JP5517268B2 - Particulate metal oxides and their applications - Google Patents
Particulate metal oxides and their applications Download PDFInfo
- Publication number
- JP5517268B2 JP5517268B2 JP2012070378A JP2012070378A JP5517268B2 JP 5517268 B2 JP5517268 B2 JP 5517268B2 JP 2012070378 A JP2012070378 A JP 2012070378A JP 2012070378 A JP2012070378 A JP 2012070378A JP 5517268 B2 JP5517268 B2 JP 5517268B2
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- particle
- particles
- oxide
- metal
- 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
- 150000004706 metal oxides Chemical class 0.000 title claims description 125
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 117
- 239000002245 particle Substances 0.000 claims description 97
- 229910052751 metal Inorganic materials 0.000 claims description 89
- 239000002184 metal Substances 0.000 claims description 70
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 229910052709 silver Inorganic materials 0.000 claims description 33
- 229910052748 manganese Inorganic materials 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 125000002252 acyl group Chemical group 0.000 claims description 11
- 239000011358 absorbing material Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 52
- 239000010408 film Substances 0.000 description 47
- 239000010419 fine particle Substances 0.000 description 46
- 239000010949 copper Substances 0.000 description 45
- 239000006185 dispersion Substances 0.000 description 42
- 239000011572 manganese Substances 0.000 description 36
- 150000002736 metal compounds Chemical class 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 26
- 239000011787 zinc oxide Substances 0.000 description 26
- 239000010944 silver (metal) Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- -1 plates Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 17
- 239000003973 paint Substances 0.000 description 17
- 238000002834 transmittance Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000012295 chemical reaction liquid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 239000007810 chemical reaction solvent Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 150000007942 carboxylates Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 239000011882 ultra-fine particle Substances 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910001111 Fine metal Inorganic materials 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(II) acetate Substances [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- BOSZBTFBHSYELP-UHFFFAOYSA-N 2-trimethoxysilylethanol Chemical compound CO[Si](OC)(OC)CCO BOSZBTFBHSYELP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- FAYGEALAEQKPDI-UHFFFAOYSA-N 4-(2-methoxyethyl)phenol Chemical compound COCCC1=CC=C(O)C=C1 FAYGEALAEQKPDI-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- AHTPEIQXPTWZNM-UHFFFAOYSA-N C(C=C)(=O)OCCC[Si](OC(C=C)=O)(OC(C=C)=O)OC(C=C)=O Chemical compound C(C=C)(=O)OCCC[Si](OC(C=C)=O)(OC(C=C)=O)OC(C=C)=O AHTPEIQXPTWZNM-UHFFFAOYSA-N 0.000 description 1
- CMCTWNKBDTVMGR-UHFFFAOYSA-K C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-] Chemical compound C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-] CMCTWNKBDTVMGR-UHFFFAOYSA-K 0.000 description 1
- KFDGIFZCOIOUIL-UHFFFAOYSA-N CCCCO[Zr](OCCCC)OCCCC Chemical compound CCCCO[Zr](OCCCC)OCCCC KFDGIFZCOIOUIL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- HICCMIMHFYBSJX-UHFFFAOYSA-N [SiH4].[Cl] Chemical compound [SiH4].[Cl] HICCMIMHFYBSJX-UHFFFAOYSA-N 0.000 description 1
- LDSQEKQMBGLXHE-UHFFFAOYSA-L [Zr+4].CCCC[O-].CCCC[O-].CC(=C)C([O-])=O.CC(=C)C([O-])=O Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CC(=C)C([O-])=O.CC(=C)C([O-])=O LDSQEKQMBGLXHE-UHFFFAOYSA-L 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- NIOLTQNBOYMEQK-UHFFFAOYSA-N butan-1-olate;zirconium(2+) Chemical compound [Zr+2].CCCC[O-].CCCC[O-] NIOLTQNBOYMEQK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000002160 cholyl group Chemical group [H]C([H])([C@]1(C([C@@]2([H])O[H])([H])[H])[H])[C@@](O[H])([H])C([H])([H])C([H])([H])[C@]1(C([H])([H])[H])[C@]1([H])[C@]2([H])[C@]2([H])C([H])([H])C([H])([H])[C@@]([C@](C([H])([H])[H])(C(C(C(=O)[*])([H])[H])([H])[H])[H])([H])[C@@]2(C([H])([H])[H])[C@](O[H])([H])C1([H])[H] 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- PFURGBBHAOXLIO-WDSKDSINSA-N cyclohexane-1,2-diol Chemical compound O[C@H]1CCCC[C@@H]1O PFURGBBHAOXLIO-WDSKDSINSA-N 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- VCVOSERVUCJNPR-UHFFFAOYSA-N cyclopentane-1,2-diol Chemical compound OC1CCCC1O VCVOSERVUCJNPR-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- DYHSMQWCZLNWGO-UHFFFAOYSA-N di(propan-2-yloxy)alumane Chemical compound CC(C)O[AlH]OC(C)C DYHSMQWCZLNWGO-UHFFFAOYSA-N 0.000 description 1
- MQVULIBSPNZEFI-UHFFFAOYSA-M di(propan-2-yloxy)alumanylium;2-methylprop-2-enoate Chemical compound CC(=C)C([O-])=O.CC(C)O[Al+]OC(C)C MQVULIBSPNZEFI-UHFFFAOYSA-M 0.000 description 1
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- VKSCZTWQDPUHIK-UHFFFAOYSA-N isocyanic acid;trimethoxy(propyl)silane Chemical group N=C=O.CCC[Si](OC)(OC)OC VKSCZTWQDPUHIK-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- ICRFXIKCXYDMJD-UHFFFAOYSA-N n'-benzyl-n'-ethenyl-n-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN(C=C)CC1=CC=CC=C1 ICRFXIKCXYDMJD-UHFFFAOYSA-N 0.000 description 1
- HZGIOLNCNORPKR-UHFFFAOYSA-N n,n'-bis(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCC[Si](OC)(OC)OC HZGIOLNCNORPKR-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N noncarboxylic acid Natural products CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical compound CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- MBSOYVMTSJAYPW-UHFFFAOYSA-N sulfanylsilane 3-trimethoxysilylpropane-1-thiol Chemical compound S[SiH3].CO[Si](OC)(OC)CCCS MBSOYVMTSJAYPW-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical group CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Images
Description
本発明は、より優れた紫外線吸収性を発揮するとともに、例えば、基材に内添もしくはコーティングした場合にも基材の透明性や色相を損なうことのない微粒子状金属酸化物に関する。 The present invention relates to a fine particle metal oxide that exhibits superior ultraviolet absorptivity and that does not impair the transparency and hue of the substrate even when the substrate is internally added or coated.
従来、紫外線遮蔽能を付与する目的で、例えば、繊維、板、フィルム等のプラスチック成形体、塗料、化粧料等に紫外線吸収性材料を内添したり、ガラス、プラスチックフィルム等に溶媒やバインダー樹脂とともに紫外線吸収性材料を含むコーティング剤をコーティングしたりすることが行われている。
例えば、化粧品、建材や自動車用あるいはディスプレイ用の窓ガラス、フラットパネルディスプレイなどの各種分野で用いられる紫外線吸収性材料には、近年、従来一般的に言われている３８０ｎｍ以下の紫外線（特に３８０ｎｍ付近の紫外線）に加え、より長波長領域の紫外線（短波長の可視光）に対しても優れた吸収性能を有することが求められるとともに、可視光を散乱させず高い可視光透過性を示し良好な透明性を有すること、黄色などの着色がなく基材の色相を変化させないこと、および、耐久性や耐熱性に優れること、が求められている。耐久性や耐熱性の点では無機系材料であることが望ましく、高い可視光透過性を示し良好な透明性を有するという可視光特性の点では、超微粒子であることが望ましい。そこで、これまでに、酸化亜鉛、酸化チタン、酸化セリウム等の金属酸化物の超微粒子が開発されているが、これらは紫外線吸収性能が不充分であり、例えば、３８０ｎｍ以下の紫外線を完全に遮蔽するには単位面積あたり多量の超微粒子を用いなければならず、膜厚が厚くなりすぎるなど、実用性に欠けるという問題があった。
Conventionally, for the purpose of imparting ultraviolet shielding ability, for example, an ultraviolet-absorbing material is internally added to plastic moldings such as fibers, plates, and films, paints, and cosmetics, and solvents and binder resins are added to glass and plastic films. In addition, a coating agent containing an ultraviolet absorbing material is coated.
For example, UV absorbing materials used in various fields such as cosmetics, building materials, window glass for automobiles or displays, and flat panel displays include ultraviolet rays of 380 nm or less (especially in the vicinity of 380 nm) which have been generally known in recent years. In addition to UV rays in the longer wavelength region (short-wavelength visible light), it is required to have an excellent absorption performance, and high visible light permeability is exhibited without scattering visible light. It is required to have transparency, to have no color such as yellow, and to not change the hue of the base material, and to be excellent in durability and heat resistance. From the viewpoint of durability and heat resistance, an inorganic material is desirable, and from the viewpoint of visible light characteristics such as high visible light transmittance and good transparency, ultrafine particles are desirable. So far, ultrafine particles of metal oxides such as zinc oxide, titanium oxide, and cerium oxide have been developed, but these have insufficient ultraviolet absorption performance, and for example, completely shielded from ultraviolet rays of 380 nm or less. In order to achieve this, a large amount of ultrafine particles must be used per unit area, and there is a problem of lack of practicality such as an excessively thick film thickness.
そこで、前記酸化亜鉛、酸化チタン、酸化セリウム等の金属酸化物からなる超微粒子の紫外線吸収性能を改善する手法として、異種金属等との複合化が提案されている。例えば、酸化亜鉛については、ｉ）ＦｅやＣｏを酸化亜鉛に含有（ドープ）させたもの（特許文献１、非特許文献１参照）、ｉｉ）Ｃｅ、Ｔｉ、Ａｌ、Ｆｅ、ＣｒおよびＺｒからなる少なくとも１種とＺｎとの複合酸化物（特許文献２参照）、ｉｉｉ）Ｃｅ、Ｔｉ、Ａｌ、Ｆｅ、Ｃｏ、ＬａおよびＮｉからなる少なくとも１種を酸化亜鉛に含有させたもの（特許文献３参照）が提案されている。
ところで、紫外線吸収材料を目的としたものではないが、酸化亜鉛に異種金属を含有させる技術として、１０の２乗ｐｐｍのＣｕを固溶させた酸化亜鉛が報告されており（非特許文献２参照）、このような酸化亜鉛についても紫外線吸収性能の改善が期待できるのではないかと考えられる。
Thus, as a technique for improving the ultraviolet absorption performance of ultrafine particles made of metal oxides such as zinc oxide, titanium oxide, and cerium oxide, compounding with different metals has been proposed. For example, with respect to zinc oxide, i) containing (doped) Fe or Co in zinc oxide (see
By the way, although not intended for an ultraviolet absorbing material, zinc oxide in which 10 2 ppm of Cu is dissolved is reported as a technique for incorporating a different metal into zinc oxide (see Non-Patent Document 2). ), It is considered that such zinc oxide can be expected to improve the ultraviolet absorption performance.
しかしながら、近年、より高い紫外線遮断能が要求される用途が増えつつあるなか、前記ｉ）〜前記ｉｉｉ）のような金属酸化物超微粒子では、その紫外線吸収能は未だ充分とは言えず、特に、最も遮蔽要求が高い３８０ｎｍ付近の紫外線に対する吸収性能についてはさらなる向上が望まれているのが現状であった。しかも、前記ｉ）のようにＦｅやＣｏを含有させた場合には、３８０ｎｍより長波長の光に対する吸収性能は高められるものの、３８０ｎｍでの吸収性能は逆に低下することになり、しかも、可視光領域に吸収帯が存在するために、Ｆｅは黄色に、Ｃｏは青色に、それぞれ強く着色することになり、紫外線吸収性材料として基材に内添あるいはコーティングすると基材の透明性や色相を損なうと言った問題が生じていた。さらに、従来の技術では、これらの金属をドープしてなるものであって単離、分散性に優れる微粒子を製造することは困難であった。 However, in recent years, the use of metal oxide ultrafine particles such as i) to iii) has not yet been sufficiently satisfactory in the applications where higher ultraviolet blocking ability is required. Further, the present situation is that further improvement is desired for the absorption performance with respect to the ultraviolet light around 380 nm, which has the highest shielding requirement. Moreover, when Fe or Co is added as in i) above, the absorption performance for light having a wavelength longer than 380 nm is enhanced, but the absorption performance at 380 nm is conversely reduced, and visible. Since there is an absorption band in the light region, Fe will be yellow and Co will be strongly colored blue, and if the substrate is internally added or coated as an ultraviolet absorbing material, the transparency and hue of the substrate will be increased. There was a problem that said it would lose. Furthermore, in the conventional technique, it has been difficult to produce fine particles that are doped with these metals and have excellent isolation and dispersibility.
前記非特許文献２に報告されているＣｕ固溶の酸化亜鉛は、水熱法で合成されたものであり、その粒子の大きさは１０〜２５ｍｍと非常に大きく、しかも、黄色に着色したものであった。したがって、このような酸化亜鉛を紫外線吸収材料とした場合、高い可視光透過性を示し良好な透明性を有するという可視特性は得られず、紫外線吸収性材料として基材に内添あるいはコーティングすると基材の透明性や色相を損なうといった問題が生じることになる。
そこで、本発明が解決しようとする課題は、より優れた紫外線吸収性を発揮するとともに、良好な透明性を有し、例えば基材に内添もしくはコーティングした場合にも基材の透明性や色相を損なうことがない、微粒子状金属酸化物を提供することにある。
The solid solution of zinc oxide reported in Non-Patent
Therefore, the problem to be solved by the present invention is to exhibit better UV absorption and good transparency, for example, when the substrate is internally added or coated, the transparency and hue of the substrate. It is an object of the present invention to provide a particulate metal oxide that does not impair the quality.
本発明者は、上記課題を解決するべく鋭意検討を行った。その結果、金属酸化物に異種金属元素を含有させて紫外線吸収性能を向上させるにあたり、含有させる異種金属元素としてはＣｕ、Ａｇ、Ｍｎが極めて優れた向上効果を発現させうること、なおかつ、Ｃｕ、Ａｇ、Ｍｎを含有させる場合には、母体となる金属酸化物として酸化亜鉛、酸化チタン、酸化セリウムのいずれかを選択することが最適であること、を見出し、このようなＣｕ、Ａｇ、Ｍｎを特定の金属酸化物に含有させてなる微粒子状金属酸化物であれば、前記課題を一挙に解決しうることを見出し、本発明を完成した。
すなわち、本発明にかかる微粒子状金属酸化物は、Ｚｎ、ＴｉおよびＣｅからなる群より選ばれる少なくとも１種を金属元素とする酸化物からなる粒子内にＣｕ、ＡｇおよびＭｎからなる群より選ばれた１種以上に由来する成分が含有されてなる。
The present inventor has intensively studied to solve the above problems. As a result, in order to improve the ultraviolet absorption performance by containing a different metal element in the metal oxide, Cu, Ag, and Mn can express an extremely excellent improvement effect as the different metal element to be included, and Cu, When Ag and Mn are contained, it is found that it is optimal to select any one of zinc oxide, titanium oxide, and cerium oxide as a base metal oxide, and such Cu, Ag, and Mn are added. The present inventors have found that the above-described problems can be solved at once by using a particulate metal oxide contained in a specific metal oxide, thereby completing the present invention.
That is, the particulate metal oxide according to the present invention is selected from the group consisting of Cu, Ag and Mn in the particle consisting of an oxide containing at least one metal element selected from the group consisting of Zn, Ti and Ce. In addition, a component derived from one or more kinds is contained.
なお、本発明において、「微粒子」とは、１次粒子径が０．１μｍ以下である粒子を意味するものである。詳しくは、前記１次粒子径は結晶子径または比表面積径を以って判断することができ、結晶子径または比表面積径のいずれかが０．１μｍ以下である粒子を「微粒子」とするものである。 In the present invention, “fine particles” mean particles having a primary particle diameter of 0.1 μm or less. Specifically, the primary particle diameter can be determined by a crystallite diameter or a specific surface area diameter, and particles having either a crystallite diameter or a specific surface area diameter of 0.1 μm or less are referred to as “fine particles”. Is.
本発明によれば、より優れた紫外線吸収性能を発揮するとともに、良好な透明性を有し、例えば基材に内添もしくはコーティングした場合にも基材の透明性や色相を損なうことがない、微粒子状金属酸化物を提供することができる。 According to the present invention, while exhibiting more excellent ultraviolet absorption performance, it has good transparency, for example, when the substrate is internally added or coated, the transparency and hue of the substrate are not impaired, A particulate metal oxide can be provided.
以下、本発明について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。
本発明の微粒子状金属酸化物は、Ｚｎ、ＴｉおよびＣｅからなる群より選ばれる少なくとも１種を金属元素とする酸化物（以下単に「特定金属酸化物」と称することもある）からなる粒子内にＣｕ、ＡｇおよびＭｎからなる群より選ばれた１種以上（以下「異種金属元素」と称することもある）に由来する成分が含有されてなる。詳しくは、本発明において、Ｃｕ、ＡｇおよびＭｎからなる群より選ばれた１種以上に由来する成分を含有するとは、前記特定金属酸化物がＣｕ、ＡｇおよびＭｎからなる群より選ばれた１種以上を含む金属酸化物であればよく、Ｃｕ、Ａｇ、Ｍｎがいかなる存在形態で含有されているかは問わない。
Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.
The fine-particle metal oxide of the present invention has an intraparticle particle made of an oxide having at least one metal element selected from the group consisting of Zn, Ti and Ce (hereinafter sometimes simply referred to as “specific metal oxide”). And a component derived from one or more selected from the group consisting of Cu, Ag and Mn (hereinafter sometimes referred to as “foreign metal element”). Specifically, in the present invention, when the component derived from one or more selected from the group consisting of Cu, Ag and Mn is contained, the specific metal oxide is selected from the group consisting of Cu, Ag and Mn. What is necessary is just a metal oxide containing more than seed | species, and it does not ask | require what Cu, Ag, and Mn are contained by what kind of presence form.
本発明の微粒子状金属酸化物において、前記特定金属酸化物に含有される異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の存在形態の具体例としては、例えば、（Ｉ）異種金属元素が特定金属酸化物の結晶に固溶して存在している形態、（ＩＩ）異種金属元素が特定金属酸化物の金属成分として含有された状態（好ましくは複合酸化物）で存在している形態、（ＩＩＩ）異種金属元素が特定金属酸化物の結晶表面に吸着している形態、（ＩＶ）異種金属元素が金属として粒子状または膜状で特定金属酸化物の表面に付着している形態、などが例示される。なかでも、特定金属酸化物の結晶中に原子状（イオン状態を含む）で均一に分散されている固溶の形態が、紫外線吸収性に優れ、しかも良好な透明性を保持させうる点で、好ましい。 In the particulate metal oxide of the present invention, specific examples of the presence form of the different metal elements (Cu, Ag, Mn) contained in the specific metal oxide include, for example, (I) the different metal element is a specific metal oxide (II) a form in which a foreign metal element is present as a metal component of a specific metal oxide (preferably a complex oxide), (III) Examples include the form in which foreign metal elements are adsorbed on the crystal surface of the specific metal oxide, and (IV) the form in which the different metal elements are attached to the surface of the specific metal oxide in the form of particles or films as metals. The Among them, in the form of a solid solution uniformly dispersed in an atomic form (including an ionic state) in a crystal of a specific metal oxide, it is excellent in ultraviolet absorption and can maintain good transparency. preferable.
本発明の微粒子状金属酸化物において、前記特定金属酸化物に含有される異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の分散状態としては、（ｉ）特定金属酸化物からなる粒子中に均一に分散して含有されていてもよく、あるいは、（ｉｉ）部分的に含有（偏析という意味ではなく、１個の粒子についてみたときに、局部的に高濃度で含有されているということ。）されていてもよい。（ｉ）の場合としては、例えば、前記（Ｉ）の形態において、特定金属酸化物の結晶中に、均一に（表面層から結晶子内部まで）固溶している場合が挙げられる。（ｉｉ）の場合としては、特定金属酸化物の結晶の表面に表面層として、異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）が固溶した酸化物固溶体相（前記（Ｉ）の形態）、あるいは、異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）と特定金属酸化物との複合酸化物相（前記（ＩＩ）の形態）を形成している場合、が挙げられる。 In the particulate metal oxide of the present invention, the dispersive state of the different metal elements (Cu, Ag, Mn) contained in the specific metal oxide is (i) uniformly dispersed in the particles made of the specific metal oxide. Or (ii) partially contained (not segregated, but contained locally at a high concentration when viewed with respect to one particle). May be. As the case of (i), for example, in the form of (I), there may be mentioned a case where the specific metal oxide is uniformly dissolved (from the surface layer to the inside of the crystallite) in the crystal of the specific metal oxide. In the case of (ii), as a surface layer on the surface of the crystal of the specific metal oxide, an oxide solid solution phase (form (I)) in which a different metal element (Cu, Ag, Mn) is dissolved, or In the case where a composite oxide phase (form (II)) of a different metal element (Cu, Ag, Mn) and a specific metal oxide is formed.
一般に、金属酸化物は、結晶性を示すもの（結晶体）と、結晶性を示さないもの（非結晶体）とに分類される。前記結晶体とは、規則的な原子配列が周期性をもって認められる結晶子からなる金属酸化物であると定義することができ、電子線回折学的および／またはＸ線回折学的に、格子定数および／または回折パターンから金属酸化物の同定ができるものを言い、そうでないものは非結晶体であると定義できる。一般に、紫外線吸収能などに優れる点では、結晶体であることが好ましく、本発明においては、特定金属酸化物は結晶体であることが好ましい。
前記結晶体は、単結晶体であっても多結晶体であってもよく、これらを構成する結晶子の形状としては、例えば、球状、楕円球状、立方体状、直方体状、多面体状、ピラミッド状、柱状、チューブ状、りん片状、（六角）板状等の薄片状や、過飽和度の高い条件下で結晶の稜や角が優先的に伸びて生成した樹枝状、骸晶状などが挙げられる。結晶子の配向性については、限定はされず、全ての結晶子の配向性が揃っていても、ランダムであっても、一部が同じ配向性で残りがランダムであってもよく、限定はされない。
In general, metal oxides are classified into those exhibiting crystallinity (crystals) and those not exhibiting crystallinity (non-crystals). The crystal body can be defined as a metal oxide composed of crystallites in which a regular atomic arrangement is recognized with periodicity, and has a lattice constant in electron diffraction and / or X-ray diffraction. And / or refers to what can identify a metal oxide from a diffraction pattern, otherwise it can be defined as amorphous. In general, in terms of excellent ultraviolet absorbing ability, a crystal is preferable, and in the present invention, the specific metal oxide is preferably a crystal.
The crystal body may be a single crystal body or a polycrystal body, and examples of the shape of the crystallite constituting the crystal body include a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a polyhedral shape, and a pyramid shape. , Columnar, tube-like, flake-like, (hexagonal) plate-like flakes, dendrites, skeletons, etc. produced by preferentially extending crystal edges and corners under conditions of high supersaturation It is done. The orientation of the crystallites is not limited, and even if all the orientations of the crystallites are uniform or random, some of them may be the same orientation and the rest may be random. Not.
本発明の微粒子状金属酸化物の形状は、限定はされないが、例えば、球状（真球状）、楕円球状、立方体状、直方体状、ピラミッド状、針状、柱状、棒状、筒状、りん片状、（六角）板状等の薄片状などが挙げられる。
本発明の微粒子状金属酸化物は、微粒子、すなわち１次粒子径が０．１μｍ以下である粒子であり、言い換えれば、前記特定金属酸化物からなる粒子の１次粒子径は０．１μｍ以下である。特定金属酸化物からなる粒子の１次粒子径は３〜５０ｎｍであることが好ましい。より好ましくは、３〜３０ｎｍ、さらに好ましくは５〜２０ｎｍである。１次粒子の平均粒子径が３ｎｍ未満であると、量子効果により紫外線吸収端が短波長側にシフトする傾向があり紫外線吸収材料として好ましくなくなり、一方、５０ｎｍを超えると、透明性が低下するおそれがある。なお、ここで、１次粒子の平均粒子径とは、結晶子径（Ｄｗ）または比表面積径（Ｄｓ）を意味するものであり、詳しくは、前記粒子が結晶体である場合には結晶子径（Ｄｗ）を、前記粒子が非結晶体である場合には比表面積径（Ｄｓ）を意味するものである。したがって、結晶子径（Ｄｗ）と比表面積径（Ｄｓ）のいずれか一方が前記範囲になることが好ましいのである。より詳しくは、結晶子径（Ｄｗ）とは、Ｘ線回折学的に結晶の場合に適用されるものであり、シェラー法により求められた結晶子の大きさのことである。該結晶子径（Ｄｗ）は、通常、金属酸化物粒子の粉末Ｘ線回折パターンを測定し、３強線（ピークが最も大きい回折線（１）、２番目に大きい回折線（２）、３番目に大きい回折線（３））について、それぞれの半値巾または積分巾よりシェラーの式から回折線（１）〜（３）に帰属される回折面に垂直方向の結晶子径Ｄ１、Ｄ２、Ｄ３を求め、これらの平均値（（Ｄ１＋Ｄ２＋Ｄ３）／３）を結晶子径（Ｄｗ）として算出することができる。他方、比表面積径（Ｄｓ）は、微粒子状金属酸化物の粉末の真比重と比表面積を測定し、下記式により算出することができる。
The shape of the particulate metal oxide of the present invention is not limited, but for example, spherical (true spherical), elliptical spherical, cubic, rectangular parallelepiped, pyramidal, needle-like, columnar, rod-like, cylindrical, flake-like And flakes such as (hexagonal) plate.
The particulate metal oxide of the present invention is a fine particle, that is, a particle having a primary particle diameter of 0.1 μm or less. In other words, the primary particle diameter of the particle made of the specific metal oxide is 0.1 μm or less. is there. The primary particle diameter of the particles made of the specific metal oxide is preferably 3 to 50 nm. More preferably, it is 3-30 nm, More preferably, it is 5-20 nm. If the average particle diameter of the primary particles is less than 3 nm, the ultraviolet absorption end tends to shift to the short wavelength side due to the quantum effect, which is not preferable as an ultraviolet absorbing material. On the other hand, if it exceeds 50 nm, the transparency may decrease. There is. Here, the average particle diameter of the primary particles means the crystallite diameter (Dw) or the specific surface area diameter (Ds). Specifically, when the particles are crystalline, the crystallites The diameter (Dw) means the specific surface area diameter (Ds) when the particles are amorphous. Accordingly, it is preferable that either the crystallite diameter (Dw) or the specific surface area diameter (Ds) falls within the above range. More specifically, the crystallite diameter (Dw) is applied in the case of crystal in X-ray diffraction, and is the size of the crystallite obtained by the Scherrer method. The crystallite diameter (Dw) is usually determined by measuring a powder X-ray diffraction pattern of metal oxide particles. Three strong lines (diffractive line having the largest peak (1), second largest diffraction line (2), 3 For the second largest diffraction line (3)), the crystallite diameters D1, D2, and D3 in the direction perpendicular to the diffraction planes assigned to the diffraction lines (1) to (3) from the Scherrer formula from the respective half widths or integral widths. The average value ((D1 + D2 + D3) / 3) can be calculated as the crystallite diameter (Dw). On the other hand, the specific surface area diameter (Ds) can be calculated by the following formula by measuring the true specific gravity and the specific surface area of the powder of the particulate metal oxide.
Ｄｓ（ｎｍ）＝６０００／（ρ×Ｓ）
但し、ρ：粒子の真比重（無次元）
Ｓ：Ｂ．Ｅ．Ｔ．法で測定される粒子の比表面積（ｍ2／ｇ）
前記特定金属酸化物が酸化亜鉛結晶である場合、Ｘ線回折測定による結晶子径のうち、格子面（００２）に垂直方向の結晶子径は３０ｎｍ以下、格子面（１１０）に垂直方向の結晶子径が１０ｎｍ以上であることが、透明性と紫外線吸収性能のいずれもが優れる点で、好ましい。より好ましくは、格子面（００２）に垂直方向の結晶子径は２０ｎｍ以下である。なお、各格子面に垂直方向の結晶子径は、前述したように、粉末Ｘ線回折測定を行い、シェラー解析を行うことにより求めることができる。
Ds (nm) = 6000 / (ρ × S)
Where ρ is the true specific gravity of the particle (dimensionless)
S: B. E. T. T. et al. Specific surface area of particles measured by the method (m 2 / g)
When the specific metal oxide is a zinc oxide crystal, out of the crystallite diameters measured by X-ray diffraction, the crystallite diameter perpendicular to the lattice plane (002) is 30 nm or less, and the crystal perpendicular to the lattice plane (110) A child diameter of 10 nm or more is preferable in that both transparency and ultraviolet absorption performance are excellent. More preferably, the crystallite diameter in the direction perpendicular to the lattice plane (002) is 20 nm or less. The crystallite diameter perpendicular to each lattice plane can be determined by performing powder X-ray diffraction measurement and Scherrer analysis as described above.
本発明の微粒子状金属酸化物は、任意の溶媒や樹脂などに分散された状態での分散粒子径が、５００ｎｍ以下となるものであることが、得られる塗膜や樹脂コンポジットの透明性を高めるうえで好ましい。より好ましくは２００ｎｍ以下、さらに好ましくは１００ｎｍ以下であり、特に、１次粒子が単分散もしくはそれに近い状態で分散されうることが望ましく、５０ｎｍ以下が最も好ましい。なお、分散粒子径は、例えば、動的光散乱式粒径分布測定装置（例えば、堀場製作所製「ＬＢ−５００」など）により測定することができる。
前記特定金属酸化物に含有させる銅（Ｃｕ）としては、Ｃｕ（０）、Ｃｕ(Ｉ)およびＣｕ(ＩＩ)が挙げられ、なかでも、固溶の場合にはＣｕ(Ｉ)およびＣｕ(ＩＩ)が好ましく、特にＣｕ(ＩＩ)が紫外線吸収性に優れる点で好ましい。
The fine particle metal oxide of the present invention has a dispersed particle diameter of 500 nm or less when dispersed in an arbitrary solvent or resin, thereby improving the transparency of the resulting coating film or resin composite. In addition, it is preferable. More preferably, it is 200 nm or less, and further preferably 100 nm or less. In particular, it is desirable that the primary particles can be dispersed in a monodispersed state or a state close thereto, and 50 nm or less is most preferable. The dispersed particle size can be measured by, for example, a dynamic light scattering type particle size distribution measuring device (for example, “LB-500” manufactured by Horiba, Ltd.).
Examples of copper (Cu) contained in the specific metal oxide include Cu (0), Cu (I), and Cu (II). In particular, in the case of solid solution, Cu (I) and Cu (II) ) Is preferable, and Cu (II) is particularly preferable in terms of excellent ultraviolet absorption.
前記特定金属酸化物に含有させる銀（Ａｇ）としてはＡｇ（０）、Ａｇ（Ｉ）が挙げられ、なかでも、固溶の場合にはＡｇ（Ｉ）が紫外線吸収性に優れる点で好ましい。
前記特定金属酸化物に含有させるマンガン（Ｍｎ）としては、１〜７価のものが挙げられ、なかでも、２価または３価のものが好ましい。
なお、これら銅（Ｃｕ）、銀（Ａｇ）およびマンガン（Ｍｎ）が固溶している場合における、それぞれの固溶形態としては、侵入型固溶体であってもよいし、置換型固溶体であってもよく、限定はされない。
本発明の微粒子状金属酸化物においては、前記特定金属酸化物に含有させる異種金属元素（Ｃｕ、Ａｇ）の含有率が、該特定金属酸化物中のＺｎ、Ｔｉ、Ｃｅの総原子数に対して、０．０１〜１０原子％であることが好ましく、より好ましくは０．１〜１０原子％、さらに好ましくは０．２〜１０原子％、さらに好ましくは０．７〜１０原子％である。これに対し、異種金属元素がＭｎの場合は０．０１〜３０原子％であることが好ましく、３〜１０原子％が特に好ましい。異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の含有率が０．０１原子％未満であると、本発明の効果が充分に発現されにくくなり、他方、それぞれの上限値を超えると、可視光透過率が低下する傾向がある。
Examples of silver (Ag) to be contained in the specific metal oxide include Ag (0) and Ag (I). In particular, Ag (I) is preferable in the case of solid solution because it has excellent ultraviolet absorptivity.
Examples of manganese (Mn) contained in the specific metal oxide include 1 to 7 valent ones, and among them, divalent or trivalent ones are preferable.
In addition, when these copper (Cu), silver (Ag), and manganese (Mn) are in solid solution, each solid solution form may be an interstitial solid solution or a substitutional solid solution. Well, it is not limited.
In the particulate metal oxide of the present invention, the content of the different metal element (Cu, Ag) contained in the specific metal oxide is based on the total number of atoms of Zn, Ti, Ce in the specific metal oxide. It is preferable that it is 0.01-10 atomic%, More preferably, it is 0.1-10 atomic%, More preferably, it is 0.2-10 atomic%, More preferably, it is 0.7-10 atomic%. On the other hand, when the dissimilar metal element is Mn, it is preferably 0.01 to 30 atomic%, particularly preferably 3 to 10 atomic%. When the content of the different metal elements (Cu, Ag, Mn) is less than 0.01 atomic%, the effect of the present invention is not sufficiently exhibited. On the other hand, when the upper limit is exceeded, the visible light transmittance is reduced. Tends to decrease.
前記特定金属酸化物に含有させる異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の存在は、本発明の微粒子状金属酸化物の１次粒子およびその集合体について、ＦＥ−ＴＥＭ（透過型電子顕微鏡）によりそれらの透過像を観察しながら、粒子のほかに金属の偏析物が認められないところを探し、高分解能ＸＭＡにより元素分析を行い、各金属元素のうち異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）に帰属するピークを検出することで確認できる。偏析物の確認は、ＦＥ−ＴＥＭで観察される透過像において、通常、ＴＥＭで確認できないレベルであれば偏析物は無いものとする。
前記特定金属酸化物に含有させる異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の含有率の測定は、蛍光Ｘ線分析、原子吸光分析およびＩＰＣ等の微量成分分析手法で行うこともできるが、前記高分解能ＸＭＡによる元素分析を所望の空間分解能（スポット径）で行い、各金属元素のうち異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）に帰属するピーク強度を測定し、その結果から算出するようにする手法で行うことが好ましい。前記スポット径は、プローブを絞ることにより下限を１ｎｍφにまでできるとともに、任意に連続的に拡大することもできる。具体的には、ＦＥ−ＴＥＭによる透過像において、偏析物の認められない約１０個の金属酸化物の粒子の集合体を選択し、これら約１０個の粒子をすべて含むような空間分解能（スポット径）で元素分析を行うこととする。
The presence of different metal elements (Cu, Ag, Mn) contained in the specific metal oxide is determined by FE-TEM (transmission electron microscope) for the primary particles of the fine metal oxide of the present invention and the aggregates thereof. While observing these transmission images, look for a place where no segregated metal other than particles is observed, conduct elemental analysis with high resolution XMA, and dissimilar metal elements (Cu, Ag, Mn) among each metal element This can be confirmed by detecting the attributed peak. The confirmation of the segregated material is that there is no segregated material in the transmission image observed with the FE-TEM if it is normally a level that cannot be confirmed with the TEM.
The content of different metal elements (Cu, Ag, Mn) contained in the specific metal oxide can be measured by a trace component analysis technique such as X-ray fluorescence analysis, atomic absorption analysis, and IPC. Method of performing elemental analysis with resolution XMA with desired spatial resolution (spot diameter), measuring peak intensity attributed to different metal elements (Cu, Ag, Mn) among each metal element, and calculating from the result It is preferable to carry out with. The lower limit of the spot diameter can be reduced to 1 nmφ by narrowing the probe, and the spot diameter can be arbitrarily increased. Specifically, in a transmission image by FE-TEM, an aggregate of about 10 metal oxide particles in which segregation is not observed is selected, and the spatial resolution (spots) including all these about 10 particles is selected. Elemental analysis is performed on the diameter).
なお、各粒子が異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）を含有しているか、あるいは、個々の粒子において粒子中にＣｕが均一に分散しているかについては、ビーム径を絞って（例えば１ｎｍφ）の局所元素分析を行うことにより確認することができる。
前記ＦＥ−ＴＥＭとしては、例えば、日立製作所製の電界放射型透過型電子顕微鏡（ＨＦ−２０００型、加速電圧２００ｋＶ）等を用いることができる。前記高分解能ＸＭＡとしては、例えば、ケヴェックス（Ｋｅｖｅｘ）社製のＸ線マイクロアナライザー（Ｓｉｇｍａ型、エネルギー分散型、ビーム径：空間分解能１０Åφ）等を用いることができる。
本発明の微粒子状金属酸化物においては、本発明の効果を損なわない範囲で、前記特定金属酸化物に異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）以外の金属元素を含有させることもできる。異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）以外の金属元素としては、特に限定されないが、例えば、Ａｌ、Ｉｎ、Ｓｎ、Ｆｅ、Ｃｏ、Ｂｉ、Ｃｅ等が好ましく挙げられる。
Whether each particle contains a different metal element (Cu, Ag, Mn) or whether Cu is uniformly dispersed in each particle is determined by narrowing the beam diameter (for example, 1 nmφ). This can be confirmed by performing local elemental analysis.
As the FE-TEM, for example, a field emission transmission electron microscope (HF-2000 type, acceleration voltage 200 kV) manufactured by Hitachi, Ltd. can be used. As the high-resolution XMA, for example, an X-ray microanalyzer (Sigma type, energy dispersion type, beam diameter: spatial resolution of 10 mmφ) manufactured by Kevex can be used.
In the particulate metal oxide of the present invention, a metal element other than the different metal element (Cu, Ag, Mn) can be contained in the specific metal oxide within a range not impairing the effects of the present invention. Although it does not specifically limit as metal elements other than a dissimilar metal element (Cu, Ag, Mn), For example, Al, In, Sn, Fe, Co, Bi, Ce etc. are mentioned preferably.
本発明の微粒子状金属酸化物においては、前記特定金属酸化物からなる粒子内に、該特定金属酸化物中のＺｎ、Ｔｉ、Ｃｅの総原子数に対するモル比で０．１〜１４モル％のアシル基が含有されていることが、分散性に優れ、透明性に優れる膜形成用組成物や膜が得られる点で、好ましい。Ｚｎ、Ｔｉ、Ｃｅのうちの１種を金属元素とする前記特定金属酸化物においては、結晶の屈折率が高くなるため可視光の散乱が起こりやすく、樹脂等のバインダーに分散させたときにヘイズの高い膜となりやすいが、前述のようなアシル基を含有する粒子であると、ヘイズの低い透明性に優れる膜となるのである。前記アシル基としては、特に炭素数１〜３であることが好ましい。 In the particulate metal oxide of the present invention, the specific metal oxide has a particle ratio of 0.1 to 14 mol% with respect to the total number of atoms of Zn, Ti, and Ce in the specific metal oxide. It is preferable that an acyl group is contained from the viewpoint of obtaining a film-forming composition or film having excellent dispersibility and transparency. In the specific metal oxide having one of Zn, Ti, and Ce as a metal element, since the refractive index of the crystal is increased, visible light is likely to be scattered, and haze when dispersed in a binder such as a resin. However, if the particles contain an acyl group as described above, the film has excellent transparency with low haze. The acyl group preferably has 1 to 3 carbon atoms.
本発明の微粒子状金属酸化物は、前述したように、アシル基が含有されている粒子であることが好ましいのと同様の理由で、以下の金属化合物（１）〜（３）の少なくとも１種で表面処理されてなる粒子であることが好ましい。
金属化合物（１）：テトラメトキシシラン、テトラブトキシシラン等の、異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）以外の金属元素からなる金属アルコキシド類。
金属化合物（２）：下記一般式（ａ）で表される有機基含有金属化合物。なお、該金属化合物中の金属元素の種類は、限定はされない。
Ｙ1 ｉＭ1Ｘ1 ｊ （ａ）
（ただし、Ｙ1は有機官能基、Ｍ1は金属原子、Ｘ1は加水分解性基である。ｉおよびｊは１〜（ｓ−１）の整数であってｉ＋ｊ＝ｓ（ｓはＭ1の原子価）を満足する。）
一般式（ａ）で表される有機基含有金属化合物としては、例えば、以下のものが挙げられる。
As described above, the particulate metal oxide of the present invention is preferably at least one of the following metal compounds (1) to (3) for the same reason that the particles preferably contain an acyl group. It is preferable that the particles are surface-treated.
Metal compound (1): Metal alkoxides composed of metal elements other than different metal elements (Cu, Ag, Mn) such as tetramethoxysilane and tetrabutoxysilane.
Metal compound (2): An organic group-containing metal compound represented by the following general formula (a). In addition, the kind of metal element in this metal compound is not limited.
Y 1 i M 1 X 1 j (a)
(Wherein, Y 1 is an organic functional group, M 1 is a metal atom, X 1 is a hydrolyzable group .i and j. 1 to (s-1) is an integer of i + j = s (s is M 1 Valence).)
As an organic group containing metal compound represented by general formula (a), the following are mentioned, for example.
Ｍ1がアルミニウムである有機基含有化合物としては、例えば、ジイソプロポキシアルミニウムエチルアセトアセテート、ジイソプロポキシアルミニウムアルキルアセトアセテート、ジイソプロポキシアルミニウムモノメタクリレート、アルミニウムステアレートオキサイドトリマー、イソプロポキシアルミニウムアルキルアセトアセテートモノ（ジオクチルホスフェート）等の各種アルミニウム系カップリング剤等が挙げられる。
Ｍ1がケイ素である有機基含有化合物としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリアセトキシシラン等のビニル系シランカップリング剤；Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、３−Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、Ｎ，Ｎ’−ビス〔３−（トリメトキシシリル）プロピル〕エチレンジアミン等のアミノ系シランカップリング剤；γ−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ系シランカップリング剤；３−クロロプロピルトリメトキシシラン等のクロル系シランカップリング剤；アクリロキシプロピルトリメトキシシラン、アクリロキシプロピルトリエトキシシラン等のアクリロキシ系シランカップリング剤；３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン等のメタクリロキシ系シランカップリング剤；３−メルカプトプロピルトリメトキシシラン等のメルカプト系シランカップリング剤；Ｎ−（１，３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン等のケチミン系シランカップリング剤；Ｎ−〔２−（ビニルベンジルアミノ）エチル〕−３−アミノプロピルトリメトキシシラン・塩酸塩等のカチオン系シランカップリング剤；メチルトリメトキシシラン、トリメチルメトキシシラン、デシルトリエトキシシラン、ヒドロキシエチルトリメトキシシラン等のアルキル系シランカップリング剤；（トリデカフルオロ−１，１，２，２−テトラヒドロオクチル）トリエトキシシラン等のフッ素含有有機基を有するシリコン化合物；イソシアン酸プロピルトリメトキシシラン等のイソシアナト基含有有機基を有するシランカップリング剤；下記一般式（ｂ）：
Ｒ’Ｏ（Ｃ2Ｈ4Ｏ）ｎＣ3Ｈ6Ｓｉ（ＯＲ’ ’）３ （ｂ）
（だだし、Ｒ’は、水素、または、メチル基等のアルキル基、シクロアルキル基、アリール基、アシル基およびアラルキル基から選ばれる少なくとも１種が置換されていてもよい基である。Ｒ’ ’は、メチル基等のアルキル基、シクロアルキル基、アリール基、アシル基およびアラルキル基から選ばれる少なくとも１種が置換されていてもよい基である。）
で表されるシランカップリング剤；γ−ウレイドプロピルトリエトキシシランやヘキサメチルジシラザン等の各種シランカップリング剤などが挙げられる。
Examples of the organic group-containing compound in which M 1 is aluminum include diisopropoxy aluminum ethyl acetoacetate, diisopropoxy aluminum alkyl acetoacetate, diisopropoxy aluminum monomethacrylate, aluminum stearate oxide trimer, and isopropoxy aluminum alkyl acetoacetate. Various aluminum-based coupling agents such as mono (dioctyl phosphate) can be used.
Examples of the organic group-containing compound in which M 1 is silicon include vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and vinyltriacetoxysilane; N- ( Amino silanes such as 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-N-phenyl-γ-aminopropyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine Coupling agent; Epoxy silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Chlorine silane cup such as 3-chloropropyltrimethoxysilane Ring agent; acryloxypropyltri Acryloxy silane coupling agents such as toxisilane and acryloxypropyltriethoxysilane; methacryloxy silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-mercaptopropyltrimethoxysilane Mercapto silane coupling agents such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, etc .; N- [2- (vinylbenzyl Amino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride cationic silane coupling agent; methyltrimethoxysilane, trimethylmethoxysilane, decyltriethoxysilane, hydroxyethyltrimethoxysilane, etc. Silane coupling agents; silicon compounds having fluorine-containing organic groups such as (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane; isocyanato group-containing organic groups such as propyltrimethoxysilane isocyanate A silane coupling agent having the following general formula (b):
R′O (C 2 H 4 O) n C 3 H 6 Si (OR ′ ′) 3 (b)
(However, R ′ is a group in which at least one selected from hydrogen or an alkyl group such as a methyl group, a cycloalkyl group, an aryl group, an acyl group, and an aralkyl group may be substituted. 'Is a group in which at least one selected from an alkyl group such as a methyl group, a cycloalkyl group, an aryl group, an acyl group and an aralkyl group may be substituted.
And various silane coupling agents such as γ-ureidopropyltriethoxysilane and hexamethyldisilazane.
Ｍ1がジルコニウムである有機基含有化合物としては、例えば、ジルコニウムジｎ−ブトキシド（ビス−２，４−ペンタンジオネート）、ジルコニウムトリｎ−ブトキシドペンタンジオネート、ジルコニウムジメタクリレートジブトキシド等の各種ジルコニウム化合物等が挙げられる。
金属化合物（３）：金属アルコキシド（金属は任意）の（部分）加水分解物または縮合物や上記（２）の（部分）加水分解物または縮合物であり、例えば、下記一般式（ｃ）で表される。
Ｒ1−（Ｏ−Ｍ（−Ｒ2 ｍ1）（−Ｒ3 ｍ2））ｎ−Ｒ4 （ｃ）
（ただし、Ｒ1、Ｒ2は水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基およびアシル基からなる群より選ばれるいずれか１種もしくは該１種が置換されていてもよい基であり、Ｒ3は加水分解性基（上記一般式（ａ）中のＸ1と同じ）または水酸基であり、Ｒ4はＲ2またはＲ3であり、Ｍは金属原子である。ｍ１、ｍ２は０または１〜（Ｍの原子価−２）までの整数であり、ｍ１＋ｍ２は（Ｍの原子価−２）であり、ｎは２から１００００までの整数である。なお、金属原子Ｍに結合するＲ2またはＲ3の種類やその数（ｍ１およびｍ２）は、金属原子Ｍの相互間ですべて同じであってもよいし少なくとも一部が異なっていてもよい。）
例えば、上記金属化合物（２）の加水分解縮合物であれば、上記一般式（ａ）中の金属原子Ｍ1に結合している加水分解性基Ｘ1の一部あるいは全部が加水分解されて該Ｘ1がＯＨ基となった化合物や、さらにＭ1−ＯＨ間での脱水縮合等の縮合反応によりＭ1−Ｏ−Ｍ1結合を形成してなる化合物等が挙げられ、具体的には、金属化合物（２）として列挙した有機基含有化合物を、加水分解縮合および／または部分加水分解縮合してなる、線状や環状の３量体をはじめとする、線状（分岐鎖を含むものを含む）や環状の加水分解縮合物が挙げられる。
Examples of the organic group-containing compound in which M 1 is zirconium include various kinds of zirconium such as zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium tri-n-butoxide pentanedionate, and zirconium dimethacrylate dibutoxide. Compounds and the like.
Metal compound (3): (partial) hydrolyzate or condensate of metal alkoxide (metal is optional) or (partial) hydrolyzate or condensate of (2) above, for example, in the following general formula (c) expressed.
R 1 - (O-M ( -
(However, R 1 and R 2 are any one selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an acyl group, or a group in which the one type may be substituted. R 3 is a hydrolyzable group (same as X 1 in the general formula (a)) or a hydroxyl group, R 4 is R 2 or R 3 , M is a metal atom, and m1 and m2 are 0 or an integer from 1 to (M valence −2), m1 + m2 is (M valence −2), and n is an integer from 2 to 10000. It is bonded to the metal atom M. The type of R 2 or R 3 and the number thereof (m1 and m2) may all be the same or at least partially different among the metal atoms M.)
For example, in the case of the hydrolysis condensate of the metal compound (2), a part or all of the hydrolyzable group X 1 bonded to the metal atom M 1 in the general formula (a) is hydrolyzed. Examples of the compound in which X 1 is an OH group, and a compound in which an M 1 -O-M 1 bond is formed by a condensation reaction such as dehydration condensation between M 1 -OH, and the like are specifically mentioned. , Linear (including branched chains), including linear and cyclic trimers, obtained by hydrolytic condensation and / or partial hydrolytic condensation of organic group-containing compounds listed as metal compounds (2) And cyclic hydrolysis condensates.
金属化合物（３）としては、例えば、チタン(ＩＶ)テトラ−ｎ−ブトキシドテトラマー（Ｃ4Ｈ9−〔Ｔｉ（ＯＣ4Ｈ9）2Ｏ〕4−Ｃ4Ｈ9）、和光純薬社製）や、シリコン(ＩＶ)テトラメトキシドテトラマー、メチルトリメトキシシランテトラマー、テトラメトキシシラン−メチルトリメトキシシラン共加水分解縮合物、アルミニウム(ＩＩＩ)トリブトキシドトリマー等が挙げられる。
本発明の微粒子状金属酸化物の製造方法については、限定はされず、公知の、金属酸化物に所望の異種金属元素を含有させた（ドープした）粒子を得ることのできる方法であれば、何れの方法も採用できる。例えば、Ｚｎ、ＴｉおよびＣｅからなる群より選ばれる少なくとも１種の化合物（以下「特定金属化合物」と称する。）および／またはその加水分解縮合物と、異種金属（Ｃｕ、Ａｇ、Ｍｎ）の化合物（以下「異種金属元素化合物」と称することもある）と、アルコールとを出発原料とし、これらの混合系を高温状態にして、金属酸化物粒子を生成させる（析出させる）工程を備える製造方法（以下、製造方法（Ａ）と称する。）が好ましい。詳しくは、製造方法（Ａ）は、出発原料としての、前記特定金属化合物および／またはその加水分解縮合物と、異種金属元素化合物とアルコールとを、混合すると同時かまたはその後に、該混合系を高温状態にする工程を備える方法である。このように高温状態にすることにより、反応系中に金属酸化物粒子を生成させることができる。
Metal compound (3) is, for example, titanium (IV) tetra -n- butoxide tetramer (C 4 H 9 - [Ti (OC 4 H 9) 2 O ] 4 -C 4 H 9), produced by Wako Pure Chemical Industries, Ltd. ), Silicon (IV) tetramethoxide tetramer, methyltrimethoxysilane tetramer, tetramethoxysilane-methyltrimethoxysilane co-hydrolysis condensate, aluminum (III) tributoxide trimer, and the like.
About the manufacturing method of the particulate metal oxide of the present invention, there is no limitation, as long as it is a known method that can obtain (doped) particles containing a desired different metal element in a metal oxide. Either method can be adopted. For example, at least one compound selected from the group consisting of Zn, Ti and Ce (hereinafter referred to as “specific metal compound”) and / or a hydrolysis condensate thereof, and a compound of a different metal (Cu, Ag, Mn) (Hereinafter also referred to as “heterogeneous metal element compound”) and alcohol as a starting material, and a mixed system thereof is brought to a high temperature state to produce (precipitate) metal oxide particles (a manufacturing method) Hereinafter, the production method (A) is preferred.) Specifically, in the production method (A), the specific metal compound and / or its hydrolysis condensate, the dissimilar metal element compound and the alcohol as a starting material are mixed with or after the mixing. It is a method provided with the process of making it into a high temperature state. Thus, by making it a high temperature state, a metal oxide particle can be produced | generated in a reaction system.
製造方法（Ａ）において用い得る前記特定金属化合物としては、限定はされないが、特定金属元素（Ｚｎ、Ｔｉ、Ｃｅ）のカルボン酸塩（カルボン酸亜鉛、カルボン酸チタン、カルボン酸セリウム）が好ましい。なお、前記特定金属化合物の加水分解縮合物とは、該化合物を加水分解および／または縮合して得られる加水分解物および／または縮合物であり、モノマー化合物から高分子化合物までを含む（以下、「特定金属化合物」は、「特定金属化合物および／またはその加水分解縮合物」を意味することがある。）。
前記特定金属元素のカルボン酸塩としては、カルボキシル基の水素原子が亜鉛原子、チタン原子、セリウム原子のうちの少なくとも１種で置換された置換基を分子内に少なくとも１つ有する化合物が好ましい。具体的には、飽和モノカルボン酸、不飽和モノカルボン酸、飽和多価カルボン酸および不飽和多価カルボン酸などの鎖式カルボン酸；環式飽和カルボン酸；芳香族モノカルボン酸および芳香族不飽和多価カルボン酸などの芳香族カルボン酸；これらカルボン酸において、さらに分子内にヒドロキシル基、アミノ基、ニトロ基、アルコキシ基、スルホン基、シアノ基およびハロゲン原子等の官能基または原子団を有する化合物；等のカルボン酸化合物中のカルボキシル基が、前記置換基となっている化合物が好ましく例示できる。
The specific metal compound that can be used in the production method (A) is not limited, but carboxylates (zinc carboxylate, titanium carboxylate, cerium carboxylate) of specific metal elements (Zn, Ti, Ce) are preferable. The hydrolyzed condensate of the specific metal compound is a hydrolyzate and / or condensate obtained by hydrolyzing and / or condensing the compound, and includes a monomer compound to a polymer compound (hereinafter, referred to as “the hydrolyzed condensate”). “Specific metal compound” may mean “specific metal compound and / or hydrolysis condensate thereof”).
As the carboxylate of the specific metal element, a compound having at least one substituent in the molecule in which a hydrogen atom of the carboxyl group is substituted with at least one of a zinc atom, a titanium atom, and a cerium atom is preferable. Specifically, a chain carboxylic acid such as a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a saturated polycarboxylic acid, and an unsaturated polycarboxylic acid; a cyclic saturated carboxylic acid; an aromatic monocarboxylic acid and an aromatic noncarboxylic acid Aromatic carboxylic acids such as saturated polyvalent carboxylic acids; these carboxylic acids further have functional groups or atomic groups such as hydroxyl groups, amino groups, nitro groups, alkoxy groups, sulfone groups, cyano groups and halogen atoms in the molecule. Preferred examples include compounds in which a carboxyl group in a carboxylic acid compound such as a compound is the above substituent.
これら特定金属元素のカルボン酸塩のなかでも、下記一般式（１）：
Ｍ（Ｏ）（ｍ−ｘ−ｙ−ｚ）／２（ＯＣＯＲ1）ｘ（ＯＨ）ｙ（ＯＲ2）ｚ （１）
（但し、Ｍは亜鉛原子、チタン原子、セリウム原子から選ばれた少なくとも１種；ｍはＭの原子価；Ｒ1は、水素原子、置換基があってもよいアルキル基、シクロアルキル基、アリール基およびアラルキル基から選ばれた少なくとも１種；Ｒ2は、置換基があってもよいアルキル基、シクロアルキル基、アリール基およびアラルキル基から選ばれた少なくとも１種；ｍ、ｘ、ｙおよびｚは、ｘ＋ｙ＋ｚ≦ｍ、０＜ｘ≦ｍ、０≦ｙ＜ｍ、０≦ｚ＜ｍを満たす。）
で表される化合物（例えば、前記例示した特定金属元素のカルボン酸塩の一部が水酸基やアルコキシ基等で置換された化合物等）、特定金属元素の飽和カルボン酸塩、不飽和カルボン酸塩および塩基性酢酸塩がより好ましく、さらに好ましくは特定金属元素のギ酸塩、酢酸塩およびプロピオン酸塩ならびにこれらの塩基性塩である。なお、特定金属元素のカルボン酸塩は、結晶水を含むカルボン酸塩の水和物であってもよいが、無水物であることが好ましい。
Among these carboxylates of specific metal elements, the following general formula (1):
M (O) (m-x -y-z) / 2 (OCOR 1) x (OH) y (OR 2) z (1)
(Wherein, M is at least one selected from a zinc atom, a titanium atom, and a cerium atom; m is a valence of M; R 1 is a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group, an aryl; At least one selected from a group and an aralkyl group; R 2 is at least one selected from an optionally substituted alkyl group, cycloalkyl group, aryl group and aralkyl group; m, x, y and z Satisfies x + y + z ≦ m, 0 <x ≦ m, 0 ≦ y <m, and 0 ≦ z <m.)
(For example, a compound in which a part of the carboxylate of the specific metal element exemplified above is substituted with a hydroxyl group, an alkoxy group or the like), a saturated carboxylate, an unsaturated carboxylate of the specific metal element, and the like Basic acetates are more preferable, and formate salts, acetate salts and propionate salts of specific metal elements and basic salts thereof are more preferable. The carboxylate of the specific metal element may be a hydrate of carboxylate containing crystal water, but is preferably an anhydride.
製造方法（Ａ）において用い得る異種金属元素化合物としては、限定はされず、例えば、Ｃｕの場合、銅の塩化物や硝酸塩などの無機塩等のほか、例えば、銅カルボン酸塩類や銅アルコキシド類等が好ましく挙げられる。
製造方法（Ａ）において用い得るアルコールとしては、限定はされないが、例えば、例えば、脂肪族１価アルコール（メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノール、ｔ−ブチルアルコール、ステアリルアルコール等）、脂肪族不飽和１価アルコール（アリルアルコール、クロチルアルコール、プロパギルアルコール等）、脂環式１価アルコール（シクロペンタノール、シクロヘキサノール等）、芳香族１価アルコール（ベンジルアルコール、シンナミルアルコール、メチルフェニルカルビノール等）、フェノール類（エチルフェノール、オクチルフェノール、カテコール、キシレノール、グアヤコール、ｐ−クミルフェノール、クレゾール、ｍ−クレゾール、ｏ−クレゾール、ｐ−クレゾール、ドデシルフェノール、ナフトール、ノニルフェノール、フェノール、ベンジルフェノール、ｐ−メトキシエチルフェノール等）、複素環式１価アルコール（フルフリルアルコール等）等の１価アルコール類；アルキレングリコール（エチレングリコール、プロピレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，１０−デカンジオール、ピナコール、ジエチレングリコール、トリエチレングリコール等）、脂環式グリコール（シクロペンタン−１，２−ジオール、シクロヘキサン−１，２−ジオール、シクロヘキサン−１，４−ジオール等）、および、ポリオキシアルキレングリコール（ポリエチレングリコール、ポリプロピレングリコール等）等のグリコール類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、３−メチル−３−メトキシブタノール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、エチレングリコールモノアセテート等の上記グリコール類のモノエーテルまたはモノエステル等の誘導体；グリセリンやトリメチロールエタン等の３価アルコール、エリスリトールやペンタエリスリトール等の４価アルコール、リピトールやキシリトール等の５価アルコール、ソルビトール等の６価アルコール等の３価以上の多価アルコール、ヒドロベンゾイン、ベンズピナコール、フタリルアルコール等の多価芳香族アルコール、カテコール、レゾルシン、ヒドロキノン等の２価フェノールや、ピロガロール、フロログルシン等の３価フェノール等の多価フェノール、および、これら多価アルコール類におけるＯＨ基の一部（１〜（ｎ−１）個（ただし、ｎは１分子当たりのＯＨ基の数））がエステル結合またはエーテル結合となった誘導体；等を挙げることができる。前記アルコールとしては、水溶性の高いアルコールが好ましく、具体的には、水に対する溶解度１重量％以上のアルコールが好ましく、水に対する溶解度１０重量％以上のアルコールがより好ましい。
The foreign metal element compound that can be used in the production method (A) is not limited. For example, in the case of Cu, in addition to inorganic salts such as copper chloride and nitrate, for example, copper carboxylates and copper alkoxides. Etc. are preferable.
The alcohol that can be used in the production method (A) is not limited. For example, aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.), aliphatic Unsaturated monohydric alcohols (allyl alcohol, crotyl alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohols (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohols (benzyl alcohol, cinnamyl alcohol, methylphenyl) Carbinol, etc.), phenols (ethylphenol, octylphenol, catechol, xylenol, guaiacol, p-cumylphenol, cresol, m-cresol, o-cresol, p-cresol, dodecylphenol, Monohydric alcohols such as phthalol, nonylphenol, phenol, benzylphenol, p-methoxyethylphenol), heterocyclic monohydric alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc.), alicyclic glycol (cyclo Pentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, etc.) and polyoxyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.) Cole: propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl Derivatives such as ethers and monoethers or monoesters of the above glycols such as ethylene glycol monoacetate; trihydric alcohols such as glycerin and trimethylolethane; tetrahydric alcohols such as erythritol and pentaerythritol; pentavalent alcohols such as lipitol and xylitol , Trihydric or higher polyhydric alcohols such as hexahydric alcohols such as sorbitol, hydrobenzoin, benzpina Polyhydric aromatic alcohols such as chol and phthalyl alcohol, dihydric phenols such as catechol, resorcin and hydroquinone, polyhydric phenols such as trihydric phenol such as pyrogallol and phloroglucin, and OH groups in these polyhydric alcohols. And a derivative in which a part (1 to (n-1) (where n is the number of OH groups per molecule)) is an ester bond or an ether bond; The alcohol is preferably a highly water-soluble alcohol, specifically an alcohol having a solubility in water of 1% by weight or more, more preferably an alcohol having a solubility in water of 10% by weight or more.
製造方法（Ａ）において、特定金属化合物、異種金属元素化合物およびアルコールの相互の使用割合（配合割合）については、限定はされないが、特定金属化合物の金属換算原子数と異種金属元素化合物の金属換算原子数との総数に対する、アルコール中の（アルコール由来の）水酸基の数の比が、０．８〜１０００であることが好ましく、より好ましくは０．８〜１００、さらに好ましくは１〜５０、特に好ましくは１〜２０である。また、特定金属化合物と異種金属元素化合物との相互の使用割合（配合割合）については、限定はされないが、特定金属化合物の金属換算原子数と異種金属元素化合物の金属換算原子数との比が、前述した異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の含有率の範囲を満たすように、適宜調整すればよい。 In the production method (A), the mutual use ratio (mixing ratio) of the specific metal compound, the different metal element compound and the alcohol is not limited, but the metal conversion atom number of the specific metal compound and the metal conversion of the different metal element compound The ratio of the number of hydroxyl groups in the alcohol (derived from the alcohol) to the total number of atoms is preferably 0.8 to 1000, more preferably 0.8 to 100, still more preferably 1 to 50, particularly Preferably it is 1-20. In addition, the mutual use ratio (mixing ratio) of the specific metal compound and the different metal element compound is not limited, but the ratio of the metal conversion atom number of the specific metal compound and the metal conversion atom number of the different metal element compound is The content of the different metal elements (Cu, Ag, Mn) described above may be adjusted as appropriate.
製造方法（Ａ）において、前記出発原料の混合系は、ペースト状、乳濁液状、懸濁液状および溶液状などの流動性のある液状であることが好ましい。必要に応じて、反応溶媒をも混合することにより、上記液状となるようにしてもよい。通常、特定金属化合物および異種金属元素化合物は、該混合系においては、粒子状で分散した状態、溶解した状態、あるいは、一部が溶解した状態で残りが粒子状で分散している状態、などの状態で存在する。
製造方法（Ａ）の製造方法において、必要に応じて用い得る反応溶媒としては、水以外の溶媒、すなわち、非水溶媒が好ましい。非水溶媒としては、例えば、炭化水素、各種ハロゲン化炭化水素、アルコール（フェノール類や、多価アルコールおよびその誘導体で水酸基を有する化合物なども含む）、エーテルおよびアセタール、ケトンおよびアルデヒド、カルボン酸エステルおよびリン酸エステル類等のエステル、アミド類、多価アルコール類のすべての水酸基の水素がアルキル基やアシル基で置換された誘導体化合物、カルボン酸およびその無水物、シリコーン油ならびに鉱物油などを挙げることができ、なかでも、親水性溶媒が特に好ましい。具体的には、常温（２５℃）において、水を５重量％以上含み溶液状態になり得る溶媒が好ましく、任意の量の水を含み均一な溶液状態になり得る溶媒がより好ましい。反応溶媒としてのアルコールとしては、出発原料となるアルコールとして先に列挙したものと同様のものが好ましく挙げられる。反応溶媒の使用量については、限定はないが、前記出発原料と反応溶媒との合計使用量に対する、前記特定金属化合物および異種金属元素化合物の合計使用量の割合が、０．１〜５０重量％であることが好ましく、金属酸化物粒子を経済的に得ることができる。
In the production method (A), the starting material mixture system is preferably a fluid liquid such as a paste, emulsion, suspension, or solution. If necessary, a reaction solvent may also be mixed to form the liquid. Usually, in the mixed system, the specific metal compound and the different metal element compound are dispersed in the form of particles, dissolved, or partially dissolved and the rest are dispersed in the form of particles, etc. It exists in the state.
In the production method of production method (A), the reaction solvent that can be used as necessary is preferably a solvent other than water, that is, a non-aqueous solvent. Non-aqueous solvents include, for example, hydrocarbons, various halogenated hydrocarbons, alcohols (including phenols, polyhydric alcohols and derivatives thereof having a hydroxyl group), ethers and acetals, ketones and aldehydes, and carboxylic acid esters. And derivatives such as esters, amides, and polyhydric alcohols in which all hydroxyl groups are substituted with alkyl groups or acyl groups, carboxylic acids and their anhydrides, silicone oils and mineral oils. Among them, a hydrophilic solvent is particularly preferable. Specifically, a solvent that can be in a solution state containing 5 wt% or more of water at room temperature (25 ° C.) is preferable, and a solvent that can be in a uniform solution state containing an arbitrary amount of water is more preferable. Preferable examples of the alcohol as the reaction solvent are the same as those listed above as the starting alcohol. The amount of the reaction solvent used is not limited, but the ratio of the total amount of the specific metal compound and the different metal element compound to the total amount of the starting material and the reaction solvent is 0.1 to 50% by weight. It is preferable that the metal oxide particles can be obtained economically.
製造方法（Ａ）において、前記出発原料の混合系を高温状態にするとは、該混合系の温度を常温よりも高い温度であって金属酸化物粒子が生成し得る温度、またはそれ以上の温度に昇温させることである。前記混合系の高温状態は、前述したように、出発原料等を混合すると同時かまたは混合した後に得られていればよく、すなわち、上記混合系を得るための出発原料等の混合と、該混合系を高温状態にするための昇温とは、別々に行ってもよいし、同時（一部同時も含む）に行ってもよく、限定はされない。具体的には、得ようとする金属酸化物粒子の種類等によっても異なるが、一般には５０℃以上であり、特に、異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）含有率が高く、異種金属元素（Ｃｕ、Ａｇ、Ｍｎ）の偏析がなく、しかも結晶性の高い金属酸化物粒子を得るためには、８０℃以上が好ましく、１００〜３００℃がより好ましく、１００〜２００℃がさらに好ましく、１２０〜１７０℃が特に好ましい。また、前記混合系の高温状態は、金属酸化物粒子の結晶性を高め、紫外線吸収性等の物性に優れたものが得られる点で、所定温度を３０分以上保持することが好ましく、より好ましくは２時間以上である。なお、生成させた金属酸化物粒子について、残存有機基の除去や、より一層の結晶成長の促進等を目的とする場合、さらに必要に応じて、生成した金属酸化物粒子を３００〜８００℃で加熱してもよい。 In the production method (A), when the mixed system of the starting materials is brought into a high temperature state, the temperature of the mixed system is higher than room temperature and the metal oxide particles can be generated or higher. It is to raise the temperature. As described above, the high temperature state of the mixed system only needs to be obtained at the same time as or after mixing the starting materials, that is, mixing the starting materials to obtain the mixed system, and the mixing The temperature raising for bringing the system into a high temperature state may be performed separately or simultaneously (including partly simultaneously), and is not limited. Specifically, although it varies depending on the type of metal oxide particles to be obtained and the like, it is generally 50 ° C. or higher, and particularly has a high content of dissimilar metal elements (Cu, Ag, Mn), dissimilar metal elements ( In order to obtain metal oxide particles having no segregation of Cu, Ag, Mn) and high crystallinity, 80 ° C. or higher is preferable, 100 to 300 ° C. is more preferable, 100 to 200 ° C. is further preferable, and 120 to 170 ° C. is particularly preferred. In addition, the high temperature state of the mixed system is preferably maintained at a predetermined temperature for 30 minutes or more in that the crystallinity of the metal oxide particles is improved and a material having excellent physical properties such as ultraviolet absorption is obtained. Is 2 hours or more. In addition, about the produced | generated metal oxide particle, when aiming at the removal of a residual organic group, promotion of further crystal growth, etc., the produced | generated metal oxide particle is further 300-800 degreeC as needed. You may heat.
本発明の微粒子状金属酸化物は、例えば、化粧品、紫外線遮断を目的とする電子材料、包装材料用等の各種フィルムやビル、家等の建築物用窓、自動車窓、サンルーフ、鉄道や飛行機の窓等に用いられるガラスやポリカーボネート等の透明プラスチックシートに含有させる粒子としてあるいは成膜し得る紫外線吸収塗料用原料粒子として有用である。詳しくは、従来の酸化亜鉛、酸化チタンおよび酸化セリウムのような酸化物粒子もしくはこれらの酸化物にＣｕ、Ａｇ、Ｍｎ以外の単一の異種金属元素を含有させた粒子では得られなかった、優れた紫外線吸収性能や無色性や可視光透過性能を同時に満足させることができるため、例えば、ＬＣＤ（液晶ディスプレイ）、ＰＤＰ（プラズマディスプレイ）、白色ＬＥＤなどの表示デバイスにおいて励起源や光源に由来する紫外線を遮断する紫外線カット材料として、また、建築物や自動車などの窓材用の紫外線吸収材料として、有用である。 The particulate metal oxide of the present invention is, for example, various films for cosmetics, electronic materials for the purpose of blocking ultraviolet rays, packaging materials, etc., windows for buildings such as buildings and houses, automobile windows, sunroofs, railways and airplanes. It is useful as a raw material particle for an ultraviolet-absorbing paint that can be formed as a particle to be contained in a transparent plastic sheet such as glass or polycarbonate used for windows or the like. Specifically, it has not been obtained with conventional oxide particles such as zinc oxide, titanium oxide and cerium oxide or particles containing a single different metal element other than Cu, Ag and Mn in these oxides. Ultraviolet rays derived from excitation sources and light sources in display devices such as LCD (Liquid Crystal Display), PDP (Plasma Display), and white LEDs, for example, because UV absorption performance, colorlessness, and visible light transmission performance can be satisfied simultaneously. It is useful as a UV-cutting material that blocks light and as an UV-absorbing material for windows for buildings and automobiles.
また、前記特定金属酸化物が酸化亜鉛の場合には、従来から化粧品用紫外線吸収剤として主に汎用されていた酸化チタンに比べて屈折率が低くなるため、より優れた透明感を与えうる化粧品用紫外線吸収剤として、有用である。他方、前記特定金属酸化物が酸化亜鉛、酸化チタンもしくは酸化セリウムの場合には、高屈折率である粒子となるため、バインダー成分となる樹脂やシリケートなどとの配合比を制御することにより、任意の屈折率を有する膜を得ることが可能となるため、反射防止性を兼ね備えた紫外線吸収膜の原料として、有用である。
さらに、本発明の微粒子状金属酸化物は、紫外線遮断を目的とした用途以外にも適用可能であり、例えば、前記特定金属酸化物が酸化亜鉛、酸化チタンもしくは酸化セリウムの場合には、高屈折率である粒子となるため、樹脂、フィルム、膜などの屈折率を高めるための高屈折率フィラーとして好適に用いることができ、特に、本発明の微粒子状金属酸化物は超微粒子であるので、反射防止膜として好適な透明で高屈折率を有する膜やフィルムを得ることができる。他方、前記特定金属酸化物が酸化亜鉛の場合には、熱伝導性に優れる粒子となるため、熱伝導性フィラーとして有用であり、例えば、放熱性が求められる白色ＬＥＤ用途や電子回路基板用途などにおいて、熱伝導性の高いシート、フィルム、膜を得る際に好適に用いることができる。また、前記特定金属酸化物が酸化亜鉛や酸化チタンの場合には、電子伝導性に優れる粒子となるため、半導体もしくは導電体として有用であり、特に、本発明の微粒子状金属酸化物は超微粒子であるので、塗料化することにより、フィルム等の透明帯電防止膜や透明導電膜として好ましく用いることができる。
In addition, when the specific metal oxide is zinc oxide, the refractive index is lower than that of titanium oxide, which has been mainly used as a cosmetic UV absorber, so that it can give a better transparency. It is useful as a UV absorber. On the other hand, when the specific metal oxide is zinc oxide, titanium oxide, or cerium oxide, it becomes particles having a high refractive index. Therefore, by controlling the blending ratio with a resin or silicate as a binder component, it is optional. Therefore, it is useful as a raw material for an ultraviolet absorbing film having antireflection properties.
Further, the particulate metal oxide of the present invention can be applied for purposes other than the purpose of blocking ultraviolet rays. For example, when the specific metal oxide is zinc oxide, titanium oxide or cerium oxide, high refractive index Therefore, since the particulate metal oxide of the present invention is an ultrafine particle, it can be suitably used as a high refractive index filler for increasing the refractive index of a resin, film, film, etc. A transparent film and film having a high refractive index suitable as an antireflection film can be obtained. On the other hand, when the specific metal oxide is zinc oxide, the particles are excellent in thermal conductivity, and thus are useful as thermal conductive fillers, such as white LED applications and electronic circuit board applications that require heat dissipation. Can be suitably used for obtaining a sheet, film, or membrane having high thermal conductivity. In addition, when the specific metal oxide is zinc oxide or titanium oxide, it becomes a particle having excellent electron conductivity, so that it is useful as a semiconductor or a conductor. In particular, the particulate metal oxide of the present invention is an ultrafine particle. Therefore, by forming a paint, it can be preferably used as a transparent antistatic film such as a film or a transparent conductive film.
以下に、実施例および比較例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。以下では、特に断りのない限り、「重量部」を単に「部」と、「重量％」を単に「ｗｔ％」と記すものとする。
実施例および比較例における評価方法を以下に示す。
なお、以下で用いる粉末試料の調製は、次のようにして行った。すなわち、微粒子状金属酸化物の生成反応により得られた反応液を遠心分離した後、沈降物の反応溶媒による洗浄（沈降物を反応溶媒に再分散させ、遠心分離すること）を３回繰り返し、その後、得られた沈降物を真空乾燥機により６０℃で１２時間真空乾燥することにより、微粒子状金属酸化物の粉末試料を得た。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, “parts by weight” is simply referred to as “parts”, and “% by weight” is simply referred to as “wt%”.
Evaluation methods in Examples and Comparative Examples are shown below.
The powder sample used below was prepared as follows. That is, after centrifuging the reaction solution obtained by the formation reaction of the particulate metal oxide, washing the precipitate with a reaction solvent (redispersing the precipitate in the reaction solvent and centrifuging) is repeated three times. Thereafter, the resulting precipitate was vacuum-dried at 60 ° C. for 12 hours using a vacuum dryer, thereby obtaining a powder sample of a particulate metal oxide.
（１）微粒子状金属酸化物の結晶同定
上記粉末試料に関し、粉末Ｘ線回折装置（理学電気株式会社製、製品名：ＲＩＮＴ２４００）を用いた粉末Ｘ線回折により、微粒子状金属酸化物の結晶性を評価した。以下に測定条件を示す。
Ｘ線：ＣｕＫα１線（波長：１．５４０５６Å）／４０ｋＶ／２００ｍＡ
走査範囲：２θ＝２０〜８０°
スキャンスピード：５°／ｍｉｎ
なお、微粒子状金属酸化物がＺｎを主金属成分とする場合において、ＺｎＯ結晶性を有するか否かは、六方晶系ＺｎＯに特有の３強線のピークが認められるか否かで判定した。具体的には、以下の３つの回折角(a)〜(c)の位置のすべてに回折ピークが存在する場合、ＺｎＯ結晶性を有すると判定した。
(1) Crystal Identification of Fine Particle Metal Oxide With respect to the above powder sample, the crystallinity of the fine particle metal oxide by powder X-ray diffraction using a powder X-ray diffractometer (manufactured by Rigaku Corporation, product name: RINT2400). Evaluated. The measurement conditions are shown below.
X-ray: CuKα1 ray (wavelength: 1.54056Å) / 40 kV / 200 mA
Scanning range: 2θ = 20-80 °
Scan speed: 5 ° / min
In the case where the fine particle metal oxide has Zn as a main metal component, whether or not it has ZnO crystallinity was determined by whether or not a peak of three strong lines peculiar to hexagonal ZnO was observed. Specifically, when diffraction peaks exist at all of the following three diffraction angles (a) to (c), it was determined to have ZnO crystallinity.
(a) ２θ＝３１．６５〜３１．９５°
(b) ２θ＝３４．３０〜３４．６０°
(c) ２θ＝３６．１０〜３６．４０°
なお、(a)の位置に存在する回折ピークは、ＺｎＯ結晶の（１００）面に対する回折線に基づくものと判定し、(b)の位置に存在する回折ピークは、ＺｎＯ結晶の（００２）面に対する回折線に基づくものと判定し、(c)の位置に存在する回折ピークは、ＺｎＯ結晶の（１０１）面に対する回折線に基づくものと判定する。
Ｚｎ以外の金属元素を主金属成分とする場合においても同様に、その金属元素の酸化物結晶に特有の３強線のピークが認められるか否かで判定した。
(a) 2θ = 31.65 to 31.95 °
(b) 2θ = 34.30 to 34.60 °
(c) 2θ = 36.10 to 36.40 °
It is determined that the diffraction peak existing at the position (a) is based on the diffraction line with respect to the (100) plane of the ZnO crystal, and the diffraction peak existing at the position (b) is the (002) plane of the ZnO crystal. The diffraction peak existing at the position (c) is determined to be based on the diffraction line for the (101) plane of the ZnO crystal.
Similarly, when a metal element other than Zn was used as the main metal component, the determination was similarly made based on whether or not a peak of three strong lines peculiar to the oxide crystal of the metal element was observed.
（２）微粒子状金属酸化物の粒子径
（２−１）１次粒子径
微粒子状金属酸化物の結晶子径（Ｄｗ）を測定し、１次粒子径として評価した。
結晶子径（Ｄｗ）は、上記粉末試料に関し、粉末Ｘ線回折装置（理学電気株式会社製、製品名：ＲＩＮＴ２４００）を用いた粉末Ｘ線回折により、微粒子状金属酸化物の結晶子径（Ｄｗ）を評価した。具体的には、得られたＸ線回折パターンにおける各回折線の回折線幅より、シェラー法解析により結晶子径Ｄｈｋｌ（ここで、ｈｋｌはミラー指数を表す。Ｄｈｋｌはミラー指数（ｈｋｌ）の格子面に垂直な方向の結晶子の大きさである。）を求めた。
(2) Particle diameter of particulate metal oxide (2-1) Primary particle diameter The crystallite diameter (Dw) of the particulate metal oxide was measured and evaluated as the primary particle diameter.
The crystallite diameter (Dw) is related to the above powder sample by powder X-ray diffraction using a powder X-ray diffractometer (manufactured by Rigaku Corporation, product name: RINT2400). ) Was evaluated. Specifically, from the diffraction line width of each diffraction line in the obtained X-ray diffraction pattern, the crystallite diameter Dhkl (where hkl represents the Miller index. Dhkl represents the Miller index (hkl) lattice) by Scherrer method analysis. The crystallite size in the direction perpendicular to the plane.).
特に断らない限り、結晶子径（Ｄｗ）は、通常、金属酸化物粒子の粉末Ｘ線回折パターンを測定し、３強線（ピークが最も大きい回折線（１）、２番目に大きい回折線（２）、３番目に大きい回折線（３）について、それぞれの半値巾または積分巾より、シェラーの式に基づき、回折線（１）〜（３）に帰属される回折面に垂直方向の結晶子径Ｄ１、Ｄ２、Ｄ３を求め、これらの平均値（（Ｄ１＋Ｄ２＋Ｄ３）／３）を結晶子径（Ｄｗ）として算出する。
（２−２）分散粒子径
得られた反応液もしくは該反応液から溶媒変換して得られた溶媒分散体を試料とし、動的光散乱式粒径分布測定装置（堀場製作所製「ＬＢ−５００」）にて測定したメジアン径を分散粒子径とした。測定に際し、希釈する場合は、反応で用いた溶媒を希釈溶媒として用いた。評価基準は以下の通りである。
Unless otherwise specified, the crystallite diameter (Dw) is usually determined by measuring the powder X-ray diffraction pattern of the metal oxide particles, three strong lines (diffractive line (1) having the largest peak, and second largest diffraction line ( 2) For the third largest diffraction line (3), the crystallites in the direction perpendicular to the diffraction plane belonging to the diffraction lines (1) to (3) based on the Scherrer's formula from the respective half width or integral width The diameters D1, D2, and D3 are obtained, and the average value ((D1 + D2 + D3) / 3) is calculated as the crystallite diameter (Dw).
(2-2) Dispersed particle size Using the obtained reaction solution or a solvent dispersion obtained by solvent conversion from the reaction solution as a sample, a dynamic light scattering particle size distribution measuring device ("LB-500" manufactured by Horiba, Ltd.) was used. The median diameter measured in “)” was defined as the dispersed particle diameter. In the case of dilution, the solvent used in the reaction was used as a dilution solvent. The evaluation criteria are as follows.
●：分散粒径＜０．０５μｍ
◎：０．０５μｍ≦分散粒径＜０．１μｍ
◎：０．１μｍ≦分散粒径＜１μｍ
×：０．１μｍ≦分散粒径
なお、塗料における微粒子の分散粒径についても、上記と同様、動的光散乱式粒径分布測定装置（堀場製作所製「ＬＢ−５００」）にて測定したメジアン径を分散粒子径とした。
（２−３）分散・凝集状態
得られた反応液を反応溶媒で粒子濃度０．１ｗｔ％に希釈したものを試料とし、透過型電子顕微鏡にて分散状態を確認した。評価基準は以下の通りである。
●: Dispersion particle size <0.05μm
A: 0.05 μm ≦ dispersed particle size <0.1 μm
A: 0.1 μm ≦ dispersed particle size <1 μm
X: 0.1 μm ≦ dispersed particle diameter The dispersed particle diameter of the fine particles in the paint was also measured by a dynamic light scattering particle size distribution measuring apparatus (“LB-500” manufactured by Horiba, Ltd.) in the same manner as described above. The diameter was defined as the dispersed particle diameter.
(2-3) Dispersion / Aggregation State The obtained reaction solution was diluted with a reaction solvent to a particle concentration of 0.1 wt%, and the dispersion state was confirmed with a transmission electron microscope. The evaluation criteria are as follows.
Ａ：１次粒子が単分散または凝集していても１次元または２次元的な凝集である
Ｂ：１次粒子が３次元的に凝集し粒状物を形成している
（３）微粒子状金属酸化物の組成
（３−１）添加金属元素の含有量
微粒子状金属酸化物の生成反応で得られた反応液を試料とし、蛍光Ｘ線分析により各金属元素の定量分析を行い、主たる金属元素（例えばＺｎ）に対する添加金属元素（例えばＣｕやＡｇ）の含有率、および、粒子生成の際に金属化合物を添加剤として用いた場合は、主たる金属元素（例えばＺｎ）に対する該金属化合物の金属元素（Ｍｓ）の含有率、を求めた。
A: Even if the primary particles are monodispersed or agglomerated, they are a one-dimensional or two-dimensional agglomeration. B: The primary particles are agglomerated three-dimensionally to form a granular material. Composition of product (3-1) Content of added metal element Using the reaction solution obtained by the formation reaction of the particulate metal oxide as a sample, quantitative analysis of each metal element is performed by fluorescent X-ray analysis, and the main metal element ( For example, when the metal compound is used as an additive in the formation of particles, the metal element of the metal compound with respect to the main metal element (for example, Zn) (for example, Zn). Ms) content was determined.
（３−２）アシル基結合量
上記粉末試料１ｇを０．１Ｎ水酸化ナトリウム水溶液に添加し、２４時間攪拌したのち、イオンクロマトによりアシル基の同定と結合量の定量を行った。
（３−３）添加金属元素の価数の評価
必要に応じて、微粒子状金属酸化物における添加金属元素（例えばＣｕやＡｇ）の価数を以下のようにして評価した。すなわち、上記粉末試料に関し、光電子分光装置（日本電子株式会社製、製品名：ＪＰＳ−９０型）を用いたＸ線光電子分光法（ＸＰＳ）により、微粒子状金属酸化物に含有される添加金属元素（例えばＣｕやＡｇ）の２ｐ３／２スペクトルを測定し、そのピーク位置より結合エネルギー値を求め、添加金属元素（例えばＣｕやＡｇ）の価数を判定した。
(3-2) Acyl group binding amount 1 g of the above powder sample was added to a 0.1N aqueous sodium hydroxide solution and stirred for 24 hours, and then the acyl group was identified and the binding amount was determined by ion chromatography.
(3-3) Evaluation of the valence of the additive metal element The valence of the additive metal element (for example, Cu or Ag) in the particulate metal oxide was evaluated as follows. That is, regarding the powder sample, an additive metal element contained in the particulate metal oxide by X-ray photoelectron spectroscopy (XPS) using a photoelectron spectrometer (product name: JPS-90 type, manufactured by JEOL Ltd.) A 2p 3/2 spectrum of (for example, Cu or Ag) was measured, a binding energy value was obtained from the peak position, and the valence of the added metal element (for example, Cu or Ag) was determined.
なお、結合エネルギー値は、帯電性によるエネルギーシフト等による測定値の誤差を低減するために、表面炭化水素のＣ１ｓピークの位置を基準にして補正して求めた。
また、比較するための既知のデータとして、日本電子株式会社発行の「Handbook of X-ray Photoelectron Spectroscopy」（１９９１年）における各種金属元素の化合物の２ｐ３／２スペクトルのピーク位置を参考とした。
（４）微粒子状金属酸化物の光学特性
（４−１）吸収特性
得られた反応液を希釈溶媒として１−ブタノールを用いて微粒子濃度０．１ｗｔ％となるように希釈したものを試料として用い、積分球付き自記分光光度計（島津製作所製「ＵＶ−３１００」）を用いて、紫外および可視領域における分光透過率曲線を測定した。
The binding energy value was obtained by correcting with reference to the position of the C1s peak of the surface hydrocarbon in order to reduce the error in the measured value due to the energy shift due to the charging property.
Further, as known data for comparison, the peak positions of 2p 3/2 spectra of compounds of various metal elements in “Handbook of X-ray Photoelectron Spectroscopy” (1991) published by JEOL Ltd. were referred to.
(4) Optical properties of particulate metal oxide (4-1) Absorption properties The reaction solution obtained was diluted with 1-butanol as a diluent solvent so that the particulate concentration would be 0.1 wt%. The spectral transmittance curves in the ultraviolet and visible regions were measured using a self-recording spectrophotometer with an integrating sphere (“UV-3100” manufactured by Shimadzu Corporation).
紫外線遮断性：３８０ｎｍ、４００ｎｍ、４２０ｎｍにおける透過率で評価した。
可視光透過性：６００ｎｍにおける透過率で評価した。
なお、成膜品における分光透過曲線についても、上記と同様、積分球付き自記分光光度計（島津製作所製「ＵＶ−３１００」）を用いて、紫外および可視領域における分光透過率曲線を測定した。
（４−２）透明性、色相の評価
微粒子分散膜を形成して評価した。すなわち、微粒子状金属酸化物の生成反応により得られた反応液を、加熱溶媒置換することにより、微粒子状金属酸化物が粒子濃度２０ｗｔ％で１−ブタノールに分散してなる分散体を得た。得られた分散体１００部に、シリケートバインダー（ＳｉＯ2換算の固形分：５１ｗｔ％）２０部および触媒（ｎ−ブチルアミン）０．５部を配合し、塗料を調製した。なお、上記粒子濃度に関しては、得られた分散体を、真空乾燥機により１２０℃で１時間真空乾燥したときの固形分を、粒子重量として計算した。
Ultraviolet ray blocking property: evaluated by transmittance at 380 nm, 400 nm, and 420 nm.
Visible light transmittance: Evaluated by transmittance at 600 nm.
As for the spectral transmission curve of the film-formed product, the spectral transmission curves in the ultraviolet and visible regions were measured using a self-recording spectrophotometer with an integrating sphere (“UV-3100” manufactured by Shimadzu Corporation) in the same manner as described above.
(4-2) Evaluation of transparency and hue Evaluation was performed by forming a fine particle dispersion film. That is, the reaction liquid obtained by the reaction for producing the fine metal oxide was replaced with a solvent to obtain a dispersion in which the fine metal oxide was dispersed in 1-butanol at a particle concentration of 20 wt%. To 100 parts of the resulting dispersion, 20 parts of a silicate binder (solid content in terms of SiO 2 : 51 wt%) and 0.5 part of a catalyst (n-butylamine) were blended to prepare a paint. In addition, regarding the said particle | grain density | concentration, solid content when the obtained dispersion was vacuum-dried at 120 degreeC with the vacuum dryer for 1 hour was computed as particle weight.
得られた塗料を、アルカリガラスにバーコーターでウエット膜厚が２４μｍとなるように塗布した。その後、２５℃で常乾することにより、表面に微粒子状金属酸化物が分散した分散膜の形成されたガラスを得た。
そして、上記分散膜付きガラスを試料として、透明性および色相を評価した。すなわち、透明性については、濁度計（日本電色工業社製「ＮＤＨ−１００１ ＤＰ」）を用いて測定したヘイズ値にて評価した。色相については、外観を目視にて観察した。なお、基材としたアルカリガラスにおけるヘイズ値は０％であった。
なお、成膜品における透明性および色相についても、上記と同様、透明性は、濁度計（日本電色工業社製「ＮＤＨ−１００１ ＤＰ」）を用いて測定したヘイズ値にて評価し、色相は、外観を目視にて観察した。
The obtained paint was applied to alkali glass with a bar coater so that the wet film thickness was 24 μm. Thereafter, the glass was dried at 25 ° C. to obtain a glass having a dispersed film in which fine metal oxides were dispersed on the surface.
Then, the transparency and hue were evaluated using the glass with a dispersion film as a sample. That is, the transparency was evaluated by a haze value measured using a turbidimeter (“NDH-1001 DP” manufactured by Nippon Denshoku Industries Co., Ltd.). The appearance of the hue was visually observed. In addition, the haze value in the alkali glass used as the base material was 0%.
In addition, as for the transparency and hue in the film-formed product, the transparency was evaluated by a haze value measured using a turbidimeter (“NDH-1001 DP” manufactured by Nippon Denshoku Industries Co., Ltd.), The appearance of the hue was visually observed.
（５）粉末試料の色相
粉末試料の外観を目視にて観察して、評価した。
（６）微粒子濃度
反応液または分散体における微粒子濃度は、反応液または分散体０．５ｇをるつぼに秤量し、１２０℃で１時間、真空乾燥した後の乾燥粉末重量を測定し、算出した。
（７）成膜品の屈折率
反射分光膜厚計（大塚電子（株）製「ＦＥ３０００」）を用い、フィルム上に形成された膜について、２３０〜７６０ｎｍの範囲で反射率を測定し、代表的な屈折率の波長分散の近似式としてｎｋＣａｕｃｈｙの分散式を引用し、未知のパラメータを絶対反射率のスペクトルの実測値から非線形最小二乗法によって求めて、波長５５０ｎｍにおける屈折率を求めた。
(5) Hue of powder sample The appearance of the powder sample was visually observed and evaluated.
(6) Fine Particle Concentration The fine particle concentration in the reaction liquid or dispersion was calculated by measuring 0.5 g of the reaction liquid or dispersion in a crucible and measuring the dry powder weight after vacuum drying at 120 ° C. for 1 hour.
(7) Refractive index of film-formed product Using a reflection spectral film thickness meter ("FE3000" manufactured by Otsuka Electronics Co., Ltd.), the reflectance of the film formed on the film was measured in the range of 230 to 760 nm. The nkCauchy's dispersion formula is cited as an approximate expression of the chromatic dispersion of the refractive index, and the unknown parameter is obtained from the measured value of the absolute reflectance spectrum by the nonlinear least square method, and the refractive index at the wavelength of 550 nm is obtained.
〔実施例１−１〕
撹拌機、添加槽に直結した添加口、温度計、留出ガス出口および窒素ガス導入口を備えた、外部より加熱し得る耐圧ガラス製反応器と、上記添加口につながった添加槽と、上記留出ガス出口につながった冷却器（トラップに直結）と、を備えた反応装置を用意した。
上記反応器内に、酢酸亜鉛無水物粉末１８３部、酢酸銅（Ｉ）無水物粉末０．１３部、および、１−ブタノール３８８５部とからなる混合物を仕込み、気相部を窒素ガスでパージした後、撹拌しながら、２０℃から昇温し、１５０℃±１℃で１０時間加熱保持して、微粒子状金属酸化物の生成反応を行った後、冷却することにより、淡い灰色を帯びた色の微粒子（本発明の微粒子状金属酸化物）を２ｗｔ％の濃度で含む反応液（１−１）を得た。
[Example 1-1]
Stirrer, addition port directly connected to the addition tank, thermometer, distillate gas outlet and nitrogen gas inlet, pressure-resistant glass reactor that can be heated from the outside, addition tank connected to the addition port, and the above A reactor equipped with a cooler (directly connected to the trap) connected to the distillate gas outlet was prepared.
The reactor was charged with a mixture consisting of 183 parts of zinc acetate anhydrous powder, 0.13 parts of copper (I) acetate anhydrous powder, and 385 parts of 1-butanol, and the gas phase part was purged with nitrogen gas. Then, the temperature was raised from 20 ° C. with stirring, and heated and held at 150 ° C. ± 1 ° C. for 10 hours to produce a fine metal oxide, and then cooled to give a light grayish color Reaction liquid (1-1) containing a fine particle (particulate metal oxide of the present invention) at a concentration of 2 wt% was obtained.
反応液（１−１）中の金属酸化物粒子について、前述の各種測定・評価を行い、その結果を表２に示した。
〔実施例１−２〜1−１３および比較例１−１〜１−２〕
実施例１−１において、仕込み原料の種類や使用量および反応条件等を、表１に示したように変更した以外は、実施例１−１と同様にして、表２に示す微粒子（金属酸化物粒子）を表２に示す濃度で含む反応液（１−２）〜（１−１３）、（ｃ１−１）、（ｃ１−２）を得た。
反応液（１−２）〜（１−１３）、（ｃ１−１）、（ｃ１−２）中の各金属酸化物粒子について、前述の各種測定・評価を行い、その結果を表２に示した。
The metal oxide particles in the reaction liquid (1-1) were subjected to the various measurements and evaluations described above, and the results are shown in Table 2.
[Examples 1-2 to 1-13 and Comparative Examples 1-1 to 1-2]
In Example 1-1, the fine particles (metal oxide) shown in Table 2 were used in the same manner as in Example 1-1 except that the type, amount used, and reaction conditions of the charged raw materials were changed as shown in Table 1. Reaction liquids (1-2) to (1-13), (c1-1) and (c1-2) containing the product particles at the concentrations shown in Table 2 were obtained.
For each metal oxide particle in the reaction liquids (1-2) to (1-13), (c1-1), and (c1-2), the above-described various measurements and evaluations were performed, and the results are shown in Table 2. It was.
なお、実施例１−２、実施例１−５、実施例１−９、実施例１−１２において得られた粒子は、粒子表面に、表面処理金属化合物として添加したＳｉ化合物またはＴｉ化合物が結合していることが確認された。 The particles obtained in Example 1-2, Example 1-5, Example 1-9, and Example 1-12 were bonded to the Si surface or Ti compound added as a surface-treated metal compound on the particle surface. It was confirmed that
実施例１−８〜実施例１−１３における結果から、本発明では、添加するＭｎ量を増やすと、紫外線遮蔽性が高まり、紫外線遮蔽性に優れた透明な膜が得られることが判る。これは、結晶子径が２０ｎｍ以下であり、反応液の段階では２次凝集していてもその凝集力は弱く、バインダーの添加により容易に分散するためであると推測される。他方、Ｍｎ量を増やすと、紫外線遮蔽性は高まるが、可視光透過率が低下している。特に、１０％を超えると（実施例１−１３）、黄色の着色が強くなる傾向があり、可視光透過率が低くなっている。これを考慮すると、本発明において、より高い紫外線遮蔽性、より高い可視光透過率、着色の程度が低いこと、を達成するには、Ｍｎの場合、その含有量は、実施例１−９および１−１０のように、Ｍｎ／Ｚｎ＝３〜１０原子％の範囲が好ましいことが判る。しかし、実施例１−１２のように、本発明においては、Ｍｎ量が１０％を超える場合であっても、表面処理金属化合物としてのＳｉ化合物またはＴｉ化合物を粒子表面に結合させることによって、紫外線遮蔽性を高めると同時に、可視光透過率をも高めることができることも明らかである。
From the results in Examples 1-8 to 1-13, it can be seen that, in the present invention, when the amount of Mn to be added is increased, the ultraviolet shielding property is increased and a transparent film excellent in ultraviolet shielding property is obtained. This is presumed to be because the crystallite diameter is 20 nm or less, and even when secondary agglomeration occurs in the reaction solution, the agglomeration force is weak and easily dispersed by the addition of a binder. On the other hand, when the amount of Mn is increased, the ultraviolet shielding property is increased, but the visible light transmittance is decreased. In particular, when it exceeds 10% (Example 1-13), yellow coloring tends to be strong, and the visible light transmittance is low. In view of this, in the present invention, in order to achieve higher UV shielding properties, higher visible light transmittance, and a low degree of coloring, in the case of Mn, the content is as in Examples 1-9 and It can be seen that the range of Mn / Zn = 3 to 10 atomic% is preferable as in 1-10. However, as in Example 1-12, in the present invention, even when the amount of Mn exceeds 10%, by combining the Si compound or the Ti compound as the surface-treated metal compound with the particle surface, ultraviolet rays can be obtained. It is also clear that the visible light transmittance can be increased at the same time that the shielding property is increased.
〔実施例１−１４〕
実施例１−１と同様の反応装置を用い、反応器内に、純水３０００部、酢酸第一セリウム（ＩＩＩ）１水和物５０部、酢酸銅（ＩＩ）無水物０．６部からなる混合物を仕込み、室温で攪拌しながら、３０％過酸化水素水５０部を添加した。撹拌しながら、室温から昇温し、９０℃±２℃で５時間加熱保持したのち、３０％過酸化水素水１０部を添加した。さらに、１時間同温度で加熱保持して、微粒子状金属酸化物の生成反応を行った後、冷却することにより、微黄色を呈する透明感の高い微粒子（本発明の微粒子状金属酸化物）を０．８ｗｔ％の濃度で含む反応液（１−１４）を得た。
[Example 1-14]
Using the same reactor as in Example 1-1, the reactor consists of 3000 parts of pure water, 50 parts of cerous acetate (III) acetate monohydrate, and 0.6 parts of copper (II) acetate anhydride. The mixture was charged and 50 parts of 30% aqueous hydrogen peroxide was added while stirring at room temperature. While stirring, the temperature was raised from room temperature and heated at 90 ° C. ± 2 ° C. for 5 hours, and 10 parts of 30% hydrogen peroxide water was added. Furthermore, by heating and holding at the same temperature for 1 hour to generate a fine particle metal oxide, cooling is performed to obtain a fine yellowish highly transparent fine particle (the fine particle metal oxide of the present invention). A reaction solution (1-14) containing 0.8 wt% concentration was obtained.
得られた反応液（１−１４）を限外ろ過膜を用いたろ過に供することにより、不純物イオン類、残存過酸化水素の除去とともに濃縮を行い、微粒子濃度７ｗｔ％の水分散体（１−１４）を得た。
水分散体（１−１４）中の金属酸化物粒子について、Ｘ線回折測定を行ったところ、ピークはブロードであるが、ＣｅＯ2と同等のパターンを示す結果となった。また、結晶子径は、ピークがブロードであったために、１次粒子径をＴＥＭ像により求めた。紫外線吸収特性、可視光透過性は、上記評価方法（４−１）により評価した。なお、測定に際し、希釈溶媒はイオン交換水を用いた。以上の結果を表３に示す。
By subjecting the obtained reaction liquid (1-14) to filtration using an ultrafiltration membrane, concentration is performed together with removal of impurity ions and residual hydrogen peroxide, and an aqueous dispersion (1- 14) was obtained.
When X-ray diffraction measurement was performed on the metal oxide particles in the aqueous dispersion (1-14), the peak was broad, but a pattern equivalent to CeO 2 was obtained. Moreover, since the peak of the crystallite diameter was broad, the primary particle diameter was obtained from a TEM image. Ultraviolet absorption characteristics and visible light transmittance were evaluated by the above evaluation method (4-1). In the measurement, ion-exchanged water was used as the dilution solvent. The above results are shown in Table 3.
〔比較例１−３〕
実施例１−１４において、酢酸銅（ＩＩ）無水物を用いないこと以外は、実施例１−１３と同様にして、微粒子濃度７ｗｔ％の水分散体（ｃ１−３）を得た。
水分散体（ｃ１−３）中の金属酸化物粒子について、実施例１−１４と同様に評価した結果を表３に示す。
[Comparative Example 1-3]
In Example 1-14, an aqueous dispersion (c1-3) having a fine particle concentration of 7 wt% was obtained in the same manner as in Example 1-13, except that copper (II) acetate anhydride was not used.
The metal oxide particles in the water dispersion (c1-3) were evaluated in the same manner as in Example 1-14. Table 3 shows the results.
実施例１と同様の反応装置を用い、反応器内に、反応溶媒としてのエチレングリコールジメチルエーテル２４００部、チタニウムメトキシプロキシド３０３部、酢酸銀（Ｉ）２．８部、酢酸２７０部とからなる混合物を仕込み、気相部を窒素ガスでパージした後、撹拌しながら、２０℃から昇温し、１８０℃±１℃で５時間加熱保持して、金属酸化物粒子の生成反応を行った後、冷却することにより、微粒子（本発明の微粒子状金属酸化物）を微粒子濃度２ｗｔ％で含む反応液（１−１５）を得た。
Using the same reaction apparatus as in Example 1, a mixture comprising 2400 parts of ethylene glycol dimethyl ether as a reaction solvent, 303 parts of titanium methoxy proxy, 2.8 parts of silver (I) acetate, and 270 parts of acetic acid in a reactor. After purging the gas phase part with nitrogen gas, the temperature was raised from 20 ° C. while stirring, and heated and held at 180 ° C. ± 1 ° C. for 5 hours to perform a metal oxide particle formation reaction, By cooling, a reaction liquid (1-15) containing fine particles (particulate metal oxide of the present invention) at a fine particle concentration of 2 wt% was obtained.
反応液（１−１５）中の金属酸化物粒子について、Ｘ線回折測定を行ったところ、アナタース型酸化チタンと同等のパターンを示す結果となり、結晶子径は６ｎｍであった。また、紫外線吸収特性、可視光透過性は、上記評価方法（４−１）により評価した。以上の結果を表４に示す。
〔実施例１−１６〕
実施例１−１５において、酢酸銀（Ｉ）の代わりに、酢酸マンガン（ＩＩ）６．５部を用いたこと以外は、実施例１−１５と同様にして、微粒子（本発明の微粒子状金属酸化物）を微粒子濃度２ｗｔ％で含む反応液（１−１６）を得た。
The metal oxide particles in the reaction liquid (1-15) were subjected to X-ray diffraction measurement. As a result, a pattern equivalent to that of anatase-type titanium oxide was obtained, and the crystallite diameter was 6 nm. Moreover, the ultraviolet-ray absorption characteristic and visible-light transmittance were evaluated by the said evaluation method (4-1). The results are shown in Table 4.
[Example 1-16]
In Example 1-15, except that 6.5 parts of manganese (II) acetate was used instead of silver (I), fine particles (particulate metal of the present invention) were used. A reaction solution (1-16) containing a fine particle concentration of 2 wt% was obtained.
反応液（１−１６）中の金属酸化物粒子について、Ｘ線回折測定を行ったところ、アナタース型酸化チタンと同等のパターンを示す結果となり、結晶子径は６ｎｍであった。また、紫外線吸収特性、可視光透過性は、上記評価方法（４−１）により評価した。以上の結果を表４に示す。
〔比較例１−４〕
実施例１−１５において、酢酸銀（Ｉ）を用いないこと以外は、実施例１−１５と同様にして、微粒子を微粒子濃度２ｗｔ％で含む反応液（ｃ１−４）を得た。
反応液（ｃ１−４）中の金属酸化物粒子について、実施例１−１５と同様に評価した結果を表４に示す。
The metal oxide particles in the reaction liquid (1-16) were subjected to X-ray diffraction measurement. As a result, a pattern equivalent to that of anatase-type titanium oxide was obtained, and the crystallite diameter was 6 nm. Moreover, the ultraviolet-ray absorption characteristic and visible-light transmittance were evaluated by the said evaluation method (4-1). The results are shown in Table 4.
[Comparative Example 1-4]
In Example 1-15, except that silver acetate (I) was not used, a reaction solution (c1-4) containing fine particles at a fine particle concentration of 2 wt% was obtained in the same manner as Example 1-15.
Table 4 shows the results of evaluation of the metal oxide particles in the reaction liquid (c1-4) in the same manner as in Example 1-15.
実施例１−１で得られた反応液（１−１）１０００部をエバポレーターで加熱して１００部になるまで濃縮したのち、置換溶媒としてプロピレングリコールメチルエーテルアセテートを添加しながら同時に溶媒成分を留去し、プロピレングリコールメチルエーテルアセテートを溶媒成分とする分散体を得た。次いで、引き続き加熱濃縮して、冷却したのち、分散剤としてチタン（ＩＶ）テトラブトキシテトラマー（和光純薬工業株式会社製）０．２部を添加して、分散体（２−１）を得た。得られた分散体の粒子濃度と分散粒径を表５に示す。
After heating 1000 parts of the reaction liquid (1-1) obtained in Example 1-1 to 100 parts by heating with an evaporator, the solvent component was simultaneously distilled while adding propylene glycol methyl ether acetate as a substitution solvent. And a dispersion containing propylene glycol methyl ether acetate as a solvent component was obtained. Subsequently, after heating and concentrating and cooling, 0.2 part of titanium (IV) tetrabutoxytetramer (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a dispersant to obtain a dispersion (2-1). . Table 5 shows the particle concentration and the dispersed particle size of the obtained dispersion.
〔実施例２−２〜２−１０〕
実施例２−１において、表５に示す反応液を用い、表５に示す置換溶媒および分散剤を用いたこと以外は、実施例２−１と同様にして、分散体（２−２）〜（２−１０）を得た。得られた各分散体の粒子濃度と分散粒径を表５に示す。
[Examples 2-2 to 2-10]
In Example 2-1, the reaction liquid shown in Table 5 was used, and the same procedure as in Example 2-1 except that the substitution solvent and the dispersant shown in Table 5 were used. (2-10) was obtained. Table 5 shows the particle concentration and the dispersed particle size of each dispersion obtained.
実施例２−１で得られた分散体（２−１）１００部に、シリケートバインダー（三菱化学社製「ＭＫＣシリケートＭＳ５６」）３６部、触媒としてのｎ−ブチルアミン１部を添加して攪拌することにより、塗料（３−１）を得た。該塗料における微粒子の分散粒径は０．０４μｍであった。
次に、アルカリガラスを基材とし、該基材上に塗料（３−１）をバーコーターにて塗布したのち常温乾燥し、その後２００℃で６０分間加熱する操作を複数回繰り返すことにより、乾燥膜厚２μｍの微粒子分散膜を有する微粒子分散膜付き基材（３−１−Ａ）と、乾燥膜厚４μｍの微粒子分散膜を有する微粒子分散膜付き基材（３−１−Ｂ）とを得た。
To 100 parts of the dispersion (2-1) obtained in Example 2-1, 36 parts of a silicate binder (“MKC silicate MS56” manufactured by Mitsubishi Chemical Corporation) and 1 part of n-butylamine as a catalyst are added and stirred. Thus, a paint (3-1) was obtained. The dispersed particle diameter of the fine particles in the paint was 0.04 μm.
Next, using alkali glass as a base material, applying paint (3-1) on the base material with a bar coater, drying at room temperature, and then heating at 200 ° C. for 60 minutes is repeated a plurality of times to dry. A base material with a fine particle dispersion film (3-1-A) having a fine particle dispersion film having a thickness of 2 μm and a base material with a fine particle dispersion film (3-1-B) having a fine particle dispersion film having a dry thickness of 4 μm are obtained. It was.
得られた微粒子分散膜付き基材（３−１−Ａ）および（３−１−Ｂ）の分光透過率曲線を、基材であるアルカリガラスのそれとともに図２に示す。
また、得られた微粒子分散膜付き基材（３−１−Ａ）および（３−１−Ｂ）の透明性と色相を評価した結果、いずれも、透明性はヘイズ０．３％、色相は無色であった。
〔実施例３−２〕
実施例２−３で得られた分散体（２−３）１００部に、シリケートバインダー（三菱化学社製「ＭＫＣシリケートＭＳ５６」）３６部、触媒としてのｎ−ブチルアミン１部を添加して攪拌することにより、塗料（３−２）を得た。該塗料における微粒子の分散粒径は０．０５μｍであった。
The spectral transmittance curves of the obtained base materials with fine particle dispersion film (3-1-A) and (3-1-B) are shown in FIG. 2 together with that of the alkali glass as the base material.
In addition, as a result of evaluating the transparency and hue of the obtained substrates (3-1-A) and (3-1-B) with the fine particle dispersion film, the transparency was haze 0.3%, and the hue was It was colorless.
[Example 3-2]
To 100 parts of the dispersion (2-3) obtained in Example 2-3, 36 parts of a silicate binder (“MKC silicate MS56” manufactured by Mitsubishi Chemical Corporation) and 1 part of n-butylamine as a catalyst are added and stirred. As a result, a paint (3-2) was obtained. The dispersed particle diameter of the fine particles in the coating material was 0.05 μm.
次に、アルカリガラスを基材とし、該基材上に塗料（３−２）をバーコーターにて塗布したのち常温乾燥し、その後２００℃で６０分間加熱する操作を複数回繰り返すことにより、乾燥膜厚３μｍの微粒子分散膜を有する微粒子分散膜付き基材（３−２）を得た。
得られた微粒子分散膜付き基材（３−２）の分光透過率曲線を基材であるアルカリガラスのそれとともに図３に示す。
また、得られた微粒子分散膜付き基材（３−２）の透明性と色相を評価した結果、透明性はヘイズ０．５％、色相は黄色であった。
〔実施例３−３〕
実施例２−９で得られた分散体（２−９）１００部に、アクリル樹脂溶液（固形分濃度：５０ｗｔ％）６０部、希釈溶媒としてのトルエン／メチルエチルケトン＝１／１（重量比）の混合溶媒２０部を添加して攪拌することにより、塗料（３−３）を得た。該塗料における微粒子の分散粒径は０．０６μｍであった。
Next, using alkali glass as a base material, applying paint (3-2) on the base material with a bar coater, drying at room temperature, and then heating at 200 ° C. for 60 minutes is repeated several times to dry. A substrate with a fine particle dispersion film (3-2) having a fine particle dispersion film with a thickness of 3 μm was obtained.
The spectral transmittance curve of the obtained substrate (3-2) with a fine particle dispersion film is shown in FIG. 3 together with that of the alkali glass as the substrate.
Further, as a result of evaluating the transparency and hue of the obtained substrate (3-2) with a fine particle dispersion film, the transparency was haze 0.5% and the hue was yellow.
[Example 3-3]
To 100 parts of the dispersion (2-9) obtained in Example 2-9, 60 parts of an acrylic resin solution (solid content concentration: 50 wt%), toluene / methyl ethyl ketone = 1/1 (weight ratio) as a diluent solvent. By adding 20 parts of the mixed solvent and stirring, a paint (3-3) was obtained. The dispersed particle diameter of the fine particles in the paint was 0.06 μm.
次に、ポリエステルフィルムを基材とし、該基材上に塗料（３−３）をバーコーターにてウェット膜厚２４μｍとなるように塗布したのち、１００℃で１０分間加熱することにより、微粒子分散膜を有する微粒子分散膜付き基材（３−３）を得た。
得られた微粒子分散膜付き基材（３−３）の分光透過率曲線を図４に示す。
また、得られた微粒子分散膜付き基材（３−３）の透明性と色相を評価した結果、透明性はヘイズ０．５％、色相はわずかに黄色であった。
〔実施例３−４〕
実施例２−２で得られた分散体（２−２）１００部に、紫外線硬化型コーティング剤（共栄化学社製「ＨＩＣ２０００」、固形分：５０ｗｔ％、屈折率：１．５８）２０部を添加して攪拌することにより、塗料（３−４）を得た。
Next, a polyester film is used as a base material, and a paint (3-3) is applied on the base material by a bar coater so as to have a wet film thickness of 24 μm, followed by heating at 100 ° C. for 10 minutes, thereby dispersing fine particles. A fine particle-dispersed substrate (3-3) having a film was obtained.
FIG. 4 shows the spectral transmittance curve of the obtained substrate (3-3) with a fine particle dispersion film.
Moreover, as a result of evaluating the transparency and hue of the obtained substrate (3-3) with a fine particle dispersion film, the transparency was haze 0.5% and the hue was slightly yellow.
[Example 3-4]
To 100 parts of the dispersion (2-2) obtained in Example 2-2, 20 parts of an ultraviolet curable coating agent (“HIC2000” manufactured by Kyoei Chemical Co., Ltd., solid content: 50 wt%, refractive index: 1.58) was added. The paint (3-4) was obtained by adding and stirring.
次に、高透明ポリエチレンテレフタレートフィルムを基材とし、該基材上に塗料（３−４）をバーコーターにて塗布したのち、１００℃で１０分間加熱し、その後、高圧水銀ランプで１０分間紫外線照射することにより、乾燥膜厚５μｍの微粒子分散膜を有する微粒子分散膜付き基材（３−４）を得た。
得られた微粒子分散膜付き基材（３−４）は、実施例３−１と同様に紫外線を遮蔽し、高い可視光透過性を有するものであった。
また、得られた微粒子分散膜付き基材（３−４）の透明性と色相を評価した結果、透明性はヘイズ０．５％、色相は無色であり、膜の屈折率は１．７であった。
Next, a highly transparent polyethylene terephthalate film is used as a base material, and a paint (3-4) is applied onto the base material with a bar coater, followed by heating at 100 ° C. for 10 minutes, and then UV irradiation with a high pressure mercury lamp for 10 minutes. By irradiation, a substrate (3-4) with a fine particle dispersion film having a fine particle dispersion film having a dry film thickness of 5 μm was obtained.
The obtained substrate (3-4) with a fine particle dispersion film shielded ultraviolet rays as in Example 3-1, and had high visible light permeability.
Moreover, as a result of evaluating the transparency and hue of the obtained substrate (3-4) with a fine particle dispersion film, the transparency was haze 0.5%, the hue was colorless, and the refractive index of the film was 1.7. there were.
本発明の微粒子状金属酸化物は、例えば、建物用窓ガラス、自動車および電車等の車両用窓ガラス、飛行機およびヘリコプター等の空輸機用窓ガラス、農業用フィルム、各種包装用フィルム、塗料、化粧料等の各種用途において、基材の透明性を損なうことなく紫外線遮蔽性を付与するための材料として好適に用いることができる。 The particulate metal oxide of the present invention includes, for example, window glass for buildings, window glass for vehicles such as automobiles and trains, window glass for air transportation such as airplanes and helicopters, agricultural films, various packaging films, paints, cosmetics. In various uses such as a material, it can be suitably used as a material for imparting ultraviolet shielding properties without impairing the transparency of the substrate.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012070378A JP5517268B2 (en) | 2012-03-26 | 2012-03-26 | Particulate metal oxides and their applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012070378A JP5517268B2 (en) | 2012-03-26 | 2012-03-26 | Particulate metal oxides and their applications |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005001035A Division JP5016193B2 (en) | 2004-02-18 | 2005-01-05 | Particulate metal oxides and their applications |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2012144431A JP2012144431A (en) | 2012-08-02 |
| JP2012144431A5 JP2012144431A5 (en) | 2013-11-28 |
| JP5517268B2 true JP5517268B2 (en) | 2014-06-11 |
Family
ID=46788402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012070378A Expired - Fee Related JP5517268B2 (en) | 2012-03-26 | 2012-03-26 | Particulate metal oxides and their applications |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5517268B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104769150B (en) * | 2012-11-08 | 2018-09-21 | 株式会社半导体能源研究所 | The forming method of metal oxide film and metal oxide film |
| US9153650B2 (en) | 2013-03-19 | 2015-10-06 | Semiconductor Energy Laboratory Co., Ltd. | Oxide semiconductor |
| TWI652822B (en) | 2013-06-19 | 2019-03-01 | 日商半導體能源研究所股份有限公司 | Oxide semiconductor film and formation method thereof |
| TWI608523B (en) | 2013-07-19 | 2017-12-11 | 半導體能源研究所股份有限公司 | Oxide semiconductor film, method of manufacturing oxide semiconductor film, and semiconductor device |
| JP6389781B2 (en) * | 2015-03-05 | 2018-09-12 | 三井金属鉱業株式会社 | Conductive zinc oxide powder and conductive composition containing the same |
| JPWO2017134910A1 (en) | 2016-02-02 | 2018-11-22 | エム・テクニック株式会社 | Zinc oxide particles with controlled color characteristics, production method thereof, and coating composition containing the zinc oxide particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08291464A (en) * | 1995-04-14 | 1996-11-05 | Mitsubishi Materials Corp | Fiber having excellent fffect on prevention of change in color and fading |
-
2012
- 2012-03-26 JP JP2012070378A patent/JP5517268B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012144431A (en) | 2012-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5517268B2 (en) | Particulate metal oxides and their applications | |
| US20070154561A1 (en) | Metal oxide particle and its uses | |
| KR102011152B1 (en) | Core-shell type tetragonal titanium oxide solid solution aqueous dispersion, method for making the same, uv-shielding silicone coating composition, and coated article | |
| JP4938985B2 (en) | Metal oxide particles and uses thereof | |
| US9273073B2 (en) | Tin dioxide nanopartcles and method for making the same | |
| US9120681B2 (en) | Method for production of zinc oxide particles | |
| WO2018042803A1 (en) | Coating composition and coated article | |
| JP2007031216A (en) | Metal oxide particle, and its use | |
| KR20190049695A (en) | The photocatalyst laminated body | |
| JP4237518B2 (en) | Method for producing organic group composite metal oxide fine particles | |
| JP5016192B2 (en) | Metal oxide particles and uses thereof | |
| JP5016193B2 (en) | Particulate metal oxides and their applications | |
| JP5258447B2 (en) | Dispersion of titanium oxide composite particles and method for producing the dispersion | |
| TW202030152A (en) | Surface-treated infrared absorbing fine particles, surface-treated infrared absorbing fine particle powder, infrared absorbing fine particle dispersion liquid using the surface-treated infrared absorbing fine particles, infrared absorbing fine particle dispersion body, and infrared absorbing substrate | |
| WO2021054471A1 (en) | Dispersion liquid containing inorganic oxide particles and zinc cyanurate particles, and coating composition | |
| JP2005305367A (en) | Particle dispersion and its application | |
| JP2017043505A (en) | Manufacturing method of uv light shielding material particulates, uv light shielding material particulate dispersoid using uv light shielding material particulates, and uv light shielding body | |
| JPWO2019017305A1 (en) | Coated inorganic fine particles and method for producing the same | |
| TWI814742B (en) | Liquid composition for forming infrared shielding film, method for producing infrared shielding film using same and infrared shielding film | |
| JP4191511B2 (en) | Film-forming agent and film | |
| JP2019172526A (en) | Titania nanoparticle and ultraviolet shielding material including the same | |
| JP2005162914A (en) | Ultraviolet light-shielding film, metal oxide particle for ultraviolet light shielding, and composition for formation of ultraviolet light shielding material | |
| JP4177709B2 (en) | Fibrous metal oxide fine particles | |
| JP2009046609A (en) | Coating liquid for forming heat ray and uv ray shielding film, heat ray and uv ray shielding film, and heat ray and uv ray shielding substrate | |
| JP7371638B2 (en) | Surface-treated infrared absorbing fine particle dispersion and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120423 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131015 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131112 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140107 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140325 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140327 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5517268 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |