JPS62275182A - Ultraviolet screening agent - Google Patents
Ultraviolet screening agentInfo
- Publication number
- JPS62275182A JPS62275182A JP15000886A JP15000886A JPS62275182A JP S62275182 A JPS62275182 A JP S62275182A JP 15000886 A JP15000886 A JP 15000886A JP 15000886 A JP15000886 A JP 15000886A JP S62275182 A JPS62275182 A JP S62275182A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- temperature
- industrial
- zinc
- water
- 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.)
- Pending
Links
- 238000012216 screening Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 86
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 61
- 239000011701 zinc Substances 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 25
- 239000004202 carbamide Substances 0.000 abstract description 25
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000007062 hydrolysis Effects 0.000 abstract description 20
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract description 11
- 239000004312 hexamethylene tetramine Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 123
- 239000000203 mixture Substances 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 60
- 239000000047 product Substances 0.000 description 56
- 230000003595 spectral effect Effects 0.000 description 42
- 238000002834 transmittance Methods 0.000 description 41
- 238000004458 analytical method Methods 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 29
- 238000005259 measurement Methods 0.000 description 27
- 238000001035 drying Methods 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 23
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- -1 inorganic acid salts Chemical class 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 229910004625 Ce—Zr Inorganic materials 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 4
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 150000003754 zirconium Chemical class 0.000 description 4
- 150000000703 Cerium Chemical class 0.000 description 3
- 229910019580 Cr Zr Inorganic materials 0.000 description 3
- 229910019817 Cr—Zr Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 description 3
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910002593 Fe-Ti Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- 241000960399 Benkara Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910003120 Zn-Ce Inorganic materials 0.000 description 1
- 229910003121 Zn‐Fe‐C Inorganic materials 0.000 description 1
- 229910003117 Zn−Fe−C Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GDQXQVWVCVMMIE-UHFFFAOYSA-N dinitrooxyalumanyl nitrate hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GDQXQVWVCVMMIE-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XHUAMSYWTDRPFK-UHFFFAOYSA-N iron nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe] XHUAMSYWTDRPFK-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- XYWJNTOURDMTPI-UHFFFAOYSA-N procodazole Chemical compound C1=CC=C2NC(CCC(=O)O)=NC2=C1 XYWJNTOURDMTPI-UHFFFAOYSA-N 0.000 description 1
- 229950000989 procodazole Drugs 0.000 description 1
- 239000011219 quaternary composite Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- PTSZYEWEQITNAC-UHFFFAOYSA-N zinc dinitrate dihydrate Chemical compound O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O PTSZYEWEQITNAC-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〈産業上の利用分野〉
本発明は波長２６０ｎｍ〜４００ｎｍの紫外線を遮蔽し
、可視光線及び近赤外線ｉ３過能を有する特定の金属の
複合酸化物粉末から成る紫外線遮蔽剤に関する。Detailed Description of the Invention 3. Detailed Description of the Invention <Industrial Application Field> The present invention is a complex oxidation method of a specific metal that blocks ultraviolet rays with a wavelength of 260 nm to 400 nm and has visible light and near-infrared i3 performance. The present invention relates to an ultraviolet shielding agent made of powder.
〈従来の技術〉
紫外線遮蔽剤は、紫外線を散乱或いは吸収して紫外線を
遮蔽するもので、サリチル酸、パラアミノ安息香酸、け
い皮酸及びこれらのエステル類、或いはヘンヅフエノン
類などの有機物、酸化チタン、酸化亜鉛、酸化鉄などの
金属酸化物粉末などが用いられており、金属酸化物粉末
による光線の遮蔽能は、粉末の粒径／光線波長の比が１
／２の所が最大であることが知られている。<Prior art> Ultraviolet screening agents scatter or absorb ultraviolet rays to block ultraviolet rays, and include salicylic acid, para-aminobenzoic acid, cinnamic acid and their esters, organic substances such as hendphenones, titanium oxide, oxidized Metal oxide powders such as zinc and iron oxide are used, and the light shielding ability of metal oxide powders is determined when the ratio of powder particle size/light wavelength is 1.
It is known that the maximum value is /2.
金属酸化物粉末は、酸化反応用触媒としても用いられ、
その製造方法として、金属の塩化物や硫酸塩にアンモニ
ア水或いは尿素を加えて加水分解し、得られる水酸化物
と焼成する方法、チタンのｉ−プロポキシド、硝酸亜鉛
をそれぞれ加水分解して得られたＴ ｉ Ｏｔ ・ｎ
Ｈ２ｏとＺｎ（ＯＨ）ｚを混練し焼成する方法等（以上
「触媒ＪＶｏ１．１９．Ｎｏ、５．１９７７゜３５０〜
３５２頁、触媒学会誌）が知られている。Metal oxide powder is also used as a catalyst for oxidation reactions,
Its production methods include adding aqueous ammonia or urea to metal chloride or sulfate and hydrolyzing the resulting hydroxide, and calcining the resulting hydroxide, and hydrolyzing titanium i-propoxide and zinc nitrate. T i Ot ・n
A method of kneading and firing H2o and Zn(OH)z, etc.
352 pages, Catalysis Society Journal) is known.
また、ケイ素とチタンのフルコキソドの混合物を加水分
解し、その加水分解生成物を焼成する方法及びその生成
物を紫外線遮蔽能を有する化粧品用添加剤とすること（
特開昭５９−２２７８１３号）も知られている。In addition, a method for hydrolyzing a mixture of silicon and titanium flucoxod and baking the hydrolyzed product, and using the product as a cosmetic additive having ultraviolet shielding ability (
JP-A-59-227813) is also known.
この他、微細な粒子のものを得る方法として、チタンの
塩化物を昇華させ、酸素または水茎気で酸化分解、加水
分解を行なわす方法があり、これによると粒径約０．０
０２μｍ〜０．０５μｍのものが得られる。In addition, there is a method to obtain fine particles by sublimating titanium chloride and oxidatively decomposing and hydrolyzing it with oxygen or water vapor. According to this method, the particle size is about 0.0
02 μm to 0.05 μm can be obtained.
酸化亜鉛では、金属亜鉛の蒸気を気相酸化させる方法が
あり、これによると粒径約０．５μｍ〜１μｍのものが
得られる。For zinc oxide, there is a method of vapor-phase oxidation of metal zinc vapor, and by this method, particles having a particle size of about 0.5 μm to 1 μm can be obtained.
〈発明が解決しようとする問題点）
このような方法で得られた酸化亜鉛、酸化チタン、酸化
鉄の粉末は、その粒径を適度に選択すれば良好な紫外線
遮蔽能を発揮するが可視光線及び近赤外線の透過性に劣
り、他方、可視光線及び近赤外線の透過性の大きい粒径
のものは紫外線遮蔽能が充分でない。<Problems to be Solved by the Invention> The zinc oxide, titanium oxide, and iron oxide powders obtained by this method exhibit good ultraviolet shielding ability if the particle size is appropriately selected, but they do not protect against visible light. On the other hand, those having a large particle size and having a large transmittance to visible light and near infrared rays do not have sufficient ultraviolet shielding ability.
また、これらの金属酸化物粉末は、酸化触媒能を有し、
用途によっては、共存する有機物を変質させる問題点が
ある。In addition, these metal oxide powders have oxidation catalytic ability,
Depending on the application, there is a problem that coexisting organic substances may be altered.
複数の金属塩を水溶液中でアンモニア水等で加水分解し
、複合酸化物を得る方法では、複合酸化物が不均一で粒
径も大きくなり、紫外線遮蔽能の充分でかつ可視光線及
び近赤外線の透過性の良好なものが得られない。In the method of obtaining a composite oxide by hydrolyzing multiple metal salts in an aqueous solution with aqueous ammonia, etc., the composite oxide is non-uniform and has a large particle size. A product with good transparency cannot be obtained.
（問題点を解決するための手段）
かかる事情下に鑑み、本発明者らは紫外線遮蔽能に優れ
、可視光線及び近赤外線の透過性が大きく、また共存す
る有機物変質等の問題のない紫外線遮蔽剤を見出すべく
鋭意検討した結果、遂に本発明を完成するに至った。(Means for Solving the Problems) In view of the above circumstances, the present inventors have developed an ultraviolet shielding method that has excellent ultraviolet shielding ability, high transmittance of visible light and near-infrared rays, and is free from problems such as alteration of coexisting organic substances. As a result of intensive studies to find a new agent, the present invention was finally completed.
すなわち、本発明は平均粒子径が約ｏ、ｏｏｔμｍ〜約
０．５μｍである、アルミニウム、鉄、クロム、セリウ
ム、ジルコニウム及びチタンから選ばれた１種以上の金
属と亜鉛との複合酸化物から成る紫外線遮蔽剤を提供す
るものである。That is, the present invention consists of a composite oxide of zinc and one or more metals selected from aluminum, iron, chromium, cerium, zirconium, and titanium, with an average particle size of about 0.00 μm to about 0.5 μm. The present invention provides an ultraviolet shielding agent.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明に於ける紫外線遮蔽剤とは、アルミニウム、鉄、
クロム、セリウム、ジルコニウム及びチタン（以下、Ａ
ｊｌ、 Ｆｅ、 Ｃｒ、 Ｃｅ、 Ｚｒ、Ｔｉと表
現する場合もある。）よりなる群から選ばれる少くとも
１種以上の金属と亜鉛（以下、Ｚｎと表現する場合もあ
る。）の複合酸化物であり、より具体的にはＺｎ−Ａｆ
ｆ、Ｚｎ−Ｆｅ、Ｚｎ−Ｃｒ、、Ｚｎ−Ｃｅ、Ｚｎ−Ｚ
ｒ。The ultraviolet screening agent in the present invention includes aluminum, iron,
Chromium, cerium, zirconium and titanium (hereinafter referred to as A
It may also be expressed as jl, Fe, Cr, Ce, Zr, or Ti. ) is a composite oxide of at least one metal selected from the group consisting of zinc (hereinafter sometimes referred to as Zn), more specifically Zn-Af
f, Zn-Fe, Zn-Cr, Zn-Ce, Zn-Z
r.
Ｚｎ−Ｔｉよりなる二成分系複合酸化物、Ｚｎ−Ａｊｌ
−Ｆｅ、 Ｚｎ−Ａ ７！−Ｃｒ Ｓ Ｚｎ−Ａ １
−Ｃｅ、Ｚｎ−Ａｌ−Ｚｒ、Ｚｎ−Ａｊｌ−Ｔｉ。Binary composite oxide consisting of Zn-Ti, Zn-Ajl
-Fe, Zn-A 7! -Cr S Zn-A 1
-Ce, Zn-Al-Zr, Zn-Ajl-Ti.
Ｚｎ−Ｆｅ−Ｃｒ、Ｚｎ−Ｆｅ−Ｃｅ、Ｚｎ−Ｆｅ−Ｚ
ｒ、Ｚｎ−Ｆｅ−Ｔｉ、、Ｚｎ−Ｃｒ−Ｃｅ５Ｚｎ−Ｃ
ｒ−Ｚｒ、Ｚｎ−Ｃｒ−Ｔｉ。Zn-Fe-Cr, Zn-Fe-Ce, Zn-Fe-Z
r, Zn-Fe-Ti, , Zn-Cr-Ce5Zn-C
r-Zr, Zn-Cr-Ti.
Ｚｎ−Ｃｅ−Ｚｒ、Ｚｎ−Ｃｅ−Ｔｉ、、Ｚｎ−Ｚｒ−
Ｔｉよりなる三成分系複合酸化物、Ｚｎ−Ａ１−Ｆｅ−
Ｃｒ、Ｚｎ−Ａｌ−Ｆｅ−Ｃｅ、Ｚｎ−Ａ／−Ｆｅ−Ｚ
ｒ、Ｚｎ−ＡＡ−Ｆｅ −Ｔｉ、Ｚｎ−Ａｆ−Ｃｒ−Ｃ
ｅ、Ｚｎ−Ａｆｆｉ−Ｃｒ−Ｚｒ、、Ｚｎ−Ａｊｌ−Ｃ
ｒ−ＴｉＳＺｎ −Ａｆｆｉ−Ｃｅ−Ｚｒ、Ｚｎ−Ａｌ
−Ｃｅ−Ｔｉ。Zn-Ce-Zr, Zn-Ce-Ti, Zn-Zr-
Ternary composite oxide consisting of Ti, Zn-A1-Fe-
Cr, Zn-Al-Fe-Ce, Zn-A/-Fe-Z
r, Zn-AA-Fe-Ti, Zn-Af-Cr-C
e, Zn-Affi-Cr-Zr, , Zn-Ajl-C
r-TiSZn-Affi-Ce-Zr, Zn-Al
-Ce-Ti.
Ｚｎ−Ａ １−Ｚｒ−Ｔｉ 、 Ｚｎ−Ｆｅ−Ｃｒ−Ｃ
ｅ、、Ｚｎ−Ｆｅ−Ｃｅ−Ｚｒ、Ｚｎ−Ｆｅ−Ｚｒ−Ｔ
ｉ＋Ｚｎ−Ｆｅ−Ｃｒ−Ｚｒ、Ｚｎ−Ｆｅ−Ｃｒ−Ｔｉ
、 Ｚｎ−Ｆｅ−Ｃｅ−Ｔｉ 、Ｚｎ−Ｃｒ−Ｃｅ−
Ｚｒ５ Ｚｎ−Ｃｒ−Ｚｒ −。Zn-A 1-Zr-Ti, Zn-Fe-Cr-C
e, , Zn-Fe-Ce-Zr, Zn-Fe-Zr-T
i+Zn-Fe-Cr-Zr, Zn-Fe-Cr-Ti
, Zn-Fe-Ce-Ti, Zn-Cr-Ce-
Zr5Zn-Cr-Zr-.
Ｔｉ、 Ｚｎ−Ｃｅ−Ｚｒ−Ｔｉ、 Ｚｎ−Ｃｒ
−Ｃｅ −Ｔ ｉ 、よりなる四成分系複合酸化物、Ｚ
ｎ−Ａｆ−Ｆｅ−Ｃｒ−Ｃｅ、 Ｚｎ−Ａｆｆｉ−Ｆｅ
−Ｃｒ−Ｚｒ、 Ｚｎ−Ａｌ２−Ｆｅ−Ｃｒ −Ｔｉ、
Ｚｎ−Ｆｅ−Ｃｒ−Ｃｅ−Ｚｒ、Ｚｎ−Ｆｅ−Ｃｒ−Ｃ
ｅ−Ｔｉ、 Ｚｎ−Ｃｒ−Ｃｅ−Ｚｒ−Ｔｉ、Ｚｎ−Ａ
ｆ−Ｃｅ−Ｚｒ−Ｔｉ、Ｚｎ−Ａｌ−Ｆｅ−Ｃｅ−Ｚｒ
、、Ｚｎ−Ａｌ−Ｆｅ−Ｃｅ−Ｔｉ５ Ｚｎ−Ａｆ−’
Ｆｅ−Ｚｒ −Ｔｉ、、 Ｚ ｎ Ａ Ｉ Ｃｒ
−Ｃｅ Ｚ ｒ −Ｚ ｎ −Ａｌ−Ｃｒ−Ｃｅ−Ｔ
ｉ、 Ｚｎ−Ａｌ−Ｃｒ−Ｚｒ−Ｔｉ、Ｚｎ−Ｆｅ−Ｃ
ｅ−Ｚｒ−Ｔｉ、Ｚｎ−Ｆｅ−Ｃｒ−Ｚｒ−Ｔｉよりな
る三成分系複合酸化物、Ｚｎ−Ａｌ−Ｆｅ−Ｃｒ−Ｃｅ
−ＺｒＳＺｎ−ＡＲ−Ｆｅ−Ｃｒ−Ｃｅ−Ｔｉ、Ｚｎ
−Ａ １−Ｆｅ−Ｃｒ−Ｚｒ−Ｔｉ 、 Ｚｎ−Ａｆｆ
−Ｆｅ−Ｃｅ−Ｚｒ−Ｔｉ、、Ｚｎ−Ａｎ −Ｃｒ−Ｃ
ｅ−Ｚｒ−Ｔｉ 、、 Ｚｎ−Ｆｅ−Ｃｒ −Ｃｅ
−Ｚｒ−Ｔｉよりなる六成分系複合酸化物、及びＺｎ−
Ａｌ−Ｆｅ−Ｃｒ−Ｃｅ−Ｚｒ −Ｔｉよりなる七成分
系複合酸化物等が挙げられる。Ti, Zn-Ce-Zr-Ti, Zn-Cr
-Ce -T i , a quaternary composite oxide consisting of Z
n-Af-Fe-Cr-Ce, Zn-Affi-Fe
-Cr-Zr, Zn-Al2-Fe-Cr-Ti,
Zn-Fe-Cr-Ce-Zr, Zn-Fe-Cr-C
e-Ti, Zn-Cr-Ce-Zr-Ti, Zn-A
f-Ce-Zr-Ti, Zn-Al-Fe-Ce-Zr
,,Zn-Al-Fe-Ce-Ti5 Zn-Af-'
Fe-Zr-Ti, ZnAICr
-Ce Z r -Z n -Al-Cr-Ce-T
i, Zn-Al-Cr-Zr-Ti, Zn-Fe-C
Ternary composite oxide consisting of e-Zr-Ti, Zn-Fe-Cr-Zr-Ti, Zn-Al-Fe-Cr-Ce
-ZrSZn-AR-Fe-Cr-Ce-Ti, Zn
-A 1-Fe-Cr-Zr-Ti, Zn-Aff
-Fe-Ce-Zr-Ti, , Zn-An -Cr-C
e-Zr-Ti, Zn-Fe-Cr-Ce
-Six-component complex oxide consisting of Zr-Ti, and Zn-
Examples include seven-component composite oxides made of Al-Fe-Cr-Ce-Zr-Ti.
これら複合酸化物は単独で使用しても良く、勿論２種以
上を混合して使用しても良い。These composite oxides may be used alone or in combination of two or more.
本発明の実施に際し、複合酸化物を構成する亜鉛とＴｉ
、Ａｊ！、Ｆｅ、Ｃｒ５Ｃｅ、、Ｚｒの群より選ばれる
他の金属の構成割合は金属により異なり、例えば亜鉛と
チタンの組合せではそれらの原子比は亜鉛１に対しチタ
ンが０．０１〜０．２５、好ましくは０．０５〜０．１
、亜鉛とアルミニウムは亜鉛ｌに対しアルミニウムが０
．００１〜０．５、好ましくは０．０１〜０．４、亜鉛
と鉄は亜鉛ｌに対し鉄が０．０００１〜０．５、好まし
くはｏ、ｏｏｏｉ〜０゜２、亜鉛とクロムは亜鉛１に対
しクロムが０゜０００５〜０．５、好ましくは０．００
０５〜０．３、亜鉛とセリウムは亜鉛ｌに対しセリウム
が０．００００５〜２、好ましくは０．００００５〜０
．５、亜鉛とジルコニウムは亜鉛１に対しｏ、ｏｏｏｓ
〜０．５、好ましくは０゜０００５〜０．３である。When implementing the present invention, zinc and Ti constituting the composite oxide
,Aj! The composition ratio of other metals selected from the group of , Fe, Cr5Ce, and Zr varies depending on the metal. For example, in the case of a combination of zinc and titanium, the atomic ratio of titanium to 1 part of zinc is preferably 0.01 to 0.25. is 0.05-0.1
, zinc and aluminum are zinc 1 and aluminum 0
．． 001 to 0.5, preferably 0.01 to 0.4, iron to 1 zinc, preferably 0.0001 to 0.5, preferably o, oooi to 0°2, zinc and chromium, 1 to 1 zinc chromium is 0°0005 to 0.5, preferably 0.00
05-0.3, zinc and cerium are 0.00005-2, preferably 0.00005-0 for 1 zinc
．． 5. Zinc and zirconium are o, ooos to 1 zinc
-0.5, preferably 0°0005-0.3.
亜鉛１原子比に対する金属の構成割合が、上記範囲外で
は紫外線遮蔽能が劣り、鉄に於いては亜鉛ｌ原子比に対
し０．５を越える場合には可視光線及び近赤外線の透過
性が低下するので好ましくない。If the ratio of metal to 1 atomic ratio of zinc is outside the above range, the UV shielding ability will be poor, and for iron, if the ratio of metal to 1 atomic ratio of zinc exceeds 0.5, the transmittance of visible light and near infrared rays will decrease. Therefore, it is not desirable.
また、亜鉛と複数の金属よりなる複合酸化物に於ける金
属の添加量は二成分系に於ける亜鉛と他金属の各々の添
加量範囲が適用され、好ましくは亜鉛と他金属の二成成
系に於ける各々の金属の好ましい範囲が適用される。In addition, the amount of metal added in a composite oxide consisting of zinc and multiple metals is determined by the amount range of each of zinc and other metals in a two-component system. Preferred ranges for each metal in the system apply.
本発明に於いて複合酸化物とは出発原料として用いた亜
鉛とＡ１、Ｆｅ、Ｃｒ、Ｃｅ、Ｚｒ、Ｔｉから選ばれた
１種以上の金属すべてが反応し複合酸化物を形成してい
る必要はなく、反応生成物が少なくとも複合酸化物を構
成し、かつその生成物が９０％以上の紫外線遮蔽能、６
０％以上の可視光線及び近赤外線透過能を有するもので
あれば、金属酸化物等を一部含有する複合酸化物であっ
てもよい。In the present invention, a composite oxide is defined as a compound in which zinc used as a starting material and one or more metals selected from A1, Fe, Cr, Ce, Zr, and Ti all react to form a composite oxide. No, the reaction product constitutes at least a composite oxide, and the product has an ultraviolet shielding ability of 90% or more, 6
A composite oxide partially containing a metal oxide or the like may be used as long as it has visible light and near-infrared transmittance of 0% or more.
本発明の紫外線遮蔽剤用複合酸化物は酸素原子を介して
金属が結合している構造を持っている。The composite oxide for ultraviolet screening agents of the present invention has a structure in which metals are bonded via oxygen atoms.
例えば亜鉛原子が酸素原子を介して他の金属と−Ｚｎ−
０−Ｔｉ４、−Ｚｎ−〇−Ａｌ＜、＞Ａｆ−０−Ｚｎ−
０−Ｔｉ（、−Ｚｎ−０−Ｆｅ＜、 Ｚｎ−０−Ｃｅ
そ、＞Ｆｅ−０−Ｚｎ−０−Ｃｅ４−５−Ｚｎ−０−Ｚ
ｒ（−１−Ｚｎ−ｏ−ｃ ｒ ＜、＞Ｃｒ −０−Ｚｎ
−０−Ｚｒそ等の結合を含んでいるもので、望ましくは
Ｚｎ原子の全てが、上記の如く酸素を介して他の金属と
結合していることが好ましい。このような構造はＪＩＳ
ＫＯ１）７に示される如く、赤外スペクトルにより確認
できる。For example, a zinc atom interacts with another metal via an oxygen atom -Zn-
0-Ti4, -Zn-〇-Al<,>Af-0-Zn-
0-Ti(,-Zn-0-Fe<, Zn-0-Ce
So,>Fe-0-Zn-0-Ce4-5-Zn-0-Z
r(-1-Zn-o-c r <,>Cr -0-Zn
-0-Zr and the like, preferably all Zn atoms are bonded to other metals via oxygen as described above. This kind of structure is JIS
As shown in KO1)7, it can be confirmed by infrared spectrum.
Ｚｎ原子がＡＲ−０−Ｚｎ−０−ＲＡ、 −Ｚｎ−０−
ＲＡ（ＲはＡ ｊ！ ｓ Ｆ ｅ ｓ Ｚ ｒ −Ｔ
ｉ １Ｃｅ、Ｃｒより選ばれた金属原子、Ａは結合手で
あり、Ｒの価数−１を示す。）等の結合を含まないもの
は単に酸化亜鉛と上記金属の酸化物粉末の混合であり、
本発明の目的とする紫外線遮蔽能に優れ、かつ可視光線
、及び近赤外線透過能に優れた粉末は得られない。Zn atoms are AR-0-Zn-0-RA, -Zn-0-
RA (R is A j! s Fe s Z r −T
i A metal atom selected from 1Ce and Cr, A is a bond, and the valence of R is -1. ) etc., which do not contain any bonds, are simply a mixture of zinc oxide and oxide powder of the above metals,
It is not possible to obtain a powder that has excellent ultraviolet shielding ability and excellent visible light and near-infrared transmission ability, which is the objective of the present invention.
本発明の紫外線遮蔽剤の大きさは平均粒径約０．５μｍ
以下、好ましくは０．２μｍ以下である。The average particle size of the ultraviolet screening agent of the present invention is approximately 0.5 μm.
The thickness is preferably 0.2 μm or less.
粒径の大きいものは紫外線遮蔽能が若干低く、加えて化
粧品とした場合の肌ざわりが悪くまた農業用マルチフィ
ルム、食品包装用フィルムへの適用では分散性が劣るの
で好ましくない。Large particle sizes are not preferred because they have slightly low ultraviolet shielding ability, have a poor texture when used in cosmetics, and have poor dispersibility when applied to agricultural mulch films and food packaging films.
他方粒径の微細なものは、紫外線遮蔽能は充分であるも
のの取扱い難くなること及び酸化触媒能が発現してくる
ことなどから平均粒径約０．００１μｍ以上、より好ま
しくは０．００５μｍ以上である。On the other hand, particles with a fine particle size have an average particle size of about 0.001 μm or more, more preferably 0.005 μm or more, because although they have sufficient ultraviolet shielding ability, they become difficult to handle and develop oxidation catalytic ability. be.
このような複合酸化物の製造方法としては、亜鉛塩と、
アルミニウム塩、鉄塩、クロム塩、セリウム塩、ジルコ
ニウム塩、及びチタン塩の中から選ばれる一種或いは二
種以上の金属塩とを、アルコール水？８液中で尿素及び
ヘキサメチレンテトラミンから選ばれる、少なくとも一
種の加水分解沈澱剤の存在下、加水分解し、次いで加水
分解生成物を焼成する方法が挙げられる。As a method for producing such a composite oxide, zinc salt and
Alcohol water and one or more metal salts selected from aluminum salts, iron salts, chromium salts, cerium salts, zirconium salts, and titanium salts. A method may be mentioned in which hydrolysis is carried out in an 8-liquid solution in the presence of at least one hydrolysis precipitant selected from urea and hexamethylenetetramine, and then the hydrolysis product is calcined.
ここで原料の亜鉛塩、アルミニウム塩、鉄塩、クロム塩
、セリウム塩、ジルコニウム塩及びチタン塩は水に可溶
な性質の無機酸塩、有機酸塩、例えば、塩化物、硫酸塩
、硝酸塩、酢酸塩等である。Here, the raw materials zinc salt, aluminum salt, iron salt, chromium salt, cerium salt, zirconium salt, and titanium salt are water-soluble inorganic acid salts, organic acid salts, such as chlorides, sulfates, nitrates, Acetate, etc.
アルミニウム塩については、ポリ塩化アルミニウムなど
も使用可能である。As for the aluminum salt, polyaluminum chloride and the like can also be used.
また、チタン塩に代えて、チタンアルコキシドも好適に
用いることができる。Moreover, titanium alkoxide can also be suitably used in place of titanium salt.
次にアルコール水溶液は、アルコール濃度で約５容量％
以上、好ましくは１０容量％以上のものが用いられる。Next, the alcohol aqueous solution has an alcohol concentration of approximately 5% by volume.
Above, preferably 10% by volume or more is used.
アルコール濃度が、約５容量％未満では生成する複合酸
化物の平均粒径を０．５μｍ以下にすることが困難とな
ることと、粒径分布が広がり大粒径のものが混在して出
来るので好ましくない。If the alcohol concentration is less than about 5% by volume, it will be difficult to reduce the average particle size of the composite oxide to 0.5 μm or less, and the particle size distribution will expand and large particles will be mixed together. Undesirable.
他方、アルコールが過剰でも可能であるが多くしでもそ
れだけの効果は出ない。On the other hand, it is possible to use too much alcohol, but even if there is too much alcohol, the effect will not be as great.
アルコールの種類としては、水への溶解度が１容量％以
上であればよく、例えば、メタノール、エタノール、イ
ソプロパツール、ノルマルプロパツールなどの１価のア
ルコール類、エチレングリコール、ジエチレングリコー
ル、プロピレングリコール、グリセリンなどの多価アル
コール類である。The type of alcohol only needs to have a solubility in water of 1% by volume or more, such as monohydric alcohols such as methanol, ethanol, isopropanol, normal propazol, ethylene glycol, diethylene glycol, propylene glycol, and glycerin. Polyhydric alcohols such as
加水分解沈澱剤は、尿素及びヘキサメチレンテトラミン
の何れか、或いは両者の混合物を水溶液として用いるの
が望ましい。As the hydrolysis precipitant, it is desirable to use either urea or hexamethylenetetramine, or a mixture of both in the form of an aqueous solution.
加水分解沈澱剤の量は、金属塩が加水分解して生成する
酸を中和するに必要な理論量の２倍以上、好ましくは３
倍量〜５倍量を用いる。The amount of the hydrolysis precipitant is at least twice the theoretical amount necessary to neutralize the acid generated by hydrolysis of the metal salt, preferably 3 times or more.
Use twice to 5 times the amount.
加水分解反応は、撹拌下で、温度を常温から１００℃、
より好ましくは７０℃以上の温度で３時間〜６時間程度
行う。反応終了は、反応液のｐＨが上昇し、７附近にな
ったことで確認すればよい。The hydrolysis reaction is carried out under stirring at a temperature ranging from room temperature to 100°C.
More preferably, it is carried out at a temperature of 70°C or higher for about 3 to 6 hours. The completion of the reaction can be confirmed when the pH of the reaction solution increases to around 7.
加水分解生成物は次いでｆ過、デカンテーションなどの
慣用の固−液分離操作で取り出し、水洗を行った後室温
ないし２００℃程度で充分乾燥し、３５０℃〜１）００
℃程度の温度で約１〜３時間焼成を行う。The hydrolyzed product is then removed by conventional solid-liquid separation operations such as filtration and decantation, washed with water, thoroughly dried at room temperature to about 200°C, and dried at 350°C to 1)00°C.
Firing is performed at a temperature of approximately 1 to 3 hours.
焼成の前後で、二次凝集粒子を粉砕（解砕）するのが望
ましく、該粉砕は、ハンマーミル、措潰機、ボールミル
、振動ミルなど慣用手段で行えばよい。It is desirable to crush (disintegrate) the secondary agglomerated particles before and after firing, and the crushing may be carried out by a conventional means such as a hammer mill, crusher, ball mill, or vibration mill.
本発明の紫外線遮蔽剤の具体的用途としては、化粧品、
塗料、農業用フィルム、食品包装用フィルムや食品容器
被覆用フィルム等への添加剤が挙げられる。勿論、本発
明の紫外線遮蔽剤はその効果を失わない範囲で、例えば
酸化チタン、酸化亜鉛、酸化鉄等の既に公知の紫外線遮
蔽剤と併用して用いる事も可能である。Specific uses of the ultraviolet screening agent of the present invention include cosmetics,
Examples include additives for paints, agricultural films, food packaging films, food container coating films, and the like. Of course, the ultraviolet screening agent of the present invention can also be used in combination with already known ultraviolet screening agents such as titanium oxide, zinc oxide, iron oxide, etc., as long as the effect is not lost.
〈発明の効果〉
以上、詳述した本発明の平均粒子径０．００１μｍ〜０
．５μｍの複合酸化物より成る紫外線遮蔽剤は波長４０
０ｎｍ以下の紫外線遮蔽能が９０％以上と優れ、しがも
可視光線及び近赤外線の透過性く波長４００ｎｍ〜３０
００ｎｍ）が６０％以上で、かつ触媒活性が殆んど無く
、共存する有機物を変質しないため紫外線遮蔽を目的と
したあらゆる分野に於いて使用し得るものでその工業的
価値は頗る大なるものである。<Effects of the Invention> The average particle diameter of the present invention detailed above is 0.001 μm to 0.
．． The UV shielding agent made of 5 μm composite oxide has a wavelength of 40
Excellent UV shielding ability of 90% or more below 0 nm, and transparent to visible light and near infrared rays with wavelengths of 400 nm to 30 nm.
00nm) of 60% or more, has almost no catalytic activity, and does not alter the coexisting organic substances, so it can be used in all fields for the purpose of blocking ultraviolet rays, and its industrial value is extremely large. be.
〈実施例〉
以下、本発明の紫外線遮蔽剤を実施例及び比較例に基づ
き詳述するが、実施例は本発明の一実施態様を示すもの
であり、何ら本発明範囲を制限するものではない。<Example> Hereinafter, the ultraviolet screening agent of the present invention will be described in detail based on Examples and Comparative Examples, but the Example shows one embodiment of the present invention and is not intended to limit the scope of the present invention in any way. .
尚、本発明の実施例、比較例で用いた各測定方法は以下
の如くである。The measurement methods used in the Examples and Comparative Examples of the present invention are as follows.
金属原子比 ： 原子吸光分析法
酸化物の粒径 ： 走査電子顕微鏡写真法複合酸化物の
原子結合状Ｂ ＝
複合酸化物粉末０．０３ｇを低密度ポリエチレン粉末０
．４７ｇと混合し、２本ロール（温度１００℃〜１６０
°Ｃ）でｔ１練７容融し厚み約５０μｍのフィルムを製
作する。Metal atomic ratio: Atomic absorption spectrometry Oxide particle size: Scanning electron microscopy Atomic bond type of composite oxide B = 0.03 g of composite oxide powder mixed with low density polyethylene powder 0
．． Mix with 47g of
°C) to produce a film with a thickness of approximately 50 μm.
対照フィルムとして複合酸化物を含まない低密度ポリエ
チレンの厚み約５０μｍのフィルムを製作する。As a control film, a film of about 50 μm thick made of low density polyethylene containing no composite oxide was produced.
両フィルムについてＪＩＳＫＯ１）７に従って赤外スペ
クトルを測定し、特性吸収から分析した。Infrared spectra of both films were measured according to JIS KO1) 7 and analyzed based on characteristic absorption.
分光透過率 ：
上記複合酸化物の結合状態を調べるのに用いたと同じフ
ィルムをＪ［５ＫＯ１）５に従い分光々変針にて測定し
た。Spectral transmittance: The same film used to examine the bonding state of the above-mentioned composite oxide was measured using a spectral variable needle according to J[5KO1)5.
実施例１
工業用９７％硝酸アルミニウム９水塩０． ４５ｇ及び
工業用９５％硝酸亜鉛６水塩３６２ｇをエタノール１２
００ｍｌ中に入れ、これを３０分間撹拌混合して溶解し
た。Example 1 Industrial 97% aluminum nitrate nonahydrate 0. 45g and 362g of industrial 95% zinc nitrate hexahydrate in ethanol 12
00ml and stirred and mixed for 30 minutes to dissolve.
続いて９９％のへキサメチレンテトラミン２８３ｇを水
１６００ｍｊ！に溶かした水？８液を加えて、更に撹拌
した。Next, add 283g of 99% hexamethylenetetramine to 1600mj of water! Water dissolved in? 8 liquid was added and further stirred.
これを加熱し、温度約８０℃にて撹拌下５時間続いて温
度約１００ ’Ｃで１時間、加水分解反応を行い加水分
解反応生成物を得た。This was heated and hydrolyzed at a temperature of about 80° C. for 5 hours with stirring, followed by a hydrolysis reaction at a temperature of about 100° C. for 1 hour to obtain a hydrolysis reaction product.
これをデ過し、水１０００ｍｊ！で洗浄し、ｌ温度１５
０℃で乾燥後、振動ミルで粉砕した。I passed this and got 1000mj of water! Wash at l temperature 15
After drying at 0°C, it was pulverized using a vibration mill.
次いで温度約７００℃にて１時間焼成して平均粒径０，
０１μｍの微粉末９１．８ｇを得た。Then, it was fired at a temperature of about 700°C for 1 hour to obtain an average particle size of 0.
91.8 g of fine powder with a diameter of 0.01 μm was obtained.
この製品粉末の組成は分析の結果Ｚｎ／Ａｌ原子比が１
００１０．１であった。As a result of analysis, the composition of this product powder has a Zn/Al atomic ratio of 1.
It was 0010.1.
分光透過率の測定結果を第１図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例２
工業用９７％硝酸アルミニウム９水塩４４゜７ｇ及び工
業用９５％硝酸亜鉛６水塩３６２ｇをエタノール１２０
０ｍ１中に入れ、これを３０分間撹拌混合して溶解した
。Example 2 44.7 g of industrial 97% aluminum nitrate nonahydrate and 362 g of industrial 95% zinc nitrate hexahydrate were added to 120 g of ethanol.
0ml and stirred and mixed for 30 minutes to dissolve.
続いて９９％のへキサメチレンテトラミン２８３ｇを水
１６００ｍｉ！に溶かした水溶液を加えて、さらに撹拌
した。Next, add 283g of 99% hexamethylenetetramine to 1600ml of water! An aqueous solution dissolved in was added and further stirred.
これを加熱し、温度約８０℃にて撹拌下５時間、続いて
温度約１００℃で１時間加水分解を行い加水分解生成物
を得た。This was heated and hydrolyzed at a temperature of about 80° C. for 5 hours with stirring, and then at a temperature of about 100° C. for 1 hour to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｆｆ１で洗浄し、°温度１
５０℃で乾燥後、振動ミルで粉砕した。This was defiltered, washed with 1000 mff1 of water, and heated to 1 °C.
After drying at 50°C, it was pulverized using a vibration mill.
次いで温度約７００℃にて１時間焼成した。Then, it was fired at a temperature of about 700°C for 1 hour.
平均粒径約０．０１μｍの微粉末９７．１ｇを得た。97.1 g of fine powder with an average particle size of about 0.01 μm was obtained.
この製品粉末の組成は分析の結果Ｚｎ／Ａｌ原子比は１
００／ｌ Ｏであった。The composition of this product powder was analyzed and the Zn/Al atomic ratio was 1.
00/lO.
生成粉末の原子結合状態を測定したところ、−Ｚｎ−０
−Ａｌ＜結合（特性吸収６５０Ｃｍ−１）が認められた
。When the atomic bonding state of the produced powder was measured, it was found that -Zn-0
-Al<bond (characteristic absorption 650 Cm-1) was observed.
上記フィルムについて、分光透過率を測定した結果を第
１図に示す。The results of measuring the spectral transmittance of the above film are shown in FIG.
実施例３
９７％硝酸アルミニウム９水塩１９３ｇ及び９９％硝酸
亜鉛２水塩２２２ｇを、１ｓｏ−プロパツール１２００
ｍ１に入れ、これを３０分間撹拌混合し、９９％へキサ
メチレンテトラミン３６７ｇと水１６００ｍｊ！水溶液
を添加して撹拌し、これを温度約８０℃にて５時間、続
いて温度約１００℃で１時間加水分解反応を行い、加水
分解生成物を得た。Example 3 193 g of 97% aluminum nitrate nonahydrate and 222 g of 99% zinc nitrate dihydrate were added to 1so-propatool 1200
ml and stirred and mixed for 30 minutes, 367 g of 99% hexamethylenetetramine and 1600 mj of water! An aqueous solution was added and stirred, followed by a hydrolysis reaction at a temperature of about 80° C. for 5 hours and then at a temperature of about 100° C. for 1 hour to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｊ！で洗浄し、温度１５０
℃で乾燥後、振動ミルで粉砕した。I passed this and got 1000mj of water! Wash at a temperature of 150
After drying at °C, it was ground in a vibrating mill.
次いで温度約７００℃、１時間焼成して約１μｍより大
なる粒子を全く含まない、平均粒径約０．０５μｍの微
粉末１０３ｇを得た。The mixture was then calcined at a temperature of about 700° C. for 1 hour to obtain 103 g of fine powder containing no particles larger than about 1 μm and having an average particle size of about 0.05 μm.
この粉末の組成は分析の結果Ｚｎ／Ａ＋原子比がｌ Ｏ
Ｏ１５０であった。As a result of analysis, the composition of this powder was found to be Zn/A+ atomic ratio l O
It was O150.
生成粉末の結合状態を測定したところ−Ｚｎ−０−Ａ＋
＜結合（特性吸収６５０ ｃｍ−’）を確認した。When the bonding state of the produced powder was measured, it was -Zn-0-A+
<Bonding (characteristic absorption 650 cm-') was confirmed.
分光透過率を測定した結果を第１図に示す。The results of measuring the spectral transmittance are shown in FIG.
実施例４
四塩化チタン２．１９ｇ及び９５％硝酸亜鉛６水塩３６
２ｇをｎ−プロパツール１２００ｍ１に加え、これを３
０分間撹拌混合して溶解した。Example 4 2.19 g of titanium tetrachloride and 36 g of 95% zinc nitrate hexahydrate
Add 2g to 1200ml of n-proper tool and add 3g of this to 1200ml of n-proper tool.
The mixture was stirred and mixed for 0 minutes to dissolve.
次に工業用尿素２５０ｇと水１６００ｍｆとの水溶液を
添加して混合した。Next, an aqueous solution of 250 g of industrial urea and 1600 mf of water was added and mixed.
これを温度約９０℃にて４時間、続いて温度約１００°
Ｃで１時間加水分解反応を行い、加水分解生成物を得た
。This was carried out at a temperature of about 90°C for 4 hours, and then at a temperature of about 100°C.
A hydrolysis reaction was carried out at C for 1 hour to obtain a hydrolysis product.
これをデ過し、水１０００ｍｊ！で洗浄し、温度１５０
℃で乾燥後、振動ミルで粉砕した。I passed this and got 1000mj of water! Wash at a temperature of 150
After drying at °C, it was ground in a vibrating mill.
次いで温度約８５０℃、１時間焼成して、約１μｍより
大なる粒子を全く含まない平均粒径約０．０８μｍの微
粉末９２．７ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 92.7 g of fine powder with an average particle size of about 0.08 μm and containing no particles larger than about 1 μm.
この粉末の組成は分析の結果Ｚ ｎ ／ Ｔ ｉ原子比
が１００／１であった。As a result of analysis, the composition of this powder was found to have a Z n /Ti atomic ratio of 100/1.
分光透過率の測定結果を第１図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例５
四塩化チタン２１．９及び９５％硝酸亜鉛６水塩３６２
ｇをｎ−プロパツール１２００ｍｆに加え、これを３０
分間撹拌混合して溶解した。Example 5 Titanium tetrachloride 21.9 and 95% zinc nitrate hexahydrate 362
g to n-proper tool 1200mf and add this to 30
Stir and mix for a minute to dissolve.
次に尿素２５０ｇを水１６００ｍｌに溶した水溶液を添
加して、混合した。Next, an aqueous solution of 250 g of urea dissolved in 1,600 ml of water was added and mixed.
これを温度約９０℃で撹拌下４時間、続いて温度約１０
０℃で１時間加水分解反応を行い、加水分解生成物を得
た。This was stirred at a temperature of about 90°C for 4 hours, followed by a temperature of about 10°C.
A hydrolysis reaction was carried out at 0°C for 1 hour to obtain a hydrolysis product.
これを′濾過１水１０００ｍｆで洗浄し、温度１５０℃
で乾燥後、振動ミルで粉砕した。This was washed with 1000 mf of filtered water at a temperature of 150°C.
After drying, it was pulverized using a vibrating mill.
次いで温度約８５０°Ｃ，１時間焼成して、約１μｍよ
り大なる粒子を全く含まない平均粒径約０．２μｍの微
粉末１０１ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 101 g of fine powder having an average particle size of about 0.2 μm and containing no particles larger than about 1 μm.
この粉末の組成は分析の結果、Ｚ ｎ ／ Ｔ ｉ原子
比が１００／１０であった。As a result of analysis, the composition of this powder was found to have a Z n /Ti atomic ratio of 100/10.
この粉末の原子結合状態は、−Ｚｎ−０−Ｔｉ（−（特
性吸収７４０ｃｍ−）であることを確認した。The atomic bonding state of this powder was confirmed to be -Zn-0-Ti (-(characteristic absorption 740 cm-)).
分光透過率を測定した結果を第１図に示す。The results of measuring the spectral transmittance are shown in FIG.
実施例６
日本曹達製チタンイソプロポキシド３２．９ｇ、９５％
硝酸亜鉛６水塩３６２ｇをｎ−プロパツール１２００ｍ
ｎに熔解し、これを３０分間攪拌混合して溶解した。Example 6 Nippon Soda titanium isopropoxide 32.9g, 95%
Zinc nitrate hexahydrate 362g to n-propatool 1200m
This was stirred and mixed for 30 minutes to dissolve.
これに尿素２７８ｇを水１６００ｍ１に溶解した水溶液
を添加して混合した。An aqueous solution of 278 g of urea dissolved in 1,600 ml of water was added and mixed.
これを温度約９０℃で撹拌下５時間加水分解を行い、加
水分解生成物を得た。This was hydrolyzed at a temperature of about 90° C. for 5 hours with stirring to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｌで洗浄し、温度１５０℃
乾燥後、振動ミルで粉砕した。This was filtered and washed with 1000ml of water at a temperature of 150°C.
After drying, it was ground in a vibrating mill.
次いで温度約８５０℃、１時間焼成して約０．５μｍよ
り大なる粒子を全く含まない、平均粒径約０．１μｍの
微粉末１０１ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 101 g of a fine powder containing no particles larger than about 0.5 μm and having an average particle size of about 0.1 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｔｉ原子
比が１００／Ｉ Ｏであった。As a result of analysis, the composition of this product powder was found to have a Z n /Ti atomic ratio of 100/I 2 O.
この粉末の原子結合状態は、−Ｚｎ−０−Ｔ１そである
ことを確認した。It was confirmed that the atomic bonding state of this powder was -Zn-0-T1.
分光透過率を測定した結果を第１図に示す。The results of measuring the spectral transmittance are shown in FIG.
実施例７
日本曹達製チタンイソプロポキシド６５．８＆、９５９
Ａ硝酸亜鉛６水塩３６２ｇと１ｓｏ−プロパツール１２
００ｍｌに溶解し、これを３０分間撹拌混合して溶解し
た。Example 7 Titanium isopropoxide 65.8 & 959 manufactured by Nippon Soda
A Zinc nitrate hexahydrate 362g and 1so-propatool 12
00 ml and stirred and mixed for 30 minutes to dissolve.
これに工業用尿素２７８ｇと水１６００ｍｊ！との水溶
液を添加して混合した。This includes 278g of industrial urea and 1600mj of water! An aqueous solution of was added and mixed.
これを温度約８０℃で撹拌下５時間、続いて温度約１０
０℃で１時間加水分解反応を行い、加水分解生成物を得
た。This was stirred at a temperature of about 80°C for 5 hours, followed by a temperature of about 10°C.
A hydrolysis reaction was carried out at 0°C for 1 hour to obtain a hydrolysis product.
これを濾過し、水１０００ｍｊ！で洗浄し、温度１５０
℃乾燥後、振動ミルで粉砕した。Filter this and get 1000mj of water! Wash at a temperature of 150
After drying at °C, it was pulverized using a vibrating mill.
次いで温度約８５０℃、１時間焼成して約０．５μｍよ
り大なる粒子を全く含まない、平均粒径０．１μｍの微
粉末１）０ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 0 g of fine powder 1) having an average particle size of 0.1 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｔ ｉ原
子比が１００／２０であった。As a result of analysis, the composition of this product powder was found to have a Z n /Ti atomic ratio of 100/20.
この粉末の原子結合状態は、−Ｚｎ−０−Ｔｉく結合（
特性吸収７４０ ｃ ｍ−’）であることを確認した。The atomic bonding state of this powder is -Zn-0-Ti bond (
It was confirmed that the characteristic absorption was 740 cm-').
分光ｉ３過率を測定した結果を第１図に示す。The results of measuring the spectral i3 pass rate are shown in FIG.
実施例８
工業用９９％硝酸第２鉄９水塩０．０５２ｇ及び工業用
９５％硝酸亜鉛６水塩３９２ｇをノルマルプロパツール
１２００ｍｊ！に入れ、これを３０分間撹拌混合し、工
業用尿素２６２ｇと水１６００ｍ１との水溶液を添加し
て撹拌し、これを温度約９０℃にて４時間、続いて温度
約１００℃で１時間加水分解反応を行い、加水分解生成
物を得た。Example 8 0.052 g of industrial 99% ferric nitrate nonahydrate and 392 g of industrial 95% zinc nitrate hexahydrate were added to 1200 mj of normal propatool! This was stirred and mixed for 30 minutes, and an aqueous solution of 262 g of industrial urea and 1,600 ml of water was added and stirred, and this was hydrolyzed at a temperature of about 90°C for 4 hours, and then at a temperature of about 100°C for 1 hour. The reaction was carried out to obtain a hydrolysis product.
これをデ過し、水１０００ｍｆｆで洗浄し、温度１５０
℃で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered, washed with 1000 mff of water, and heated to 150 ml of water.
After drying at °C, it was ground in a hammer mill and a vibration mill.
次いで温度６００℃、１時間焼成して約１μｍより大な
る粒子を全く含まない平均粒径約０．０６μｍの微粉末
９７．４ｇを得た。The mixture was then calcined at a temperature of 600° C. for 1 hour to obtain 97.4 g of fine powder with an average particle size of about 0.06 μm and no particles larger than about 1 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｆ ｅ原
子比が１００１０．０１であった。Analysis of the composition of this product powder revealed that the Z n /Fe atomic ratio was 10010.01.
分光透過率の測定結果を第１図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例９
実施例８において、原料鉄塩量を５１ｇに、尿素量を３
０２ｇに代えた他は同一処理することで、約１μｍより
大なる粒子を全く含まない平均粒径約０．０８μｍの微
粉末１）０ｇを得た。Example 9 In Example 8, the amount of raw material iron salt was changed to 51 g, and the amount of urea was changed to 3.
By performing the same treatment except that 0.02 g was used, 0 g of fine powder 1) having an average particle size of about 0.08 μm and containing no particles larger than about 1 μm was obtained.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｆ ｅ原
子比が１００／ｌ Ｏであった。Analysis of the composition of this product powder revealed that the Zn/Fe atomic ratio was 100/lO.
生成粉末の結合状態を測定したところ−Ｚｎ−Ｏ−Ｆｅ
＜結合（特性吸収５３０ ｃｍ−’）を確認した。When the bonding state of the produced powder was measured, it was found that -Zn-O-Fe
<Bonding (characteristic absorption 530 cm-') was confirmed.
分光透過率の測定結果を第２図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１０
工業用９５％硝酸亜鉛６水塩３９２ｇ及び硝酸第１セリ
ウム６水塩０．０２７ｇをイソブタノール１２００ｍｆ
に入れ、これを３０分間撹拌混合し、工業用尿素２６２
ｇと水１６００ｍ１との水溶液を添加して撹拌し、これ
を温度約９０℃にて約４時間、続いて温度約１００℃で
１時間加水分解反応を行い、加水分解生成物を得た。Example 10 392 g of industrial 95% zinc nitrate hexahydrate and 0.027 g of cerous nitrate hexahydrate were mixed with 1200 mf of isobutanol.
The mixture was stirred and mixed for 30 minutes, and industrial urea 262
An aqueous solution of g and 1600 ml of water was added and stirred, and the mixture was subjected to a hydrolysis reaction at a temperature of about 90° C. for about 4 hours, and then at a temperature of about 100° C. for 1 hour to obtain a hydrolyzed product.
これをデ過し、水１０００ｍ／で洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered and washed with 1000 m/s of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次いで温度６００℃、１時間焼成して約１μｍより大な
る粒子を全く含まない平均粒径約０゜０１μｍの微粉末
９７．５ｇを得た。The mixture was then calcined at a temperature of 600° C. for 1 hour to obtain 97.5 g of fine powder having an average particle size of about 0.01 μm and containing no particles larger than about 1 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｃｅ原子
比が１００１０．００５であった。As a result of analysis, the composition of this product powder was found to have a Z n /Ce atomic ratio of 10010.005.
分光通過率の測定結果を第２図に示す。The measurement results of the spectral transmission rate are shown in FIG.
実施例１）
工業用９５％硝酸亜鉛６水塩３９２ｇ及び硝酸第１セリ
ウム６水塩０．０５５ｇをイソブタノール１２００ｍ１
に入れ、これを３０分間撹拌混合し、工業用尿素２６２
ｇと水１６００ｍβとの水？８液を添加して撹拌し、こ
れを温度約９０℃にて約４時間、続いて温度約１００
’Ｃで１時間加水分解反応を行い、加水分解生成物を得
た。Example 1) 392 g of industrial 95% zinc nitrate hexahydrate and 0.055 g of cerous nitrate hexahydrate were added to 1200 ml of isobutanol.
The mixture was stirred and mixed for 30 minutes, and industrial urea 262
g and water 1600mβ? 8 liquid was added and stirred, and this was heated at a temperature of about 90°C for about 4 hours, and then at a temperature of about 100°C.
A hydrolysis reaction was carried out at C for 1 hour to obtain a hydrolysis product.
これを′ｆｉｆｆ、、、水１０００ｍＩＴ：？’！ｃ浄
Ｌ、温度１５０℃で乾燥後、ハンマーミル及び振動ミル
で粉砕した。This is 'fiff..., water 1000 mIT:? '! After drying at a temperature of 150° C., it was pulverized using a hammer mill and a vibration mill.
次いで温度６００℃、１時間焼成して約１μｍより大な
る粒子を全く含まない平均粒径約０゜０１μｍの微粉末
９７．５ｇを得た。The mixture was then calcined at a temperature of 600° C. for 1 hour to obtain 97.5 g of fine powder having an average particle size of about 0.01 μm and containing no particles larger than about 1 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ ｃ６原子
比が１００１０．０１であった。As a result of analysis, the composition of this product powder was found to have a Z n /c6 atomic ratio of 10010.01.
分光透過率の測定結果を第２図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１２
実施例１）において、原料亜鉛塩量を７２゜１ｇに原料
セリウム塩量を２００ｇに代えた他は同一処理すること
で、約１μｍより大なる粒子を全く含まない平均粒径内
０．０３μｍの微粉末９７．１ｇを得た。Example 12 By carrying out the same treatment as in Example 1) except that the amount of raw material zinc salt was changed to 72°1 g and the amount of raw material cerium salt was changed to 200 g, the average particle size was 0.000, containing no particles larger than about 1 μm. 97.1 g of fine powder of .03 μm was obtained.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｃｅ原子
比が１００／２００であった。As a result of analysis, the composition of this product powder was found to have a Z n /Ce atomic ratio of 100/200.
生成粉末の結合状態を測定したところ−Ｚｎ−０−Ｃｅ
そ結合（特性吸収４１０ ａｍ−’）を確認した。When the bonding state of the produced powder was measured, it was found that -Zn-0-Ce
The bond (characteristic absorption 410 am-') was confirmed.
分光通過率の測定結果を第２図に示す。The measurement results of the spectral transmission rate are shown in FIG.
実施例１３
工業用９５％硝酸第２クロム９水塩０．２６４ｇ及び工
業用９５％硝酸亜鉛６水塩３９２ｇをノルマルブタノー
ル１２００ｍ１に入れ、これを３０分間撹拌混合し、工
業用９９％へキサメチレンテトラミン２６６ｇと水１６
００ｍ１との水溶液を添加して撹拌し、これを温度約９
０℃にて５時間加水分解反応を行い、加水分解生成物を
得た。Example 13 0.264 g of industrial 95% chromic nitric acid nonahydrate and 392 g of industrial 95% zinc nitrate hexahydrate were added to 1200 ml of n-butanol, and the mixture was stirred and mixed for 30 minutes to produce 99% industrial hexamethylene. 266g of tetramine and 16g of water
00 ml of aqueous solution was added and stirred, and the temperature was about 9
A hydrolysis reaction was carried out at 0°C for 5 hours to obtain a hydrolysis product.
これをデ過し、水１０００ｍ＋２で洗浄し、温度１５０
℃で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered, washed with water 1000m+2, and heated to a temperature of 150m.
After drying at °C, it was ground in a hammer mill and a vibration mill.
次いで温度６００℃、１時間焼成して杓０゜５μｍより
大なる粒子を全く含まない平均粒径約０．０１μｍの微
粉末９７．６ｇを得た。The mixture was then calcined at a temperature of 600° C. for 1 hour to obtain 97.6 g of fine powder with an average particle size of about 0.01 μm and containing no particles larger than 0.5 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｃｒ原子
比が１００１０．０５であった。As a result of analysis, the composition of this product powder was found to have a Z n /Cr atomic ratio of 10010.05.
分光透過率の測定結果を第２図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１４
工業用９５％硝酸第２クロム９水塩０．５２７ｇ及び工
業用９５％硝酸亜鉛６水塩３９２ｇをノルマルブタノー
ル１２００ｍ＋＋に入れ、これを３０分間撹拌混合し、
工業用９９％へキサメチレンテトラミン２６６ｇと水１
６００ｍｊ！との水溶液を添加して攪拌し、これを温度
約９０℃にて５時間加水分解反応を行い、加水分解生成
物を得た。Example 14 0.527 g of industrial 95% chromic nitric acid nonahydrate and 392 g of industrial 95% zinc nitrate hexahydrate were added to 1200 m++ of n-butanol, and the mixture was stirred and mixed for 30 minutes.
Industrial grade 99% hexamethylenetetramine 266g and water 1
600mj! An aqueous solution of was added and stirred, and a hydrolysis reaction was carried out at a temperature of about 90° C. for 5 hours to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｊ！で洗浄し、温度１５０
℃で乾燥後、ハンマーミル及び振動ミルで粉砕した。I passed this and got 1000mj of water! Wash at a temperature of 150
After drying at °C, it was ground using a hammer mill and a vibration mill.
次いで温度６００℃、１時間焼成して約０゜５μｍより
大なる粒子を全く含まない平均粒径約０．０１μｍの微
粉末９７．６ｇを得た。The mixture was then calcined at a temperature of 600° C. for 1 hour to obtain 97.6 g of fine powder having an average particle size of about 0.01 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果Ｚｎ／Ｃｒ原子比が１
００１０．１であった。As a result of analysis, the composition of this product powder has a Zn/Cr atomic ratio of 1.
It was 0010.1.
分光透過率の測定結果を第２図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１５
実施例１４において、原料亜鉛塩量を３１３ｇに原料ク
ロム塩量を２１）ｇに、ヘキサメチレンテトラミン量を
３７２ｇに代えた他は同一処理することで、約１μｍよ
り大なる粒子を全く含まない平均粒径約０．０４μｍの
微粉末１２６ｇを得た。Example 15 By performing the same treatment as in Example 14 except that the amount of raw material zinc salt was changed to 313 g, the amount of raw material chromium salt was changed to 21) g, and the amount of hexamethylenetetramine was changed to 372 g, particles larger than about 1 μm were completely removed. 126 g of fine powder with an average particle diameter of about 0.04 μm was obtained.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｃｒ原子
比が１００１５０であった。As a result of analysis, the composition of this product powder was found to have a Z n /Cr atomic ratio of 100,150.
生成粉末の結合状態を測定したところ−Ｚｎ−〇−Ｃｒ
く結合（特性吸収６１０ ｃｍ−’）を確認した。When the bonding state of the produced powder was measured, it was found that -Zn-〇-Cr
A strong bond (characteristic absorption 610 cm-') was confirmed.
分光透過率の測定結果を第２図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１６
オキシ塩化ジルコニウム８水塩０．２０１ｇ及び工業用
９５９Ａ硝酸亜鉛６水塩３９２ｇをエタノール５００ｍ
ｊ！に入れ、これを３０分間攪拌混合し、工業用尿素２
２５ｇと水２３００ｍｅとの水７８液を添加して撹拌し
、これを温度約８０℃にて５時間、続いて温度約【００
°Ｃで１時間加水分解反応を行い、加水分解生成物を得
た。Example 16 0.201 g of zirconium oxychloride octahydrate and 392 g of industrial grade 959A zinc nitrate hexahydrate were added to 500 m of ethanol.
j! The mixture was stirred and mixed for 30 minutes, and industrial urea 2
Add 78 liquids of 25g and 2300me of water, stir, and heat at a temperature of about 80°C for 5 hours, then at a temperature of about 00°C.
A hydrolysis reaction was carried out at °C for 1 hour to obtain a hydrolysis product.
これをデ過し、水１０００ｍｊ！で洗浄し、温度１５０
℃で乾燥後、ハンマーミル及び振動ミルで粉砕した。I passed this and got 1000mj of water! Wash at a temperature of 150
After drying at °C, it was ground in a hammer mill and a vibration mill.
次いで温度６５０℃、１時間焼成して約０゜５μｍより
大なる粒子を全く含まない平均粒径約０，０１μｍの微
粉末９８１ｇを得た。The mixture was then calcined at a temperature of 650° C. for 1 hour to obtain 981 g of fine powder having an average particle size of about 0.01 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｚ ｒ原
子比が１００１０．０５であった。Analysis of the composition of this product powder revealed that the Zn/Zr atomic ratio was 10010.05.
分光透過率の測定結果を第３図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１７
実施例１６において、原料ジルコニウム塩量を４．０３
ｇに、加水分解沈澱剤として尿素をヘキサメチレンテト
ラミン３１０ｇに代えて使用する他は同一処理すること
により約０．５μｍより大なる粒子を全く含まない平均
粒径約０．０１μｍの微粉末１０１ｇを得た。この製品
粉末の組成は分析の結果、Ｚ ｎ ／ Ｚ ｒ原子比が
１００／１であった。Example 17 In Example 16, the amount of raw material zirconium salt was 4.03
g, 101 g of fine powder with an average particle size of about 0.01 μm containing no particles larger than about 0.5 μm was obtained by the same treatment except that 310 g of hexamethylenetetramine was replaced with urea as a hydrolysis precipitant. Obtained. Analysis of the composition of this product powder revealed that the Zn/Zr atomic ratio was 100/1.
分光透過率の測定結果を第 図に示す。The measurement results of spectral transmittance are shown in Figure.
実施例１８
実施例１６において、原料亜鉛塩量を３１３ｇに、原料
ジルコニウム塩量を１２９ｇに、尿素量を２７０ｇに代
えた他は同一処理することで、約０．５μｍより大なる
粒子を全く含まない平均粒径約０．０２μｍの微粉末１
２７ｇを得た。Example 18 By carrying out the same treatment as in Example 16 except that the amount of raw material zinc salt was changed to 313 g, the amount of raw material zirconium salt was changed to 129 g, and the amount of urea was changed to 270 g, no particles larger than about 0.5 μm were contained. Fine powder 1 with an average particle size of approximately 0.02 μm
27g was obtained.
この製品粉末の組成は分析の結果Ｚｎ／Ｚ「原子比が１
００／４０であった。As a result of analysis, the composition of this product powder was found to be Zn/Z with an atomic ratio of 1.
It was 00/40.
生成粉末の結合状態を測定してところ−Ｚｎ−０−Ｚｒ
４結合（特性吸収６４０ ｃ ｍ−’）を確認した。When the bonding state of the produced powder was measured -Zn-0-Zr
4 bonds (characteristic absorption 640 cm-') were confirmed.
分光透過率の測定結果を第３図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例１９
四基チタン１８．７ｇを９７％硝酸アルミニウム９水塩
１５２ｇ及び９５％硝酸亜鉛６水塩３０８ｇをエチレン
グリコール２００ｍｊ！に溶解した。Example 19 18.7 g of quaternary titanium, 152 g of 97% aluminum nitrate nonahydrate, and 308 g of 95% zinc nitrate hexahydrate were mixed with 200 mj of ethylene glycol! dissolved in.
これに尿素３１９ｇを水２６００ｍｊ！に溶解した水溶
液を添加し、混合した。Add 319g of urea and 2600mj of water! was added and mixed.
これを温度約１００℃にて、攪拌下３時間加水分解を行
い、加水分解生成物を得た。This was hydrolyzed at a temperature of about 100°C for 3 hours with stirring to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｊ＋で洗浄、温度１５０℃
で乾燥後、振動ミルで粉砕した。This was defiltered and washed with 1000 mj+ of water at a temperature of 150°C.
After drying, it was pulverized using a vibrating mill.
次いで温度８５０℃、１時間焼成して約１μｍより大な
る粒子を全く含まない、平均粒径約０．２μｍの微粉末
１０８ｇを得た。The mixture was then calcined at a temperature of 850° C. for 1 hour to obtain 108 g of fine powder containing no particles larger than about 1 μm and having an average particle size of about 0.2 μm.
この粉末の組成は、分析の結果Ｚ ｎ ／ Ａ １ ／
Ｔｉ原子比が１００／４０／ｌ Ｏであった。As a result of analysis, the composition of this powder is Z n / A 1 /
The Ti atomic ratio was 100/40/lO.
この粉末の原子結合状態を測定したところ）Ｔｉ −０
−Ｚｎ−０−Ａ１＜結合（特性吸収６５０ ｃ ｍ−’
、７４０ ｃ ｍ−’）を確認した。When the atomic bonding state of this powder was measured) Ti -0
-Zn-0-A1<bond (characteristic absorption 650 cm m-'
, 740 cm-').
分光透過率を測定した結果を第３図に示す。The results of measuring the spectral transmittance are shown in FIG.
実施例２０
工業用四塩化チタン２１．９ｇ、硫酸第１セリウム８水
塩２．０６ｇ及び工業用９５％硝酸亜鉛６水塩３６２ｇ
をジエチレングリコール１２００ｍＩｌに入れ３０分間
撹拌混合した。Example 20 21.9 g of industrial titanium tetrachloride, 2.06 g of ceric sulfate octahydrate, and 362 g of industrial 95% zinc nitrate hexahydrate
was added to 1200 ml of diethylene glycol and mixed with stirring for 30 minutes.
次に工業用尿素２５２ｇと水１６００ｍｊ！との水溶液
を添加して混合した。Next, 252g of industrial urea and 1600mj of water! An aqueous solution of was added and mixed.
これを撹拌下に温度約１００℃、３時間加水分解反応を
行い、加水分解生成物を得た。This was subjected to a hydrolysis reaction at a temperature of about 100° C. for 3 hours while stirring to obtain a hydrolysis product.
これをデ過し、水１０１００Ｏで洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered, washed with 10,100O water, and heated to 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次いで温度約８５０℃、１時間焼成して約０．５μｍよ
り大なる粒子を全く含まない平均粒径約０．０２μｍの
微粉末１０４ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 104 g of fine powder having an average particle size of about 0.02 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ｃｅ／
Ｔ ｉ原子比が１００１０．５／１０であった。As a result of analysis, the composition of this product powder is Z n / Ce /
The Ti atomic ratio was 10010.5/10.
この粉末の原子結合状態は−Ｚｎ−０−Ｔｉ（−結合（
特性吸収６００ｃｍ６’、７４０ ｃ ｍ−’）である
ことを認めた。The atomic bonding state of this powder is -Zn-0-Ti (- bond (
It was found that the characteristic absorption was 600 cm6', 740 cm-').
分光透過率の測定結果を第１図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例２１
工業用９７％硝酸アルミニウム９水塩４４゜７ｇ、工業
用９５％硝酸亜鉛６水塩３６２ｇ及び硝酸第２鉄９水塩
４．７２ｇをエタノール１２００−に入れ、これを３０
分間攪拌混合して溶解した。続いて工業用９９％へキサ
メチレンテトラミン２８６ｇを水１６０（ｌｄに？容か
した水溶液を加えて、更に攪拌した。Example 21 44.7 g of industrial 97% aluminum nitrate nonahydrate, 362 g of industrial 95% zinc nitrate hexahydrate, and 4.72 g of ferric nitrate nonahydrate were added to 1200 g of ethanol, and
Dissolved by stirring and mixing for a minute. Subsequently, an aqueous solution of 286 g of industrial grade 99% hexamethylenetetramine in 160 ml of water was added and further stirred.
これを撹拌下に加熱し、温度約８０℃にて５時間、続い
て温度約ｌＯＯ℃で１時間加水分解反応を行い、加水分
解生成物を得た。これを濾過し、水１０００−で洗浄し
、温度１５０℃で乾燥後、ハンマーミル及び振動ミルで
粉砕した。This was heated with stirring to carry out a hydrolysis reaction at a temperature of about 80° C. for 5 hours and then at a temperature of about 100° C. for 1 hour to obtain a hydrolyzed product. This was filtered, washed with 1,000 ml of water, dried at a temperature of 150°C, and then ground with a hammer mill and a vibration mill.
次いで温度約７００℃１時間後、焼成して、約１μｍよ
り大なる粒子を全く含まない平均粒径約０．０１μｍの
肌ざわりの良好な微粉末である淡黄色の製品９８．５ｇ
を得た。Then, after 1 hour at a temperature of about 700°C, it was fired to give 98.5 g of a pale yellow product, which is a fine powder with a good texture and an average particle size of about 0.01 μm, containing no particles larger than about 1 μm.
I got it.
この製品粉末の組成は分析の結果Ｚｎ／Ａｆｆ／Ｆｅ原
子比が１００／ｌ Ｏ／１であった。As a result of analysis, the composition of this product powder was found to have a Zn/Aff/Fe atomic ratio of 100/l O/1.
生成粉末の原子結合状態を測定したところ、−Ｚｎ−ｏ
−Ａｆ＜結合（特性吸収６５０ ｃ ｍ−’）が認めら
れた。When the atomic bonding state of the produced powder was measured, it was found that -Zn-o
-Af<binding (characteristic absorption 650 cm-') was observed.
分光透過率の測定結果を第３図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例２２
工業用９７％硝酸アルミニウム９水塩４４゜７ｇ、工業
用９５％硝酸亜鉛６水塩３６２ｇ及び硝酸第１セリウム
６水塩５．０２ｇをエチレングリコール１２００−に入
れ、３０分間攪拌ｌ昆合した。Example 22 44.7 g of industrial grade 97% aluminum nitrate hexahydrate, 362 g of industrial grade 95% zinc nitrate hexahydrate, and 5.02 g of cerous nitrate hexahydrate were added to 1200 g of ethylene glycol and stirred for 30 minutes. It matched.
次いで、工業用９９％へキサメチレンテトラミン２８６
ｇと水１６００−との水溶液を天下混合した。Then, industrial 99% hexamethylenetetramine 286
An aqueous solution of 1,600 g of water and 1,600 g of water was mixed together.
これを撹拌下に、温度約１００℃、３時間加水分解反応
を行い加水分解生成物を得た。これを濾過し、水１００
０−で洗浄し、温度１５０℃で乾燥後、ハンマーミル及
び振動ミルで粉砕した。While stirring, a hydrolysis reaction was carried out at a temperature of about 100° C. for 3 hours to obtain a hydrolysis product. Filter this and add 100% water
After washing at 0- and drying at a temperature of 150°C, it was pulverized using a hammer mill and a vibration mill.
次いで、温度約７００℃、１時間焼成して約０．５μｍ
より大なる粒子を全く含まない平均粒径０．０２μｍの
微粉末９８．７ｇを得た。Next, it is baked at a temperature of about 700°C for 1 hour to obtain a thickness of about 0.5 μm.
98.7 g of a fine powder with an average particle size of 0.02 μm, containing no larger particles, was obtained.
生成粉末の原子結合状態を測定したところ、−Ｚｎ−０
−Ａｌ＜結合（特性吸収６５０ ｃｍ−’）が認められ
た。When the atomic bonding state of the produced powder was measured, it was found that -Zn-0
-Al<bond (characteristic absorption 650 cm-') was observed.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ａ １／
Ｃｅ原子比が１００／１０／ｌであった。The composition of this product powder is the result of analysis Z n / A 1 /
The Ce atomic ratio was 100/10/l.
分光透過率の測定結果を第３図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例２３
工業用四塩化チタン２１．９ｇ、工業用９９％硝酸第２
鉄９水塩４．７２ｇ及び工業用９５％硝酸亜鉛６水塩３
６２ｇを、ノルマルプロパツール１２００ｍに入れ、こ
れを３０分間撹拌混合した。Example 23 21.9 g of industrial titanium tetrachloride, 21.9 g of industrial 99% nitric acid
Iron nonahydrate 4.72g and industrial 95% zinc nitrate hexahydrate 3
62 g was placed in a normal propatool 1200 m, and the mixture was stirred and mixed for 30 minutes.
次に工業用尿素２５３ｇと水１６００ｍとの水溶液を添
加混合した。Next, an aqueous solution of 253 g of industrial urea and 1600 m of water was added and mixed.
これを攪拌下、温度約９０℃５時間加水分解反応を行い
、加水分解生成物を得た。これを濾過し、水１０００−
で洗浄し、温度１５０℃乾燥後、ハンマーミル及び、振
動ミルで粉砕した。This was subjected to a hydrolysis reaction at a temperature of about 90° C. for 5 hours while stirring to obtain a hydrolyzed product. Filter this and water 1000-
After washing with water and drying at a temperature of 150°C, the powder was pulverized with a hammer mill and a vibration mill.
次いで温度約８５０℃１時間焼成して約０゜５μｍより
大なる粒子を全く含まない平均粒径約０．０３ｐｍの微
粉末１０４ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 104 g of fine powder having an average particle size of about 0.03 pm and containing no particles larger than about 0.5 μm.
この粉末の組成は分析の結果、Ｚ ｎ ／ Ｆ ｅ ／
Ｔ１原子比が１００／１／１０であった。As a result of analysis, the composition of this powder was found to be Z n / Fe /
The T1 atomic ratio was 100/1/10.
この粉末の原子結合状態は−Ｚｎ−〇−Ｔｉそ結合（特
性吸収６００ｃｍ−’、７４０ ｃ ｍ−’）であるこ
とを認めた。It was confirmed that the atomic bonding state of this powder was -Zn-〇-Ti bond (characteristic absorption 600 cm-', 740 cm-').
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
実施例２４
工業用９９％酢酸亜鉛２水塩２７７ｇ、工業用９７％硝
酸アルミニウム９水塩４Ｂ、３ｇ工業用９９％硝酸第２
鉄９水塩５．１ｇ及び硫酸第１セリウム８水塩２．２４
ｇをエタノール３００ｍｌに入れ、３０分間攪拌混合し
た。Example 24 277 g of industrial 99% zinc acetate dihydrate, 3 g of industrial 97% aluminum nitrate nonahydrate 4B, 3 g of industrial 99% nitric acid dihydrate
Iron nonahydrate 5.1g and ceric sulfate octahydrate 2.24g
g was added to 300 ml of ethanol and stirred and mixed for 30 minutes.
次に工業用尿素２６４ｇと水２５００ｍｊ＋との水溶液
を添加してｔ１合した。Next, an aqueous solution of 264 g of industrial urea and 2500 mj+ of water was added and combined for t1.
これを撹拌下に温度約８０℃、５時間続いて温度約１０
０℃、１時間加水分解反応を行い、加水分解生成物を得
た。This was stirred at a temperature of about 80°C for 5 hours, and then heated at a temperature of about 10°C for 5 hours.
A hydrolysis reaction was carried out at 0°C for 1 hour to obtain a hydrolysis product.
これをデ過し、水１０００ｍｊ！で洗浄し、温度１５０
℃で乾燥後、ハンマーミル及び振動ミルで粉砕した。I passed this and got 1000mj of water! Wash at a temperature of 150
After drying at °C, it was ground using a hammer mill and a vibration mill.
次いで温度７５０℃、１時間焼成して約０゜５μｍより
大なる粒子を全く含まない平均粒径約０２０１μｍの微
粉末１）０ｇを得た。The mixture was then calcined at a temperature of 750° C. for 1 hour to obtain 0 g of fine powder 1) having an average particle size of about 0.201 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果Ｚｎ／Ａｚ／ Ｆ ｅ
／ Ｃｅ原子比が１００／１０／１）０゜５であった
。As a result of analysis, the composition of this product powder is Zn/Az/Fe
/Ce atomic ratio was 100/10/1)0°5.
この粉末の原子結合状態は−Ｚｎ−０−Ａｌｌ＜結合（
特性吸収６５０Ｃｍ−’）であることを認めた。The atomic bond state of this powder is -Zn-0-All<bond (
It was confirmed that the characteristic absorption was 650 Cm-').
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
実施例２５
工業用９５％硝酸亜鉛６水塩３０８ ｇ’−工業用９７
％硝酸アルミニウム９水塩１５２ｇ、工業用９９％硝酸
第２鉄９水塩２．０１ｇ及び工業用四塩化チタン１８．
７ｇをプロピレングリコール４００ｍｊ！に入れ、３０
分間攪拌混合した。Example 25 Industrial 95% zinc nitrate hexahydrate 308 g'-Industrial 97
% aluminum nitrate nonahydrate 152 g, industrial 99% ferric nitrate nonahydrate 2.01 g and industrial titanium tetrachloride 18.
7g of propylene glycol 400mj! Put it in, 30
Mix by stirring for a minute.
次に工業用尿素３２０ｇと水１６００ｍｆとの水？８液
を添加して混合した。Next, 320g of industrial urea and 1600mf of water? 8 liquids were added and mixed.
これを攪拌下に、温度約ｌＯＯ°Ｃ１３時間加水分解反
応を行い、加水分解生成物を得た。While stirring, a hydrolysis reaction was carried out at a temperature of about 100° C. for 13 hours to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｌで洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was filtered and washed with 1000ml of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次いで温度約８５０℃、１時間焼成して約１μｍより大
なる粒子を全く含まない平均粒径約０．０４μｍの微粉
末１０８ ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 108 g of a fine powder having an average particle size of about 0.04 μm and containing no particles larger than about 1 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ａ Ｒ／
Ｆ ｅ ／ Ｔ ｉ原子比が１００／４０１０．５／
１０であった。The composition of this product powder is based on the analysis result Z n / A R /
Fe/Ti atomic ratio is 100/4010.5/
It was 10.
この粉末の原子結合状態は−）Ｔｉ −０−Ｚｎ−Ｏ−
Ａｌ＜結合（特性吸収６５０ｃｍ−’、７４０ Ｃｍ−
’）であることを認めた。The atomic bonding state of this powder is -)Ti -0-Zn-O-
Al< bond (characteristic absorption 650 cm-', 740 Cm-
').
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
実施例２６
工業用９５％硝酸亜鉛６水塩３０８ｇ、工業用９７％硝
酸アルミニウム９水塩ｔ５２ｇ、ＩＸ？酸第１セリウム
８水塩２．２４ｇ及び工業用四塩化チタン１８．７ｇを
イソプロパツール１２Ｑ Ｑｍｆｆｉに入れ、３０分間
攪拌混合した。Example 26 308 g of industrial 95% zinc nitrate hexahydrate, 52 g of industrial 97% aluminum nitrate nonahydrate, IX? 2.24 g of ceric acid octahydrate and 18.7 g of industrial titanium tetrachloride were placed in an isopropanol 12Q Qmffi and stirred and mixed for 30 minutes.
次に工業用尿素３２０ｇと水１６００ｍｊ！との水溶液
を添加して混合した。Next, 320g of industrial urea and 1600mj of water! An aqueous solution of was added and mixed.
これを攪拌下に、温度約８０℃、４時間、続いて温度約
１００℃、１時間加水分解反応を行い、加水分解生成物
を得た。This was subjected to hydrolysis reaction at a temperature of about 80° C. for 4 hours and then at a temperature of about 100° C. for 1 hour while stirring to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｌで洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was filtered and washed with 1000ml of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次いで温度約８５０℃、１時間焼成して約０．５μｍよ
り大なる粒子を全く含まない平均粒径約０．０５μｍの
微粉末１０９ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 109 g of fine powder having an average particle size of about 0.05 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ａ １／
Ｃｅ ／ Ｔ ｉ原子比がｔｏｏ／４０１０．５／１
０であった。The composition of this product powder is the result of analysis Z n / A 1 /
Ce/Ti atomic ratio is too/4010.5/1
It was 0.
この粉末の原子結合状態は−＞Ｔｉ −０−Ｚｎ−ｏ−
Ａｅ＜結合（特性吸収６５０ｃｍ−’、７４０ Ｃｍ６
’）であることを認めた。The atomic bonding state of this powder is ->Ti -0-Zn-o-
Ae<bond (characteristic absorption 650 cm-', 740 Cm6
').
分光透過率の測定結果を第２図に示す。The measurement results of the spectral transmittance are shown in FIG.
実施例２７
工業用９５％硝酸亜鉛６水塩３６２ｇ、工業用９９％硝
酸第２鉄９水塩４．７２ｇ、硫酸第１セリウム日水塩２
．２４ｇ及び日本曹達製チタンイソプロポキシド３’２
．９ｇをイソプロパツール１２００ｍｌに入れ、３０分
間攪拌混合した。Example 27 362 g of industrial 95% zinc nitrate hexahydrate, 4.72 g of industrial 99% ferric nitrate nonahydrate, 2 ceric sulfate dihydrate
．． 24g and Nippon Soda titanium isopropoxide 3'2
．． 9 g was added to 1200 ml of isopropanol and stirred and mixed for 30 minutes.
次に工業用尿素２５５ｇと水１６００ｍｊ！との水溶液
を添加して混合した。Next, 255g of industrial urea and 1600mj of water! An aqueous solution of was added and mixed.
これを攪拌下に、温度約８０℃、４時間、続いて温度約
１００℃、１時間加水分解反応を行い、加水分解生成物
を得た。This was subjected to hydrolysis reaction at a temperature of about 80° C. for 4 hours and then at a temperature of about 100° C. for 1 hour while stirring to obtain a hydrolyzed product.
これをデ過し、水１０００ｍｆで洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered and washed with 1000mf of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次いで温度８５０℃、１時間焼成して約０゜５μｍより
大なる粒子を全く含まない平均粒径約０．０３μｍの微
粉末１０５ｇを得た。The mixture was then calcined at a temperature of 850° C. for 1 hour to obtain 105 g of a fine powder with an average particle size of about 0.03 μm and containing no particles larger than about 0.5 μm.
この製品粉末の組成は分析の結果、Ｚ ｎ ／ Ｆｅ
／ Ｃｅ ／ Ｔ ｉ原子比が１００／１）０．５／１
０であった。As a result of analysis, the composition of this product powder was found to be Zn/Fe
/ Ce / Ti atomic ratio is 100/1) 0.5/1
It was 0.
この粉末の原子結合状態は−Ｚｎ−〇−Ｔｉく結合（特
性吸収６００ｃｍ”、７４ Ｑ ｃｍ−’）であること
を認めた。It was confirmed that the atomic bond state of this powder was -Zn-〇-Ti bond (characteristic absorption 600 cm'', 74 Q cm-').
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
実施例２８
工業用９５％硝酸亜鉛６水塩３０８ｇ、工業用９７％硝
酸アルミニウム９水塩１５２ｇ、工業用９９％硝酸第２
鉄９水塩２．０１ｇ、硝酸第１セリウ６水塩２．１４ｇ
及び工業用四塩化チタン１８．７ｇをグリセリン４００
ｍｌに入れ、３０分間攪拌混合した。Example 28 308 g of industrial 95% zinc nitrate hexahydrate, 152 g of industrial 97% aluminum nitrate nonahydrate, 99% industrial nitric acid 2
Iron nonahydrate 2.01g, Serium nitric acid hexahydrate 2.14g
and 18.7 g of industrial titanium tetrachloride in 400 g of glycerin.
ml and stirred and mixed for 30 minutes.
次に工業用尿素３２２ｇと水１６００ｍｆｆ１との水溶
液を添加して混合した。Next, an aqueous solution of 322 g of industrial urea and 1600 mff1 of water was added and mixed.
これを撹拌下に、温度約１００℃、３時間加水分解反応
を行い、加水分解生成物を得た。While stirring, a hydrolysis reaction was carried out at a temperature of about 100° C. for 3 hours to obtain a hydrolyzed product.
これをデ過し、水１０００ｍＪで洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered and washed with 1000mJ of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次い、で温度約８５０℃、１時間焼成して約１μｍより
大なる粒子を全く含まない平均粒径約０．０５μｍの微
粉末１０９ｇを得た。The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 109 g of fine powder with an average particle size of about 0.05 μm and no particles larger than about 1 μm.
この製品粉末の組成は分析の結果Ｚ ｎ ／ Ａ １Ｆ
ｅ ／ Ｃｅ ／ Ｔ ｊ原子比が１００／４０１０
゜５１０．５／１０であった。The composition of this product powder is the result of analysis Z n / A 1F
e / Ce / T j atomic ratio is 100/4010
It was 510.5/10.
この粉末の原子結合状態は）Ｔｉ −０−Ｚｎ−Ｏ−Ａ
１＜結合（特性吸収６５０ｃｍ−’、７４０ Ｃｍ−’
）であることを認めた。The atomic bonding state of this powder is )Ti-0-Zn-O-A
1< bond (characteristic absorption 650 cm-', 740 Cm-'
).
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
実施例２９
工業用９５％硝酸亜鉛６水塩６２．６ｇ、工業用９７％
硝酸アルミニウム１８水塩３４，４ｇ１工業用９９％硝
酸第２鉄９水塩８．１５ｇ、工業用９５％硝酸第２クロ
ム９水塩２５．３ｇ、硫酸第１セリウム日水塩１４３ｇ
及び工業用硫酸チタニル６．４ｇを水５００ｍｊ！に入
れ３０分間攪拌混合した。Example 29 62.6 g of industrial 95% zinc nitrate hexahydrate, 97% industrial
Aluminum nitrate 18 hydrate 34.4 g 1 Industrial 99% ferric nitrate nonahydrate 8.15 g, Industrial 95% chromic nitric acid nonahydrate 25.3 g, Ceric sulfate dihydrate 143 g
And 6.4g of industrial titanyl sulfate and 500mj of water! and stirred and mixed for 30 minutes.
次いでエタノール１２００ｍ１並びに工業用尿素２８０
ｇと水１）００ｍｊ！との水溶液を添加混合した。Then 1200 ml of ethanol and 280 ml of industrial urea
g and water 1) 00mj! An aqueous solution of was added and mixed.
これを攪拌下に、温度約８０℃、５時間次いで温度約１
００℃、１時間加水分解反応を行い加水分解生成物を得
た。This was stirred at a temperature of about 80°C for 5 hours, and then at a temperature of about 1°C.
A hydrolysis reaction was carried out at 00°C for 1 hour to obtain a hydrolysis product.
これをデ過し、水１０００ｍｆで洗浄し、温度１５０℃
で乾燥後、ハンマーミル及び振動ミルで粉砕した。This was defiltered and washed with 1000mf of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.
次いで温度８５０℃、１時間焼成して約１μｍより大な
る粒子を全く含まない平均粒径約０．０８μｍの微粉末
１０１ｇを得た。The mixture was then calcined at a temperature of 850° C. for 1 hour to obtain 101 g of fine powder with an average particle size of about 0.08 μm and containing no particles larger than about 1 μm.
生成粉末の原子結合状態を測定したところ、−Ｚｎ−０
−ＡＩ＜結合、−Ｚｎ−０−Ｆｅ＜結合、 Ｚｎ−０−
Ｃｒ＜結合、−Ｚｎ−○−Ｃｅそ結合及び−Ｚｎ−○−
Ｔｉ（−結合を確認した。When the atomic bonding state of the produced powder was measured, it was found that -Zn-0
-AI<bond, -Zn-0-Fe<bond, Zn-0-
Cr< bond, -Zn-○-Ce bond and -Zn-○-
Ti(- bond was confirmed.
この製品粉末の組成は分析の結果、Ｚ ｎ ／ Ａ１
／ Ｆ ｅ ／ Ｃｒ ／ Ｃｅ ／ Ｔ ｉ原子比が
１００１５０／１０／３０／２００／２０であった。As a result of analysis, the composition of this product powder is Z n / A1
/ Fe / Cr / Ce / Ti atomic ratio was 100150/10/30/200/20.
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
実施例３０
実施例２９における各原料塩とオキシ塩化ジルコニウム
８水塩３２．２ｇを水５００ｍ１に入れ３０分間撹拌混
合した。Example 30 Each raw material salt in Example 29 and 32.2 g of zirconium oxychloride octahydrate were added to 500 ml of water and mixed with stirring for 30 minutes.
次いでエタノール１２００ｍｊ！並びに工業用尿素３１
０ｇと水１）００ｍｌとの水溶液を添加混合した。Next, 1200 mj of ethanol! and industrial urea 31
An aqueous solution of 0 g and 1) 00 ml of water was added and mixed.
以下、実施例２９と同様に、反応、デ過、洗浄、乾燥、
粉砕、焼成して約０．５μｍより大なる粒子を全く含ま
ない平均粒径０．０１μｍの微粉末１）１ｇを得た。Hereinafter, in the same manner as in Example 29, reaction, filtration, washing, drying,
The powder was crushed and calcined to obtain 1 g of fine powder 1) having an average particle size of 0.01 μm and containing no particles larger than about 0.5 μm.
生成粉末の原子結合状態を測定したところ、−Ｚｎ−０
−ＡＩ＜結合、−Ｚｎ−０−Ｆｅ＜結合、−Ｚｎ−０−
Ｃｒ＜結合、−Ｚｎ−０−Ｃｅ（結合、−Ｚｎ−０−Ｔ
ｉ（−結合及び−Ｚｎ−０−Ｚｒ（−結合を確認した。When the atomic bonding state of the produced powder was measured, it was found that -Zn-0
-AI<bond, -Zn-0-Fe<bond, -Zn-0-
Cr<bond, -Zn-0-Ce (bond, -Zn-0-T
i(- bond and -Zn-0-Zr(- bond) were confirmed.
この製品粉末の組成は分析の結果、Ｚｎ／ＡＩ ／ Ｆ
ｅ ／ Ｃｒ ／ Ｃｅ ／ Ｔ ｉ ／ Ｚ ｒ原
子比が１であった。As a result of analysis, the composition of this product powder is Zn/AI/F.
The e/Cr/Ce/Ti/Zr atomic ratio was 1.
分光透過率の測定結果を第４図に示す。The measurement results of spectral transmittance are shown in FIG.
比較例１
和光純薬工業製工業用酸化アルミニウム粉末２３．９ｇ
及び山田薬品製工業用酸化亜鉛７６．１ｇをボールミル
で６時間粉砕混合した後、温度約７００℃で１時間焼成
した。Comparative Example 1 Wako Pure Chemical Industries industrial aluminum oxide powder 23.9g
After pulverizing and mixing 76.1 g of industrial zinc oxide manufactured by Yamada Pharmaceutical Co., Ltd. in a ball mill for 6 hours, the mixture was fired at a temperature of about 700° C. for 1 hour.
得られた粉末のＺ ｎ ／ Ａ １原子比は１００１５
０で平均粒径は約０．２μｍであった。The Z n /A 1 atomic ratio of the obtained powder was 10015
0 and the average particle size was about 0.2 μm.
この粉末の原子結合状態を測定したところ、−Ｚｎ−ｏ
−Ａ１＜結合は認められず、単なる酸化亜鉛と酸化アル
ミニウムの混合粉末であることが確認された。When the atomic bonding state of this powder was measured, it was found that -Zn-o
-A1< No bond was observed, and it was confirmed that the powder was simply a mixed powder of zinc oxide and aluminum oxide.
分光透過率を測定した結果を第５図に示す。The results of measuring the spectral transmittance are shown in FIG.
比較例２
和光純薬工業製工業用酸化チタン粉末９．２４ｇ及び山
田薬品製工業用酸化亜鉛粉末９４゜１ｇをボールミルで
６時間粉砕混合した後、温度約８５０℃１時間焼成した
。Comparative Example 2 9.24 g of industrial titanium oxide powder manufactured by Wako Pure Chemical Industries, Ltd. and 94° 1 g of industrial zinc oxide powder manufactured by Yamada Pharmaceutical were pulverized and mixed in a ball mill for 6 hours, and then fired at a temperature of about 850° C. for 1 hour.
得られた粉末のＺ ｎ ／ Ｔ ｉ原子比は１００／１
０で、平均粒径は約０．２μｍであった。The Z n / Ti atomic ratio of the obtained powder was 100/1
0, the average particle size was approximately 0.2 μm.
この粉末の原子結合状態を測定したところ、−Ｚｎ−〇
−Ｔ ｉ ４結合は認められず、単なる酸化亜鉛と酸化
チタンの混合粉末であることが確認された。When the atomic bonding state of this powder was measured, no -Zn-〇-Ti4 bond was observed, and it was confirmed that the powder was simply a mixed powder of zinc oxide and titanium oxide.
分光ｉ３過率を測定した結果を第５図に示す。The results of measuring the spectral i3 pass rate are shown in FIG.
比較例３
和光純薬工業製工業用酸化チタン粉末９．２４ｇ及び同
酸化アルミニウム粉末２３．６及び山田薬品製工業用酸
化亜鉛粉末９４．１ｇをボールミルで６時間粉砕混合し
た後、温度約８５０℃、１時間焼成した。Comparative Example 3 After pulverizing and mixing 9.24 g of industrial titanium oxide powder manufactured by Wako Pure Chemical Industries, Ltd. and 23.6 g of the same aluminum oxide powder and 94.1 g of industrial zinc oxide powder manufactured by Yamada Pharmaceutical Co., Ltd. for 6 hours in a ball mill, the temperature was about 850°C. , baked for 1 hour.
得られた粉末のＺ ｎ ／ Ａβ／Ｔｉ原子比は１００
／４０／１０で、平均粒径は約０．２ｐｍ以下であった
。The Zn/Aβ/Ti atomic ratio of the obtained powder was 100
/40/10, and the average particle size was about 0.2 pm or less.
この粉末の原子結合状態を測定したところ、−）Ｔｉ
−０−Ｚｎ−０−Ａｊ！＜結合は認められず単なる酸化
亜鉛、酸化アルミニウム及び酸化チタンの混合粉末であ
ることが確認された。When the atomic bonding state of this powder was measured, it was found that -)Ti
-0-Zn-0-Aj! <No bond was observed, and it was confirmed that the powder was simply a mixed powder of zinc oxide, aluminum oxide, and titanium oxide.
分光透過率を測定した結果を第５図に示す。The results of measuring the spectral transmittance are shown in FIG.
比較例４
日本べんから工業製酸化鉄粉末３２．９ｇ及び山田薬品
製工業用酸化亜鉛６７．１ｇをボールミルで６時間粉砕
混合した後、温度約６００℃、１時間焼成した。Comparative Example 4 32.9 g of iron oxide powder manufactured by Nippon Benkara Kogyo and 67.1 g of industrial zinc oxide manufactured by Yamada Pharmaceutical were pulverized and mixed in a ball mill for 6 hours, and then fired at a temperature of about 600° C. for 1 hour.
得られた粉末のＺ ｎ ／ Ｆ ｅ原子比は１００／５
０で平均粒径は約０．２μｍであった。The Zn/Fe atomic ratio of the obtained powder was 100/5
0 and the average particle size was about 0.2 μm.
この粉末の原子結合状態を測定したところ、−Ｚｎ−０
−Ｆｅ＜結合は認められず、酸化亜鉛と酸化鉄の単なる
混合粉末であることが確認された。When the atomic bonding state of this powder was measured, it was found that -Zn-0
-Fe< bond was not observed, and it was confirmed that the powder was simply a mixed powder of zinc oxide and iron oxide.
分光透過率の測定結果を第５図に示す。The measurement results of the spectral transmittance are shown in FIG.
比較例５
和光純薬製酸化セリウム０．０２２ｇ及び山田薬品製工
業用酸化亜鉛１０２ｇをボールミルで６時間粉砕混合し
た後、温度約６００℃、１時間焼成した。Comparative Example 5 0.022 g of cerium oxide manufactured by Wako Pure Chemical Industries, Ltd. and 102 g of industrial zinc oxide manufactured by Yamada Pharmaceutical were pulverized and mixed in a ball mill for 6 hours, and then baked at a temperature of about 600° C. for 1 hour.
得られた粉末のＺ ｎ ／ Ｃｅ原子比は１００１０．
０１で平均粒径は約０．２μｍであった。The Z n /Ce atomic ratio of the obtained powder was 10010.
01, the average particle size was about 0.2 μm.
分光透過率の測定結果を第５図に示す。The measurement results of the spectral transmittance are shown in FIG.
比較例６
日本ぺんから工業製酸化鉄粉末１ｇ、和光純薬製酸化ア
ルミニウム６．３７ｇ及び山田薬品製工業用酸化亜鉛粉
末１０２ｇをボールミルで６時間粉砕混合した後、温度
約６００℃、１時間焼成した。Comparative Example 6 1 g of iron oxide powder manufactured by Nippon Penkara, 6.37 g of aluminum oxide manufactured by Wako Pure Chemical Industries, and 102 g of industrial zinc oxide powder manufactured by Yamada Pharmaceutical were ground and mixed in a ball mill for 6 hours, and then baked at a temperature of about 600°C for 1 hour. did.
得られた粉末のＺ ｎ ／ Ａ！／ Ｆ ｅ原子比はＩ
Ｑ Ｏ／ｌ Ｇ／ｌで、平均粒径は約０．２ｐｍであっ
た。Zn/A! of the obtained powder! / Fe atomic ratio is I
Q O/l G/l, and the average particle size was approximately 0.2 pm.
分光透過率の測定結果を第５図に示す。The measurement results of the spectral transmittance are shown in FIG.
比較例７，８，９，１０．１）．１２
比較例１〜６で使用された市ｐＦｉ酸化アルミニウム、
酸化亜鉛、同酸化チタン、日本べんがら工業製酸化鉄、
デグッサ製超微粒子酸化チタン及び酸化セリウムの各粉
末の分光透過率を測定した結果を第５図に示す。Comparative Examples 7, 8, 9, 10.1). 12 City pFi aluminum oxide used in Comparative Examples 1 to 6,
Zinc oxide, titanium oxide, iron oxide manufactured by Nippon Bengara Industries,
The results of measuring the spectral transmittance of each powder of ultrafine titanium oxide and cerium oxide manufactured by Degussa are shown in FIG.
本比較例で使用した各酸化物の粒度を第１表に示す。Table 1 shows the particle size of each oxide used in this comparative example.
第１表
比較例１３
実施例１のエタノール１２００ｍ１に代えて、水１２０
０ｒｒ＋ｌを用いた以外は同様に加水分解を行い続いて
乾燥、焼成を行った。Table 1 Comparative Example 13 Instead of 1200ml of ethanol in Example 1, 120ml of water
Hydrolysis was carried out in the same manner except that 0rr+l was used, followed by drying and firing.
その結果、平均粒径約１μｍの粉末９８．２ｇを得た。As a result, 98.2 g of powder with an average particle size of about 1 μm was obtained.
この製品粉末の組成はＺ ｎ ／ Ａβ原子比が１００
／１０であった。The composition of this product powder is that the Zn/Aβ atomic ratio is 100.
/10.
この粉末の原子結合状態を測定したところ、−Ｚｎ−０
−ＡＪ＜結合（特性吸収６５０ Ｃｍ−１）が認められ
た。When the atomic bonding state of this powder was measured, it was found that -Zn-0
-AJ<bonding (characteristic absorption 650 Cm-1) was observed.
分光透過率を測定した結果を第５図に示す。The results of measuring the spectral transmittance are shown in FIG.
尚、得られた微粒子複合酸化物及び比較例で用、いた原
料酸化物粉末の触媒活性を調べた結果、デグフサ製超微
粒子酸化チタンのみが触媒活性が高く、フィルム化は困
難でたんざ（状になったが、他は特に触媒活性能は認め
られなかった。In addition, as a result of examining the catalytic activity of the obtained fine particle composite oxide and the raw material oxide powder used in the comparative example, only the ultrafine particle titanium oxide made by Degufusa had a high catalytic activity, and it was difficult to form into a film. However, no particular catalytic activity was observed in the others.
第１〜４図は、実施例１〜３０で得られた複合金属酸化
物粉末の紫外線〜可視光線域における分光透過率曲線図
であり、図中の数字は実施例番号に対応する。
第５図は、比較例１〜６で得られた金属酸化物粉末、比
較例１３で得られた複合金屈酸化物粉末及び比較例１〜
６で扱った原料金属酸化物粉末の紫外線−可視光線域に
おける分光透過率曲線図であり、図中の数字は比較例番
号に対応する。
第１図
波長（ｎｍ）
波長（ｎ ｍｌ
波長（ｎ ｍ）1 to 4 are spectral transmittance curves in the ultraviolet to visible light range of the composite metal oxide powders obtained in Examples 1 to 30, and the numbers in the figures correspond to the example numbers. Figure 5 shows the metal oxide powders obtained in Comparative Examples 1 to 6, the composite metal oxide powders obtained in Comparative Example 13, and the composite metal oxide powders obtained in Comparative Examples 1 to 6.
6 is a spectral transmittance curve diagram in the ultraviolet-visible light range of the raw metal oxide powder treated in Section 6, and the numbers in the figure correspond to comparative example numbers. Figure 1 Wavelength (nm) Wavelength (n ml Wavelength (n m)
Claims (1)
、アルミニウム、鉄、クロム、セリウム、ジルコニウム
、及びチタンから選ばれた１種以上の金属と亜鉛との複
合酸化物から成る紫外線遮蔽剤。(1) Ultraviolet screening agent made of a composite oxide of zinc and one or more metals selected from aluminum, iron, chromium, cerium, zirconium, and titanium, with an average particle size of 0.001 μm to 0.5 μm. .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-12866 | 1986-01-23 | ||
| JP1286686 | 1986-01-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62275182A true JPS62275182A (en) | 1987-11-30 |
Family
ID=11817332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15000886A Pending JPS62275182A (en) | 1986-01-23 | 1986-06-26 | Ultraviolet screening agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62275182A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424055A (en) * | 1992-03-23 | 1995-06-13 | Mitsui Mining & Smelting Co., Ltd. | Ultraviolet screening composited oxide and process for producing the same |
| WO2004052786A1 (en) * | 2002-12-09 | 2004-06-24 | Tayca Corporation | Titanium oxide particles having useful properties and method for production thereof |
| DE10259860A1 (en) * | 2002-12-20 | 2004-07-08 | Degussa Ag | Powder mixture consisting of titanium dioxide, zinc oxide and zinc-titanium mixed oxide |
| WO2004058645A1 (en) * | 2002-12-25 | 2004-07-15 | Cf High Tech Co., Ltd. | Electroconductive zinc oxide powder and method for production thereof, and electroconductive composition |
| JP2005162695A (en) * | 2003-12-04 | 2005-06-23 | Lion Corp | Infrared ray-shielding substance-containing cosmetic |
| JP2005263612A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| JP2005263620A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| WO2005076752A3 (en) * | 2004-02-18 | 2005-10-06 | Nippon Catalytic Chem Ind | Metal oxide particle and its uses |
| JP2006188386A (en) * | 2005-01-05 | 2006-07-20 | Nippon Shokubai Co Ltd | Particulate metal oxide and use of the same |
| JP2007031216A (en) * | 2005-07-27 | 2007-02-08 | Nippon Shokubai Co Ltd | Metal oxide particle, and its use |
| WO2015098945A1 (en) | 2013-12-24 | 2015-07-02 | 堺化学工業株式会社 | Cerium-oxide-coated zinc oxide particles, method for producing same, ultraviolet ray shielding agent, and cosmetic |
| WO2015098992A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| WO2015098993A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| WO2019225491A1 (en) | 2018-05-23 | 2019-11-28 | 株式会社コーセー | Novel titanium oxide powder and cosmetic formulated therewith |
| US10696563B2 (en) | 2014-02-07 | 2020-06-30 | Sakai Chemical Industry Co., Ltd. | Hexagonal plate-shaped zinc oxide particles, method for production of the same, and cosmetic, filler, resin composition, infrared reflective material, and coating composition containing the same |
-
1986
- 1986-06-26 JP JP15000886A patent/JPS62275182A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424055A (en) * | 1992-03-23 | 1995-06-13 | Mitsui Mining & Smelting Co., Ltd. | Ultraviolet screening composited oxide and process for producing the same |
| JP4546834B2 (en) * | 2002-12-09 | 2010-09-22 | テイカ株式会社 | Titanium oxide particles having beneficial properties and method for producing the same |
| WO2004052786A1 (en) * | 2002-12-09 | 2004-06-24 | Tayca Corporation | Titanium oxide particles having useful properties and method for production thereof |
| JPWO2004052786A1 (en) * | 2002-12-09 | 2006-04-13 | テイカ株式会社 | Titanium oxide particles having beneficial properties and method for producing the same |
| DE10259860A1 (en) * | 2002-12-20 | 2004-07-08 | Degussa Ag | Powder mixture consisting of titanium dioxide, zinc oxide and zinc-titanium mixed oxide |
| WO2004058645A1 (en) * | 2002-12-25 | 2004-07-15 | Cf High Tech Co., Ltd. | Electroconductive zinc oxide powder and method for production thereof, and electroconductive composition |
| US7378152B2 (en) | 2002-12-25 | 2008-05-27 | Cf High Tech Co., Ltd. | Electroconductive zinc oxide powder and method for production thereof, and electroconducitve composition |
| JP2005162695A (en) * | 2003-12-04 | 2005-06-23 | Lion Corp | Infrared ray-shielding substance-containing cosmetic |
| JP2005263612A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| JP2005263620A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| WO2005076752A3 (en) * | 2004-02-18 | 2005-10-06 | Nippon Catalytic Chem Ind | Metal oxide particle and its uses |
| JP2006188386A (en) * | 2005-01-05 | 2006-07-20 | Nippon Shokubai Co Ltd | Particulate metal oxide and use of the same |
| JP2007031216A (en) * | 2005-07-27 | 2007-02-08 | Nippon Shokubai Co Ltd | Metal oxide particle, and its use |
| WO2015098945A1 (en) | 2013-12-24 | 2015-07-02 | 堺化学工業株式会社 | Cerium-oxide-coated zinc oxide particles, method for producing same, ultraviolet ray shielding agent, and cosmetic |
| WO2015098992A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| WO2015098993A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| US9775787B2 (en) | 2013-12-27 | 2017-10-03 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particle, method for producing the same, ultraviolet shielding agent, and cosmetic |
| US9789037B2 (en) | 2013-12-27 | 2017-10-17 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particle, method for producing the same, ultraviolet shielding agent, and cosmetic |
| US10696563B2 (en) | 2014-02-07 | 2020-06-30 | Sakai Chemical Industry Co., Ltd. | Hexagonal plate-shaped zinc oxide particles, method for production of the same, and cosmetic, filler, resin composition, infrared reflective material, and coating composition containing the same |
| WO2019225491A1 (en) | 2018-05-23 | 2019-11-28 | 株式会社コーセー | Novel titanium oxide powder and cosmetic formulated therewith |
| KR20210012999A (en) | 2018-05-23 | 2021-02-03 | 가부시키가이샤 코세 | New titanium oxide powder and cosmetics containing the same |
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