing infrared absorbing material fine particles and a solvent, and more specifically, the infrared absorbing material fine particles include composite tungsten oxide fine particles, and the solvent includes water.
- the present invention relates to a fine particle dispersion and a method for producing the same.
- a light-shielding member used for a window material or the like a light-shielding member using an inorganic pigment such as carbon black or titanium black having an absorption characteristic from a visible light region to a near-infrared region, and having a strong absorption characteristic only in a visible light region.
- Various light-blocking members have been proposed, such as a light-blocking member using a black pigment containing an organic pigment such as aniline black, and a half-mirror-type light-blocking member in which a metal such as aluminum is deposited.
- Patent Document 1 on a transparent glass substrate, as a first layer from the substrate side, it was selected from the group consisting of Group IIIa, Group IVa, Group Vb, Group VIb and Group VIIb of the periodic table.
- a composite tungsten oxide film containing at least one metal ion is provided, a transparent dielectric film is provided as a second layer on the first layer, and a group IIIa of the periodic table is provided as a third layer on the second layer;
- a composite tungsten oxide film containing at least one metal ion selected from the group consisting of IVa group, Vb group, VIb group and VIIb group is provided, and the refractive index of the transparent dielectric film of the second layer is set to the above-mentioned value.
- the composite tungsten oxide film of the first layer and the third layer can be suitably used in a part where high visible light transmittance and good infrared blocking performance are required. Infrared cut-off glass that may have been proposed.
- Patent Document 2 in the same manner as Patent Document 1, a first dielectric film is provided as a first layer from a substrate side on a transparent glass substrate, and tungsten oxide is formed as a second layer on the first layer.
- An infrared shielding glass in which a film is provided and a second dielectric film is provided as a third layer on the second layer has been proposed.
- Patent Document 3 a composite tungsten oxide film containing a metal element similar to that of Patent Document 1 is provided on a transparent glass substrate as a first layer on the transparent glass substrate in the same manner as in Patent Document 1, A heat ray blocking glass in which a transparent dielectric film is provided as a second layer on a layer has been proposed.
- Patent Document 4 tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ), niobium pentoxide (Nb 2 O 5 ), and tantalum pentoxide containing additional elements such as hydrogen, lithium, sodium and potassium
- tungsten trioxide (WO 3 ) molybdenum trioxide (MoO 3 ), niobium pentoxide (Nb 2 O 5 ), and tantalum pentoxide containing additional elements such as hydrogen, lithium, sodium and potassium
- a metal oxide film selected from one or more of (Ta 2 O 5 ), vanadium pentoxide (V 2 O 5 ), and vanadium dioxide (VO 2 ) is coated by a CVD method or a spray method, 250 ° C.
- a solar control glass sheet having solar light shielding properties formed by being thermally decomposed to a certain degree has been proposed.
- Patent Literature 5 proposes a solar light-modulated light-insulating material using tungsten oxide obtained by hydrolyzing tungstic acid and adding an organic polymer having a specific structure called polyvinylpyrrolidone to the tungsten oxide.
- the sunlight is irradiated with the sunlight, the ultraviolet light in the light is absorbed by the tungsten oxide to generate excited electrons and holes, and a small amount of the ultraviolet light significantly increases the appearance amount of pentavalent tungsten.
- the coloring reaction increases to increase the coloring reaction, and accordingly, the coloring concentration increases.
- the pentavalent tungsten is very quickly oxidized to hexavalent and the decoloring reaction is increased.
- Patent Document 6 the present inventors dissolve tungsten hexachloride in alcohol and evaporate the medium as it is, or heat and reflux, evaporate the medium, and then heat it at 100 ° C. to 500 ° C. To obtain tungsten oxide fine particles comprising tungsten trioxide, a hydrate thereof, or a mixture of both. Then, it was disclosed that an electrochromic element can be obtained using the tungsten oxide fine particles, that optical properties of the film can be changed when protons are introduced into the film by forming a multilayer laminate, and the like. .
- Patent Document 7 discloses that a dried product of a mixed aqueous solution is heated at a heating temperature of about 300 to 700 ° C. using a meta-type ammonium tungstate and various water-soluble metal salts as raw materials.
- a hydrogen gas to which an active gas (addition amount: about 50 vol% or more) or water vapor (addition amount: about 15 vol% or less) is added, a general formula MxWO 3 (where M is an alkali, alkaline earth, rare earth, or the like)
- a method for producing various tungsten bronze represented by the following metal element, 0 ⁇ x ⁇ 1) has been proposed. Then, it has been proposed to carry out the operation on a support to produce various tungsten bronze-coated composites and use them as electrode catalyst materials for fuel cells and the like.
- Patent Document 8 an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium such as a resin, and the optical characteristics, conductivity, and manufacturing method of the infrared shielding material fine particle dispersion. was disclosed.
- the infrared shielding material fine particles are fine particles of tungsten oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ⁇ z / y ⁇ 2.999), and / or Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, and I, at least one element selected from the group consisting of W, tungsten, O, oxygen, 0.001 ⁇ x / y ⁇ 1, 2.2 ⁇ z / y ⁇ 3. 0) fine particles of the composite tungsten oxide represented by
- an infrared absorbing material fine particle dispersion in which the infrared absorbing material fine particles are dispersed in a medium such as a resin an infrared absorbing material fine particle dispersion in which the infrared absorbing material fine particles are dispersed in a solvent is prepared. Then, a method of dissolving a resin or the like in the dispersion liquid of the infrared absorbing material fine particles to form a coating liquid, applying the coating liquid to a substrate, for example, and then drying the coating liquid may be adopted.
- the solvent in the above-mentioned coating liquid contains water.
- the present inventors have conducted research and found that the infrared absorbing material fine particle dispersion has excellent long-term preservability when it has a predetermined zeta potential value. And completed the present invention.
- a first invention for solving the above-mentioned problem is: An infrared absorbing material fine particle dispersion containing infrared absorbing material fine particles and a solvent,
- the infrared absorbing material fine particles may have a general formula MxWOy (where M is at least one element selected from Cs, Rb, K, Tl, and Ba, 0.1 ⁇ x ⁇ 0.5, 2.2 ⁇ y). ⁇ 3.0), comprising composite tungsten oxide fine particles represented by the following formula:
- the solvent includes water, An infrared absorbing material fine particle dispersion, wherein the absolute value of the zeta potential of the infrared absorbing material fine particle dispersion is 5 mV or more and 100 mV or less.
- the second invention is The infrared absorbing material fine particle dispersion according to the first invention, wherein the value of the zeta potential is -100 mV or more and -5 mV or less.
- the third invention is The infrared absorbing fine particle dispersion according to the first or second invention, wherein the pH value is 4 or more.
- the fourth invention is The infrared absorbing material fine particle dispersion according to any one of the first to third inventions, wherein the composite tungsten oxide fine particles have a particle diameter of 800 nm or less.
- the fifth invention is The dispersion liquid of the infrared absorbing material fine particles according to any one of the first to fourth inventions, further comprising one or more dispersants.
- the sixth invention is The infrared absorbing material fine particle dispersion according to the fifth invention, wherein the dispersant contains at least one of an amino group and an oxo acid.
- the seventh invention is The content according to any one of the first to sixth inventions, wherein the content of the infrared absorbing material fine particles contained in the infrared absorbing material fine particle dispersion is 0.01% by mass or more and 80% by mass or less. It is a dispersion of the infrared absorbing material fine particles described in the above.
- the eighth invention is A method for producing an infrared absorbing material fine particle dispersion containing infrared absorbing material fine particles and a solvent, To the solvent containing water, a general formula MxWOy (where M is at least one element selected from Cs, Rb, K, Tl, and Ba, 0.1 ⁇ x ⁇ 0.5, 2.2 ⁇ y ⁇ 3.0) by dispersing the infrared absorbing material fine particles containing the composite tungsten oxide fine particles represented by A method for producing a fine particle dispersion of an infrared absorbing material, characterized in that the absolute value of the zeta potential of the fine particle dispersion of an infrared absorbing material is 5 mV or more and 100 mV or less.
- the ninth invention is The method for producing an infrared-absorbing fine particle dispersion according to the eighth invention, wherein the pH value of the infrared-absorbing material fine particle dispersion is 4 or more.
- the present invention it is possible to obtain an infrared absorbing material fine particle dispersion having excellent long-term storage properties while using a solvent containing water. In addition, it is possible to suppress the occurrence of bleed-out when a film is formed by mixing the dispersion of the infrared absorbing material fine particles and a binder.
- the infrared absorbing material fine particle dispersion according to the present invention is an infrared absorbing material fine particle dispersion containing infrared absorbing material fine particles and a solvent, wherein the infrared absorbing material fine particles have a general formula MxWOy (where M element is Cs, Rb, K, Tl, at least one element selected from Ba, and 0.1 ⁇ x ⁇ 0.5, 2.2 ⁇ y ⁇ 3.0).
- MxWOy where M element is Cs, Rb, K, Tl, at least one element selected from Ba, and 0.1 ⁇ x ⁇ 0.5, 2.2 ⁇ y ⁇ 3.0.
- the solvent contains water, and the absolute value of the zeta potential of the infrared ray absorbing material fine particle dispersion is 510 mV or more and 100 mV or less.
- the fine particles of the infrared-absorbing material according to the present invention are referred to as [1] fine particles of the infrared-absorbing material, [2] a solvent used for the fine particles of the infrared-absorbing material, [3] a fine particle dispersion of the infrared-absorbing material, and [4] infrared.
- a dispersant added to the dispersion of fine particles of the absorbing material [5] a method of producing fine particles of the infrared absorbing material, [6] a method of producing a fine particle of the infrared absorbing material, and [7] a method of using the fine particle of the infrared absorbing material. It will be described in order.
- the infrared absorbing material fine particle dispersion according to the present invention contains at least a general formula MxWyOz (where M element is one selected from Cs, Rb, K, Tl, and Ba) as infrared absorbing material fine particles.
- M element is one selected from Cs, Rb, K, Tl, and Ba
- These include the composite tungsten oxide fine particles represented by the above elements, 0.1 ⁇ x ⁇ 0.5, 2.2 ⁇ y ⁇ 3.0).
- the infrared absorbing material fine particles according to the present invention will be described by taking composite tungsten oxide fine particles as an example.
- a material containing free electrons exhibits a reflection-absorption response to an electromagnetic wave around a solar ray region having a wavelength of 200 nm to 2600 nm due to plasma vibration.
- the particles of the powder of such a substance are formed into fine particles having a particle size smaller than the wavelength of light, geometric scattering in the visible light region (wavelength from 380 nm to 780 nm) is reduced, and transparency in the visible light region is obtained.
- “transparency” is used to mean “there is little scattering and high transmittance with respect to light in the visible light region”.
- the infrared absorbing material fine particles using both the control of the oxygen amount and the addition of the M element for generating free electrons have a general formula of MxWyOz (where M is 1 selected from Cs, Rb, K, Tl, and Ba). (W is tungsten and O is oxygen.) And infrared rays satisfying the relationship of 0.001 ⁇ x / y ⁇ 1, 2.2 ⁇ z / y ⁇ 3. Absorption material fine particles.
- the value of x / y indicating the amount of addition of the element M
- the value of x / y is larger than 0.001
- a sufficient amount of free electrons is generated in the composite tungsten oxide, and the desired infrared absorption effect is reduced. Can be obtained.
- the addition amount of the M element increases, the supply amount of free electrons increases and the infrared absorption efficiency also increases, but the effect is saturated when the value of x / y is about 1.
- the value of x / y is smaller than 1 because generation of an impurity phase in the infrared absorbing material fine particles can be avoided.
- the composite tungsten oxide fine particles have a hexagonal crystal structure
- transmission of the fine particles in the visible light region is improved, and absorption in the infrared region is improved.
- the addition amount of the M element is preferably 0.2 or more and 0.5 or less in terms of x / y, more preferably 0.33.
- the value of x / y is 0.33, it is considered that the above-described M element is arranged in all the hexagonal voids.
- the hexagonal crystal is easily formed.
- the M element is one or more elements selected from Cs, Rb, K, Tl, and Ba
- a hexagonal crystal is easily formed.
- Typical examples are Cs 0.33 WO z , Cs 0.03 Rb 0.30 WO z , Rb 0.33 WO z , K 0.33 WO z , Ba 0.33 WO z (2.0 ⁇ z ⁇ 3.0) and the like.
- other elements may be used as long as the above-mentioned M element is present in the hexagonal void formed by WO 6 units, and is not limited to the above-described elements.
- the addition amount of the M element is preferably 0.2 or more and 0.5 or less in terms of x / y, and more preferably 0. 33.
- the value of x / y is 0.33, it is considered that the above-described M element is arranged in all the hexagonal voids.
- tetragonal and cubic composite tungsten oxides other than hexagonal are also effective as infrared absorbing material fine particles.
- the absorption position in the infrared region tends to change depending on the crystal structure, and the absorption position tends to move to the longer wavelength side in the order of cubic crystal ⁇ tetragonal crystal ⁇ hexagonal crystal.
- the absorption in the visible light region is low in the order of hexagonal, tetragonal and cubic. Therefore, it is preferable to use a hexagonal composite tungsten oxide for applications in which light in the visible light region is more transmitted and light in the infrared region is more absorbed.
- the tendency of the optical characteristics described here is only a rough tendency and varies depending on the type of the added element, the added amount, and the amount of oxygen, and the present invention is not limited to this.
- the transmission color tone is often from blue to green.
- the fine particles of the infrared absorbing material according to the present invention preferably have a particle size of 1 nm or more and 800 nm or less, and more preferably 100 nm or less.
- the particle diameter of the fine particles is preferably 1 nm or more and 40 nm or less, more preferably 1 nm or more and 30 nm or less, and most preferably 1 nm or more and 25 nm or less. It is.
- Such a particle size is preferable because scattering due to Mie scattering and Rayleigh scattering of the fine particles is sufficiently suppressed, visibility in a visible light wavelength region is maintained, and transparency can be efficiently maintained.
- the particle size is the average value of the diameters of the individual non-aggregated infrared absorbing material fine particles, and is the average value of the individual non-aggregated infrared absorbing material fine particles contained in the infrared absorbing material fine particle dispersion described below.
- the average particle diameter of the infrared absorbing material fine particles is measured and calculated from an electron microscope image of the infrared absorbing material fine particles.
- the solvent used in the infrared absorbing material fine particle dispersion according to the present invention contains water in its constitution.
- “contains water in the composition” means that the solvent contains water in an amount of 1% by mass or more, and an organic solvent compatible with water, for example, alcohols or glycols, and water.
- This is a concept that includes a mixed solvent.
- the concept includes a solvent composed of only water.
- water is a concept including ion-exchanged water from which anions such as chlorine have been removed with an ion-exchange resin, ultrapure water, and the like.
- the infrared absorbing material fine particle dispersion according to the present invention is a dispersion in which the above-described infrared absorbing material fine particles are dispersed in a solvent.
- the fine particle dispersion of the infrared absorbing material according to the present invention is a dispersion having an absolute value of the zeta potential of 5 mV or more and 100 mV or less. That is, the dispersion has a zeta potential value of 5 mV or more and 100 mV or less, or -100 mV or more and -5 mV or less.
- the absolute value of the zeta potential of the infrared absorbing material fine particle dispersion according to the present invention is in the range of 5 mV or more and 100 mV or less, preferably, in the case where the absolute value of the zeta potential is in the range of 10 mV or more and 100 mV or less. It has been found that gelation and sedimentation of particles can be avoided for 6 months or more at a temperature of 25 ° C. From this viewpoint, the zeta potential is preferably -100 mV or more and -5 mV or less, and more preferably the zeta potential is -100 mV or more and -10 mV or less.
- the dispersed particle size of the infrared absorbing material fine particles in the infrared absorbing material fine particle dispersion according to the present invention can be selected depending on the purpose of use.
- the dispersed particle diameter of the infrared absorbing material fine particles is a concept that is different from the particle diameter of the infrared absorbing material fine particles described above and includes the particle size of the aggregate of the infrared absorbing material fine particles.
- the infrared absorbing material fine particle dispersion according to the present invention preferably have a dispersed particle diameter of 800 nm or less in the dispersion. This is because particles having a dispersed particle diameter of less than 800 nm do not completely block light due to scattering, maintain visibility in the visible light region, and at the same time can efficiently maintain transparency. .
- the dispersed particle diameter of the infrared absorbing material fine particles in the dispersion is preferably 200 nm or less, more preferably 100 nm or less. The reason is that if the dispersed particle diameter of the infrared absorbing material fine particles is small, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometrical scattering or Mie scattering is reduced. And clear transparency can no longer be obtained.
- the dispersed particle diameter of the infrared absorbing material fine particles in the dispersion becomes 200 nm or less, the geometric scattering or Mie scattering is reduced, and the dispersion becomes a Rayleigh scattering region.
- the scattered light is proportional to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved with a decrease in the dispersed particle diameter.
- the dispersed particle diameter is 100 nm or less, the scattered light is very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle diameter is small. If the dispersed particle diameter is 1 nm or more, industrial production is easy.
- the haze value of the infrared absorbing material fine particle dispersion in which the infrared absorbing material fine particles according to the present invention are dispersed in a medium has a visible light transmittance of 85% or less and a haze of 30% or less. It can be.
- the haze value is less than 30%, the appearance of the infrared-absorbing material fine particle dispersion does not look like frosted glass, and clear transparency can be obtained.
- the dispersed particle diameter of the infrared absorbing material fine particles can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method.
- the zeta potential of the infrared absorbing material fine particle dispersion according to the present invention can be controlled by adjusting the pH of the dispersion and adding a dispersant to the dispersion. Specifically, it is preferable that the pH value of the dispersion liquid of the infrared absorbing material fine particles is 3 or more and 10 or less, and it is more preferable that the pH value is 4 or more and 7 or less. For the pH adjustment, addition of a weak acid or the like to the dispersion is also effective.
- a dispersant when added to the infrared absorbent material fine particle dispersion according to the present invention, it is preferable to add a water-soluble dispersant having an amino group.
- a water-soluble dispersant having an amino group for example, as a commercially available dispersant, Disperbyk 183, Disperbyk 185, Disperbyk 184, Disperbyk 190, Disperbyk 191 and Disperbyk 2010 (manufactured by Big Chemie) can be preferably exemplified.
- amino acids such as serine and phenylalanine may be added as a dispersant.
- a water-soluble dispersant having oxo acid can be mentioned.
- the oxo acid is preferably a carboxyl group.
- Solsperse 41090, Solsperse 43000, Solsperse 44000, Solsperse 46000, Solsperse 47000, Solsperse 53095 manufactured by Lubrizol Co., Ltd.
- Solsperse 41090, Solsperse 43000, Solsperse 44000, Solsperse 46000, Solsperse 47000, Solsperse 53095 manufactured by Lubrizol Co., Ltd.
- Solsperse 53095 manufactured by Lubrizol Co., Ltd.
- the dispersant added to the infrared absorbing material fine particle dispersion is a polymer dispersant
- a large amount of the additive causes a decrease in the absolute value of the zeta potential, but the effect of the polymer dispersant is long-term stability. May be kept.
- bleed-out occurs when a film is formed by further mixing with a binder.
- the amount of the polymer dispersant added to the dispersion of the infrared absorbing material fine particles does not cause a decrease in the absolute value of the zeta potential, no significant bleed-out occurs.
- the dispersant to be added to the infrared absorbing material fine particle dispersion is a low molecular dispersant, no significant bleed-out occurs.
- bleed-out is to prepare a mixed solution in which a binder such as a resin is added to a dispersion of fine particles of an infrared-absorbing material, apply the mixed solution to a substrate to obtain a coating film, and further obtain a dried film by heating and drying. Means the occurrence of spots due to the liquid mixture generated on the dried film. Significant bleed-out can be visually confirmed.
- a binder such as a resin
- a suitable addition amount is less than 2 parts by mass per 1 part by mass of the infrared-absorbing material fine particles. . More preferably, the content is 0.2 parts by mass or more and 1.5 parts by mass or less per 1 part by mass of the infrared absorbing material fine particles, and even more preferably 0.3 parts by mass or more and 1.2 parts by mass per 1 part by mass of the infrared absorbing material fine particles. Not more than parts by mass.
- tungsten compound and an M element compound are used as a raw material.
- the tungsten compound include tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, and tungsten hexachloride dissolved in alcohol, which is hydrolyzed by adding water, and then the solvent is evaporated to obtain a tungsten hydrate.
- the general formula MxWyOz (where M is one or more elements selected from Cs, Rb, K, Tl, and Ba; 0.001 ⁇ x / y ⁇ 1, 2.2 ⁇ z /Y ⁇ 3.0)
- the M element compound used in the production of the raw material of the composite tungsten oxide fine particles represented by the formula (I) is selected from oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of the M element. It is preferable that one or more types be used.
- a mixed powder can be produced by wet mixing of a tungsten compound and an M element compound.
- the produced mixed powder is fired in one step under an atmosphere of an inert gas alone or a mixed gas of an inert gas and a reducing gas.
- the firing temperature is preferably close to the temperature at which the composite tungsten oxide fine particles start to crystallize.
- the firing temperature is preferably 1000 ° C. or lower, more preferably 800 ° C. or lower, and even more preferably 800 ° C. or lower and 500 ° C. or higher.
- the infrared absorbing material fine particle dispersion it is important that the dispersion state of the infrared absorbing material fine particles is ensured during the pulverization and dispersion treatment steps, and that the fine particles are not aggregated. That is, particles of the infrared absorbing material are added to the solvent, and pulverization / dispersion treatment is performed until the particle diameter becomes the above-mentioned. At this time, it is preferable to appropriately add the above-described dispersant and adjust the pH value.
- the absolute value of the zeta potential of the dispersion liquid of the infrared absorbing material fine particles after the pulverization / dispersion treatment can be maintained at 5 mV or more and 100 mV or less.
- pulverization / dispersion treatment examples include, for example, pulverization / dispersion treatment methods using devices such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer.
- pulverization / dispersion treatment methods using devices such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer.
- pulverizing and dispersing with a medium stirring mill such as a bead mill, a ball mill, a sand mill, and a paint shaker are necessary to reach a desired dispersed particle diameter. This is preferable because the time is short.
- the content of the infrared absorbing material fine particles contained in the infrared absorbing material fine particle dispersion according to the present invention is 0.01% by mass or more and 80% by mass from the viewpoint of ease of use of the dispersion and stability. % Is preferable.
- the substrate is glass
- the dispersion liquid and the coating liquid of the infrared absorbing material fine particles according to the present invention are not limited to the use for the infrared shielding window, but can be widely used in a site where the infrared absorbing material is required. Further, the dispersion liquid and the coating liquid of the infrared absorbing material fine particles according to the present invention can be applied to a known coating method such as ink jet or spray coating.
- Example 1 0.216 kg of Cs 2 CO 3 was added to and dissolved in 0.330 kg of water, and the obtained solution was added to 1.000 kg of H 2 WO 4, sufficiently stirred, and dried to obtain a dried product.
- the dried product was heated while supplying 5% H 2 gas using N 2 gas as a carrier, and calcined at 800 ° C. for 1 hour. Thereafter, a composite tungsten oxide (Cs 0.33 WO 3 ) was obtained by a solid-phase method in which the mixture was baked at 800 ° C. for 2 hours in an N 2 gas atmosphere.
- Example 1 40 g (20% by mass) of the obtained composite tungsten oxide, 160 g (80% by mass) of ion-exchanged water as a solvent, and 750 g of ⁇ 0.3 zirconia beads were charged into a paint shaker, and pulverized and dispersed. An infrared absorbing material fine particle dispersion according to Example 1 was obtained.
- the zeta potential of the obtained fine particle dispersion of the infrared absorbing material was measured using a zeta potential meter (DT-200, manufactured by Nippon Lucas Co., Ltd.) and found to be -62 mV.
- the pH was measured using a pH meter (manufactured by Horiba, Ltd .: portable pH meter D-71) and was 4.1. The results are shown in Table 1.
- a silica binder having a solid content of 25% was mixed with the obtained infrared absorbing material fine particle dispersion in an amount of 3 parts by mass per 1 part by mass of the infrared absorbing material fine particles to obtain a mixed solution.
- the mixed solution was coated on a glass plate and dried at 180 ° C. for 30 minutes to obtain a dried film according to Example 1.
- Table 1 shows the measurement results. In addition, when the dried film according to Example 1 was visually confirmed, no bleed-out was confirmed.
- Example 2 40 g (20% by mass) of the composite tungsten oxide produced in Example 1, 16 g (8% by mass) of a commercially available polymer dispersant A (compound containing an organic oxo acid), and 144 g (72% by mass) of water And 750 g of ⁇ 0.3 zirconia beads were loaded into a paint shaker, and crushed and dispersed in the same manner as in Example 1 to obtain a dispersion liquid of the infrared absorbing material fine particles according to Example 2 and a dried film. The obtained infrared absorbing material fine particle dispersion liquid and the dried film according to Example 2 were evaluated and confirmed in the same manner as in Example 1. The zeta potential was -40 mV and the pH value was 6.9. Table 1 shows the evaluation and confirmation results.
- Example 3 40 g (20% by mass) of the composite tungsten oxide produced in Example 1, 40 g (20% by mass) of phenylalanine as low molecular dispersant B, 120 g (60% by mass) of water, and 750 g of ⁇ 0.3 zirconia beads.
- Example 3 40 g (20% by mass) of the composite tungsten oxide produced in Example 1, 40 g (20% by mass) of phenylalanine as low molecular dispersant B, 120 g (60% by mass) of water, and 750 g of ⁇ 0.3 zirconia beads.
- Example 3 40 g (20% by mass) of the composite tungsten oxide produced in Example 1
- 40 g (20% by mass) of phenylalanine as low molecular dispersant B 120 g (60% by mass) of water, and 750 g of ⁇ 0.3 zirconia beads.
- the obtained infrared absorbing material fine particle dispersion liquid and the dried film according to Example 3 were evaluated and confirmed in the same manner
- Example 4 40 g (20% by mass) of the composite tungsten oxide produced in Example 1, 16 g (8% by mass) of a commercially available polymer dispersant C (block copolymer having an amino group), and 144 g (72% by mass) of water And 750 g of ⁇ 0.3 zirconia beads were loaded into a paint shaker, and pulverized and dispersed in the same manner as in Example 1 to obtain a dispersion liquid of infrared absorbing material fine particles according to Example 4 and a dried film. The obtained infrared absorbing material fine particle dispersion liquid and the dried film according to Example 4 were evaluated and confirmed in the same manner as in Example 1. The zeta potential was -23 mV and the pH value was 6.5. Table 1 shows the evaluation and confirmation results.
- Example 1 The same procedures as in Example 1 were carried out except that the zeta potential value and the pH value were adjusted by adding hydrochloric acid of a reagent as an acid agent to the dispersion liquid of the infrared-absorbing material fine particles according to Example 1, and according to Comparative Example 1. An infrared absorbing material fine particle dispersion and a dried film were obtained. The obtained infrared absorbing material fine particle dispersion and the dried film were evaluated and confirmed in the same manner as in Example 1. The zeta potential was 2 mV and the pH value was 2.4. Table 1 shows the evaluation and confirmation results.
- Example 2 The same procedure as in Example 1 was carried out, except that the zeta potential value and the pH value were adjusted by adding hydrochloric acid of a reagent as an acid agent to the fine particle dispersion of the infrared-absorbing material according to Example 2, to obtain Comparative Example 2. An infrared absorbing material fine particle dispersion and a dried film were obtained. The obtained infrared-absorbing material fine particle dispersion and the dried film were evaluated and confirmed in the same manner as in Example 1. The zeta potential was -1 mV and the pH value was 2.5. Table 1 shows the evaluation and confirmation results.
- Example 3 The same procedure as in Example 1 was carried out, except that the zeta potential value and the pH value were adjusted by adding hydrochloric acid of a reagent as an acid agent to the fine particle dispersion of the infrared-absorbing material according to Example 3, and the procedure of Comparative Example 3 was repeated. An infrared absorbing material fine particle dispersion and a dried film were obtained. The obtained infrared absorbing material fine particle dispersion and the dried film were evaluated and confirmed in the same manner as in Example 1. The zeta potential was 1 mV and the pH value was 4.1. Table 1 shows the evaluation and confirmation results.
- Example 4 The same procedure as in Example 1 was carried out, except that the zeta potential value and the pH value were adjusted by adding hydrochloric acid of a reagent as an acid agent to the fine particle dispersion of the infrared-absorbing material according to Example 4, and the method of Comparative Example 4 was repeated. An infrared absorbing material fine particle dispersion and a dried film were obtained. The obtained infrared absorbing material fine particle dispersion and the dried film were evaluated and confirmed in the same manner as in Example 1. The zeta potential was 1 mV and the pH value was 4.5. Table 1 shows the evaluation and confirmation results.
- Example 5 40 g (20% by mass) of the composite tungsten oxide produced in Example 1, 80 g (40% by mass) of a commercially available polymer dispersant C (block copolymer having an amino group), and 80 g (40% by mass) of water And 750 g of ⁇ 0.3 zirconia beads were loaded into a paint shaker and subjected to pulverization and dispersion treatment to obtain a dispersion of fine particles of an infrared absorbing material according to Comparative Example 5 and a dried film. The obtained infrared absorbing material fine particle dispersion and the dried film were evaluated and confirmed in the same manner as in Example 1. The zeta potential was -0.5 mV and the pH value was 7.2. Table 1 shows the evaluation and confirmation results.
- the infrared absorbing material fine particle dispersions according to Comparative Examples 1 to 4 in which the absolute value of the zeta potential was out of the range of 5 mV or more and 100 mV or less were all stored at 25 ° C. for 6 months, and then the state of the bottom of the sample bottle was observed. Was visually observed to find that precipitation occurred and the stability was poor.
- the infrared absorbent material fine particle dispersion according to Comparative Example 5 was stored at 25 ° C. for 6 months, and then the appearance of the bottom of the sample bottle was visually confirmed. No precipitation occurred, and the stability was good.
- the dried film according to Example 5 produced significant bleed-out.
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Abstract
Description
これらの赤外線吸収体に係る提案を、機能的観点から俯瞰してみる。
すると、例えば、各種建築物や車両の窓材等の分野において、可視光線を十分に取り入れながら近赤外領域の光を遮蔽することにより、明るさを維持しつつ室内の温度上昇を抑制することを目的としたものがある。
すると、例えば窓材等に使用される遮光部材として、可視光領域から近赤外線領域に吸収特性があるカーボンブラック、チタンブラック等の無機顔料を用いた遮光部材、可視光領域のみに強い吸収特性のあるアニリンブラック等の有機顔料等を含む黒色系顔料を用いた遮光部材、さらに、アルミ等の金属を蒸着したハーフミラータイプの遮光部材、といった各種の遮光部材が提案されている。
当該太陽光可変調光断熱材料は太陽光が照射されると、光線中の紫外線が酸化タングステンに吸収されて励起電子とホールとが発生し、少量の紫外線量により5価タングステンの出現量が著しく増加して着色反応が速くなり、これに伴って着色濃度が高くなるものである。他方、光が遮断されることによって、前記5価タングステンが極めて速やかに6価に酸化されて消色反応が高くなるものである。当該着色/消色特性を用い、太陽光に対する着色および消色反応が速く、着色時に近赤外域の波長1250nmに吸収ピークが現れ、太陽光の近赤外線を遮断することが出来る太陽光可変調光断熱材料が得られることが提案されている。
尚、前記赤外線遮蔽材料微粒子は、一般式WyOz(但し、Wはタングステン、Oは酸素、2.2≦z/y≦2.999)で表記されるタングステン酸化物の微粒子、または/および、一般式MxWyOz(但し、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi、Iのうちから選択される1種類以上の元素、Wはタングステン、Oは酸素、0.001≦x/y≦1、2.2≦z/y≦3.0)で表記される複合タングステン酸化物の微粒子であって、当該赤外線遮蔽材料微粒子の粒子直径は1nm以上800nm以下である。
ここで、近年、各種の工業材料において環境負荷を低減することが求められており、上述した塗工液においても、溶媒が水を含むことを求められている。
本発明は上述の状況の下で為されたものであり、その課題とするところは、溶媒が水を含む場合、または、溶媒が全て水である場合であっても、長期保存性に優れる赤外線吸収材料微粒子分散液とその製造方法を提供することである。
赤外線吸収材料微粒子と溶媒とを含む赤外線吸収材料微粒子分散液であって、
前記赤外線吸収材料微粒子は、一般式MxWOy(ただし、Mは、Cs、Rb、K、Tl、Baから選択される1種類以上の元素、0.1≦x≦0.5、2.2≦y≦3.0)で表される複合タングステン酸化物微粒子を含み、
前記溶媒は水を含み、
前記赤外線吸収材料微粒子分散液のゼータ電位の絶対値が、5mV以上100mV以下であることを特徴とする赤外線吸収材料微粒子分散液である。
第2の発明は、
前記ゼータ電位の値が、-100mV以上-5mV以下であることを特徴とする第1の発明に記載の赤外線吸収材料微粒子分散液である。
第3の発明は、
pH値が4以上であることを特徴とする第1または第2の発明に記載の赤外線吸収微粒子分散液である。
第4の発明は、
前記複合タングステン酸化物微粒子の粒子径が、800nm以下であることを特徴とする第1から第3の発明のいずれかに記載の赤外線吸収材料微粒子分散液である。
第5の発明は、
さらに、1種以上の分散剤を含むことを特徴とする第1から第4の発明のいずれかに記載の赤外線吸収材料微粒子分散液である。
第6の発明は、
前記分散剤が、アミノ基、オキソ酸のいずれか1種以上を含むことを特徴とする第5の発明に記載の赤外線吸収材料微粒子分散液である。
第7の発明は、
前記赤外線吸収材料微粒子分散液中に含有されている赤外線吸収材料微粒子の含有量が、0.01質量%以上80質量%以下であることを特徴とする第1から第6の発明のいずれかに記載の赤外線吸収材料微粒子分散液である。
第8の発明は、
赤外線吸収材料微粒子と溶媒とを含む赤外線吸収材料微粒子分散液の製造方法であって、
水を含む前記溶媒へ、一般式MxWOy(ただし、Mは、Cs、Rb、K、Tl、Baから選択される1種類以上の元素、0.1≦x≦0.5、2.2≦y≦3.0)で表される複合タングステン酸化物微粒子を含む前記赤外線吸収材料微粒子を分散させて、赤外線吸収材料微粒子分散液とし、
前記赤外線吸収材料微粒子分散液のゼータ電位の絶対値を、5mV以上100mV以下とすることを特徴とする赤外線吸収材料微粒子分散液の製造方法である。
第9の発明は、
前記赤外線吸収材料微粒子分散液のpH値を、4以上とすることを特徴とする第8の発明に記載の赤外線吸収微粒子分散液の製造方法である。
以下、本発明に係る赤外線吸収材料微粒子分散液を、[1]赤外線吸収材料微粒子、[2]赤外線吸収材料微粒子分散液に用いられる溶媒、[3]赤外線吸収材料微粒子分散液、[4]赤外線吸収材料微粒子分散液へ添加される分散剤、[5]赤外線吸収材料微粒子の製造方法、[6]赤外線吸収材料微粒子分散液の製造方法、[7]赤外線吸収材料微粒子分散液の使用方法、の順に説明する。
本発明に係る赤外線吸収材料微粒子分散液は、赤外線吸収材料微粒子として、少なくとも一般式MxWyOz(但し、M元素はCs、Rb、K、Tl、Baから選択される1種類以上の元素、0.1≦x≦0.5、2.2≦y≦3.0)で表記される複合タングステン酸化物微粒子を含んでいる。
以下、複合タングステン酸化物微粒子を例として、本発明に係る赤外線吸収材料微粒子について説明する。
尚、本発明において「透明性」とは、「可視光領域の光に対して散乱が少なく透過性が高い。」という意味で用いている。
この酸素量の制御と、自由電子を生成するM元素の添加とを併用した赤外線吸収材料微粒子は、一般式をMxWyOz(但し、Mは、Cs、Rb、K、Tl、Baから選択される1種類以上の元素であることが好ましい、Wはタングステン、Oは酸素である。)と記載したとき、0.001≦x/y≦1、2.2≦z/y≦3の関係を満たす赤外線吸収材料微粒子である。
そして、六方晶の結晶構造を有する複合タングステン酸化物微粒子が均一な結晶構造を有するとき、M元素の添加量は、x/yの値で0.2以上0.5以下が好ましく、さらに好ましくは0.33である。x/yの値が0.33となることで、上述したM元素が六角形の空隙の全てに配置されると考えられる。
従って、可視光領域の光をより透過し、赤外線領域の光をより吸収する用途には、六方晶の複合タングステン酸化物を用いることが好ましい。ただし、ここで述べた光学特性の傾向は、あくまで大まかな傾向であり、添加元素の種類や、添加量、酸素量によって変化するものであり、本発明がこれに限定されるわけではない。
本発明に係る赤外線吸収材料微粒子分散液に用いられる溶媒は、その構成に水を含むものである。本発明において「構成に水を含む」とは、当該溶媒中に水を1質量%以上含むもののことであり、水と相溶する有機溶媒、例えば、アルコール類やグリコール類等と、水との混合溶媒を包括する概念である。さらに、水のみで構成される溶媒も包括する概念である。
尚、本発明において水とは、塩素などの陰イオンをイオン交換樹脂で除去したイオン交換水、超純水等を含む概念である。
本発明に係る赤外線吸収材料微粒子分散液は、上述した赤外線吸収材料微粒子を溶媒に分散させた分散液である。
本発明に係る赤外線吸収材料微粒子分散液は、ゼータ電位の絶対値が5mV以上100mV以下の範囲にある分散液である。即ち、ゼータ電位の値が、5mV以上100mV以下、または、-100mV以上-5mV以下の範囲にある分散液である。
本発明において、赤外線吸収材料微粒子の分散粒子径とは、上述した赤外線吸収材料微粒子の粒子径とは異なり、赤外線吸収材料微粒子の凝集体の粒径も含む概念である。
この粒子による散乱の低減を重視するとき、当該分散液中における赤外線吸収材料微粒子の分散粒子径は200nm以下、好ましくは100nm以下が良い。この理由は、赤外線吸収材料微粒子の分散粒子径が小さければ、幾何学散乱もしくはミー散乱による、波長400nm~780nmの可視光線領域の光の散乱が低減される結果、赤外線吸収膜が曇りガラスのようになり、鮮明な透明性が得られなくなるのを回避できるからである。即ち、当該分散液中における赤外線吸収材料微粒子の分散粒子径が200nm以下になると、上記幾何学散乱もしくはミー散乱が低減し、レイリー散乱領域になる。レイリー散乱領域では、散乱光は粒子径の6乗に比例しているため、分散粒子径の減少に伴い散乱が低減し透明性が向上するからである。
さらに分散粒子径が100nm以下になると、散乱光は非常に少なくなり好ましい。光の散乱を回避する観点からは、分散粒子径が小さい方が好ましく、分散粒子径が1nm以上あれば工業的な製造は容易である。
尚、赤外線吸収材料微粒子の分散粒子径は、動的光散乱法を原理とした大塚電子株式会社製ELS-8000等を用いて測定することができる。
本発明に係る赤外線吸収材料微粒子分散液のゼータ電位は、当該分散液のpH調整、当該分散液への分散剤の添加により制御出来る。
具体的には、赤外線吸収材料微粒子分散液のpH値を3以上10以下とすることが好ましく、pH値を4以上7以下とすることがより好ましい。当該pH調整には、当該分散液への弱酸等の添加も有効である。
また、セリン、フェニルアラニン等のアミノ酸を、分散剤として添加してもよい。
また、好ましい分散剤として、オキソ酸を備える水溶性の分散剤を挙げることも出来る。ここで、オキソ酸としてはカルボキシル基を好ましく挙げることができる。例えば市販の分散剤として、ソルスパース41090、ソルスパース43000、ソルスパース44000、ソルスパース46000、ソルスパース47000、ソルスパース53095(ルーブリゾール社製)等を好ましく挙げることが出来る。
これに対し、赤外線吸収材料微粒子分散液へ添加する分散剤が低分子分散剤の場合、著しいブリードアウトを生じることはない。
本発明に係る赤外線吸収材料微粒子分散液に含まれる赤外線吸収材料微粒子の製造方法について、例として、固相反応による複合タングステン酸化物微粒子の製造例を用いて説明する。
タングステン化合物としては、タングステン酸(H2WO4)、タングステン酸アンモニウム、六塩化タングステン、アルコールに溶解した六塩化タングステンに水を添加して加水分解した後、溶媒を蒸発させたタングステンの水和物、から選ばれる1種以上であることが好ましい。
本発明に係る赤外線吸収材料微粒子と溶媒とを含む赤外線吸収材料微粒子分散液の製造方法は、上述した溶媒へ、一般式MxWOyで表される複合タングステン酸化物微粒子を含む前記赤外線吸収材料微粒子を分散させて赤外線吸収材料微粒子分散液を製造し、当該分散液のゼータ電位の絶対値を所定の値の範囲内とするものである。
そして、当該粉砕・分散処理後における赤外線吸収材料微粒子分散液のゼータ電位の絶対値を5mV以上100mV以下に維持できればよい。
本発明に係る赤外線吸収材料微粒子分散液へ、バインダーとして水溶性のポリスチレン、水溶性のスチレン‐ブタジエン共重合物、水溶性のアクリル酸エステル共重合物のエマルジョン等を加え混合することで、本発明に係る赤外線吸収材料微粒子を含む水溶性の塗工液を製造することが出来る。
製造された塗工液を、ガラス等の基材に塗布し、乾燥させれば、塗工液の塗布した膜が硬化し、赤外線吸収材料微粒子分散体を得ることが出来る。例えば、基材がガラスならば、赤外線吸収材料微粒子分散体を備えたガラスを得ることが出来るので、これを窓等に用いると赤外線遮蔽窓を得ることが出来る。
また、本発明に係る赤外線吸収材料微粒子分散液や塗工液は、インクジェットやスプレー塗装など公知の塗布方法に適用出来る。
水0.330kgへCs2CO30.216kgを加えて溶解し、得られた溶液をH2WO41.000kgへ添加して十分攪拌した後、乾燥して乾燥物を得た。N2ガスをキャリアーとした5%H2ガスを供給しながら当該乾燥物を加熱し、800℃の温度で1時間焼成した。その後、さらにN2ガス雰囲気下800℃で2時間焼成する固相法によって、複合タングステン酸化物(Cs0.33WO3)を得た。
実施例1にて製造した複合タングステン酸化物40g(20質量%)と、市販の高分子分散剤A(有機オキソ酸を含む化合物)16g(8質量%)と、水144g(72質量%)と、φ0.3ジルコニアビーズ750gとをペイントシェーカーに装填し、実施例1と同様に粉砕・分散処理を行って、実施例2に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた実施例2に係る赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は-40mV、pH値は6.9であった。当該評価、確認結果を表1に示す。
実施例1にて製造した複合タングステン酸化物40g(20質量%)と、低分子分散剤Bとしてフェニルアラニン40g(20質量%)と、水120g(60質量%)と、φ0.3ジルコニアビーズ750gとをペイントシェーカーに装填し、実施例1と同様に粉砕・分散処理を行って、実施例3に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた実施例3に係る赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は-70mV、pH値は5.3であった。当該評価、確認結果を表1に示す。
実施例1にて製造した複合タングステン酸化物40g(20質量%)と、市販の高分子分散剤C(アミノ基を持つブロック共重合体)16g(8質量%)、水144g(72質量%)と、φ0.3ジルコニアビーズ750gとをペイントシェーカーに装填し、実施例1と同様に粉砕・分散処理を行って、実施例4に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた実施例4に係る赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は-23mV、pH値は6.5であった。当該評価、確認結果を表1に示す。
実施例1に係る赤外線吸収材料微粒子分散液へ、酸剤である試薬の塩酸を添加してゼータ電位値、pH値を調整した以外は実施例1と同様に操作して、比較例1に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は2mV、pH値は2.4であった。当該評価、確認結果を表1に示す。
実施例2に係る赤外線吸収材料微粒子分散液へ、酸剤である試薬の塩酸を添加してゼータ電位値、pH値を調整した以外は実施例1と同様に操作して、比較例2に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた赤外線吸収材料微粒子分散液をと乾燥膜と、実施例1と同様の方法で評価、確認した。ゼータ電位は-1mV、pH値は2.5であった。当該評価、確認結果を表1に示す。
実施例3に係る赤外線吸収材料微粒子分散液へ、酸剤である試薬の塩酸を添加してゼータ電位値、pH値を調整した以外は実施例1と同様に操作して、比較例3に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は1mV、pH値は4.1であった。当該評価、確認結果を表1に示す。
実施例4に係る赤外線吸収材料微粒子分散液へ、酸剤である試薬の塩酸を添加してゼータ電位値、pH値を調整した以外は実施例1と同様に操作して、比較例4に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は1mV、pH値は4.5であった。当該評価、確認結果を表1に示す。
実施例1にて製造した複合タングステン酸化物40g(20質量%)と、市販の高分子分散剤C(アミノ基を持つブロック共重合体)80g(40質量%)、水80g(40質量%)と、φ0.3ジルコニアビーズ750gとをペイントシェーカーに装填し粉砕・分散処理を行って、比較例5に係る赤外線吸収材料微粒子分散液と乾燥膜とを得た。
得られた赤外線吸収材料微粒子分散液と乾燥膜とを、実施例1と同様の方法で評価、確認した。ゼータ電位は-0.5mV、pH値は7.2であった。当該評価、確認結果を表1に示す。
構成に水を含む溶媒中に、赤外線吸収材料微粒子として、一般式CsWOyで表される複合タングステン酸化物微粒子を分散し、そのゼータ電位の絶対値が5mV以上100mV以下である実施例1~3に係る赤外線吸収材料微粒子分散液は、いずれも25℃にて6ヶ月保管した後、サンプル瓶底の様子を目視で確認したところ沈殿発生はなく、安定性は良好であった。
一方、ゼータ電位の絶対値が5mV以上100mV以下の範囲外であった比較例1~4に係る赤外線吸収材料微粒子分散液は、いずれも25℃にて6ヶ月保管した後、サンプル瓶底の様子を目視で確認したところ沈殿の発生があり、安定性に劣るものであった。
比較例5にかかる係る赤外線吸収材料微粒子分散液は、25℃にて6ヶ月保管した後、サンプル瓶底の様子を目視で確認したところ沈殿発生はなく、安定性は良好であったが、比較例5に係る乾燥膜には著しいブリードアウトを生じた。
Claims (9)
- 赤外線吸収材料微粒子と溶媒とを含む赤外線吸収材料微粒子分散液であって、
前記赤外線吸収材料微粒子は、一般式MxWOy(ただし、Mは、Cs、Rb、K、Tl、Baから選択される1種類以上の元素、0.1≦x≦0.5、2.2≦y≦3.0)で表される複合タングステン酸化物微粒子を含み、
前記溶媒は水を含み、
前記赤外線吸収材料微粒子分散液のゼータ電位の絶対値が、5mV以上100mV以下であることを特徴とする赤外線吸収材料微粒子分散液。 - 前記ゼータ電位の値が、-100mV以上-5mV以下であることを特徴とする請求項1に記載の赤外線吸収材料微粒子分散液。
- pH値が4以上であることを特徴とする請求項1または2に記載の赤外線吸収微粒子分散液。
- 前記複合タングステン酸化物微粒子の粒子径が、800nm以下であることを特徴とする請求項1から3のいずれかに記載の赤外線吸収材料微粒子分散液。
- さらに、1種以上の分散剤を含むことを特徴とする請求項1から4のいずれかに記載の赤外線吸収材料微粒子分散液。
- 前記分散剤が、アミノ基、オキソ酸のいずれか1種以上を含むことを特徴とする請求項5に記載の赤外線吸収材料微粒子分散液。
- 前記赤外線吸収材料微粒子分散液中に含有されている赤外線吸収材料微粒子の含有量が、0.01質量%以上80質量%以下であることを特徴とする請求項1から6のいずれかに記載の赤外線吸収材料微粒子分散液。
- 赤外線吸収材料微粒子と溶媒とを含む赤外線吸収材料微粒子分散液の製造方法であって、
水を含む前記溶媒へ、一般式MxWOy(ただし、Mは、Cs、Rb、K、Tl、Baから選択される1種類以上の元素、0.1≦x≦0.5、2.2≦y≦3.0)で表される複合タングステン酸化物微粒子を含む前記赤外線吸収材料微粒子を分散させて、赤外線吸収材料微粒子分散液とし、
前記赤外線吸収材料微粒子分散液のゼータ電位の絶対値を、5mV以上100mV以下とすることを特徴とする赤外線吸収材料微粒子分散液の製造方法。 - 前記赤外線吸収材料微粒子分散液のpH値を、4以上とすることを特徴とする請求項8に記載の赤外線吸収微粒子分散液の製造方法。
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