JPH01275763A - Production of alumina-containing thin film by sol-gel process - Google Patents
Production of alumina-containing thin film by sol-gel processInfo
- Publication number
- JPH01275763A JPH01275763A JP10275988A JP10275988A JPH01275763A JP H01275763 A JPH01275763 A JP H01275763A JP 10275988 A JP10275988 A JP 10275988A JP 10275988 A JP10275988 A JP 10275988A JP H01275763 A JPH01275763 A JP H01275763A
- Authority
- JP
- Japan
- Prior art keywords
- added
- alkoxide
- thin film
- mole
- alumina
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000003980 solgel method Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 20
- -1 aluminum alkoxide Chemical class 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 14
- 239000010408 film Substances 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 abstract description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明のコーチイブ薄膜は化学的、機械的に安定強固な
保護膜であり、そのコーティング薄膜の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The Coachive thin film of the present invention is a chemically and mechanically stable and strong protective film, and relates to a method for producing the coating thin film.
装飾性、耐蝕性、耐摩耗性の向上を目的として金属や非
金属の保護薄膜を施す事は、従来より所謂電気メツキ、
溶融メツキ、容射法、浸透法あるいは陽極酸化、化成処
理等の表面酸化処理が行われている。又、ホウロウ処理
などの無機粉末の溶融あるいは焼結によってガラスある
いはセラミックスの保護膜を形成することが行われてい
る。Applying a protective thin film of metal or nonmetal for the purpose of improving decoration, corrosion resistance, and abrasion resistance has traditionally been done by so-called electroplating.
Surface oxidation treatments such as hot plating, spraying, infiltration, anodic oxidation, and chemical conversion treatments are performed. Furthermore, a protective film of glass or ceramics is formed by melting or sintering inorganic powder, such as by enameling.
しかし、保護膜としての効果を向上させることからも、
その膜厚は１０μ〜数ａｍと非常に厚く、保護膜として
の効果を十分に維持させたまま薄くすることは技術的に
困難であった。However, since it improves the effect as a protective film,
The film thickness is very thick, ranging from 10 μm to several am, and it is technically difficult to reduce the thickness while maintaining the effect as a protective film.
又、オキシ水酸化鉄黄色顔料、チタン白顔料や磁気記録
媒体用原料の磁性鉄微粒子の製造などの無機微粉末の表
面改質として耐候性、耐熱性あるいは親和性の向上のた
めにケイ酸塩、アルミニウム化合物の加水分解、均−沈
澱法あるいは水熱処理等による沈着により行われている
。しかし、これらの方法では共存するナトリウムイオン
等のアルカリや硫酸根、塩化物イオン等が水洗を十分に
行っても残りやすく、したがってコーテイング膜の純度
が低く、その効果が十分に発揮されない場合もあった。In addition, silicates are used to improve weather resistance, heat resistance, or affinity for surface modification of inorganic fine powders such as iron oxyhydroxide yellow pigments, titanium white pigments, and magnetic iron fine particles used as raw materials for magnetic recording media. This is carried out by hydrolysis of an aluminum compound, precipitation by a homogeneous precipitation method, hydrothermal treatment, or the like. However, with these methods, coexisting alkalis such as sodium ions, sulfate radicals, chloride ions, etc. tend to remain even after thorough washing with water, and therefore the purity of the coating film is low and its effectiveness may not be fully demonstrated. Ta.
〔文献、「顔料」３０巻ｐ、 １７９２ （１９８６）
、「窯素」９５巻ｐ、４４２（１９８７） ）最近、エ
レクトロニクスなどの先端技術の発達に伴うて新しい薄
膜形成方法が開発され、例えば、真空蒸着法、分子線エ
ピタキシー法、イオンブレーティング法、スパッタリン
グ法、ＣＶＤ法などがそれであり、従来技術に比べて非
常に薄くまた新しい組成、機能の薄膜も形成されている
が、高価な装置を用いる必要があること、あるいは大面
積、大量生産に適当でない等の欠点があった。[Reference, “Pigments” Vol. 30, p. 1792 (1986)
, "Kiln" Vol. 95, p. 442 (1987)) Recently, with the development of advanced technologies such as electronics, new thin film forming methods have been developed, such as vacuum evaporation, molecular beam epitaxy, ion blating, These methods include sputtering and CVD, which are much thinner than conventional techniques and can also form thin films with new compositions and functions, but they require the use of expensive equipment or are not suitable for large areas or mass production. There were drawbacks such as:
そこで、金属アルコキシドを出発物質とするゾル−ゲル
法が注目されてきた。この方法によれば例えば、ＳｉＯ
２，ＡＬｚＯｓ、 ＳｉＯ□−ＴｉＯｔ＋ＳｉＯ□−Ａ
Ｌｚ（ｈ、５ｉ０ｚ−ＺｒＯｔ＋５ｉＯｔ−Ｂ＊Ｏｓ、
Ｓｎｏｗ−１ｎｚＯｚ＋ＮａｚＯ−５ｉＯ２−Ｚｒ
Ｏｌなどの純度が高く多成分系について均質性の高いガ
ラスまたはセラミックスが比較的低温の加熱で製造でき
る。Therefore, the sol-gel method using metal alkoxide as a starting material has attracted attention. According to this method, for example, SiO
2, ALzOs, SiO□-TiOt+SiO□-A
Lz(h, 5i0z-ZrOt+5iOt-B*Os,
Snow-1nzOz+NazO-5iO2-Zr
Glasses or ceramics with high purity and high homogeneity of multi-component systems such as Ol etc. can be produced by heating at a relatively low temperature.
更に、他の方法では製造出来ない新しい組成、機能のガ
ラスまたはセラミックスが製造できる。Furthermore, glasses or ceramics with new compositions and functions that cannot be produced by other methods can be produced.
これらの特徴は、コーティング薄膜を形成する場合や顔
料の表面コーティングの場合にもあてはまる。すなわち
、金属アルコキシドの多くが極めて加水分解されやすい
ので雰囲気、溶媒等の水分に注意しながら、禁水性雰囲
気においてアルコール等に溶解も温度、水の添加量、触
媒の種類、添加量、添加速度、溶媒の蒸発速度、湿度等
を制御することによりバルク、繊維、シート、コーテイ
ング膜、微粒子のガラスあるいは非晶質を製造すること
ができる。These characteristics also apply to the formation of coating thin films and the surface coating of pigments. In other words, many metal alkoxides are extremely easily hydrolyzed, so be careful of moisture in the atmosphere, solvent, etc., and dissolve them in alcohol etc. in a water-free atmosphere. By controlling the evaporation rate, humidity, etc. of the solvent, it is possible to produce glass in bulk, fibers, sheets, coating films, fine particles of glass, or amorphous materials.
上述の様に、従来技術における金属アルコキシドを出発
物質とするゾル−ゲル法によるガラス、セラミックス、
酸化物薄膜製造あるいは顔料の表面コーティングにおけ
る問題の一つは出発物質である金属アルコキシドの多（
が極めて加水分解されやすい為、製造工程における雰囲
気中の湿度や添加水分量、加水分解速度の制御が極めて
微妙で難しいことである。As mentioned above, glass, ceramics,
One of the problems in producing thin oxide films or coating the surface of pigments is the large number of starting metal alkoxides (
Because it is extremely easy to hydrolyze, it is extremely delicate and difficult to control the humidity in the atmosphere, the amount of added water, and the rate of hydrolysis during the manufacturing process.
本発明者等は、上記課題につき鋭意研究を行い従来のゾ
ル−ゲル法によるガラス、セラミックスあるいは酸化物
薄膜製造の基礎研究を続けた結果、出発物質である金属
アルコキシド溶液の水に対する安定性を向上させること
により容易に非常に透明性の高いガラスあるいは薄膜を
製造することが出来、尚且つ製造工程が単純で安価な本
発明に到達した。The inventors of the present invention have conducted intensive research on the above-mentioned problems and continued basic research on the production of glass, ceramics, or oxide thin films using the conventional sol-gel method. As a result, they have improved the stability of the metal alkoxide solution, which is the starting material, against water. By doing so, we have achieved the present invention in which very transparent glass or thin films can be easily manufactured, and the manufacturing process is simple and inexpensive.
すなわち、本発明のゾル−ゲル法によるアルミナ含有薄
膜の製造方法は、アルミニウムアルコキシドを用いてア
ルミニウム酸化物薄膜を形成するに際し、前記アルコキ
シド溶液に１．３−あるいはβ−ジケトン基を含有する
化合物をアルミニウムアルコキシドに対して０．１〜１
０．０倍モル添加し、更に必要に応じて水を添加するこ
とを特徴とする製造方法、更には、シリコン、チタン、
ジルコニウム、リン、ホウ素のアルコキシドから選ばれ
た一種以上のアルコキシドとアルミニウムアルコキシド
を用いてアルミニウム含有酸化＠ｆｆ薄膜を形成するに
際し、前記アルコキシド溶液に１．３−あるいはβ−ジ
ケトン基を含有する化合物を混合アルコキシドに対して
０．１〜１０．０倍モル添加し、更に必要に応じて水を
添加することを特徴とするものである。That is, in the method for producing an alumina-containing thin film by the sol-gel method of the present invention, when forming an aluminum oxide thin film using aluminum alkoxide, a compound containing a 1,3- or β-diketone group is added to the alkoxide solution. 0.1-1 for aluminum alkoxide
A manufacturing method characterized by adding 0.0 times the mole and further adding water as necessary, furthermore, silicon, titanium,
When forming an aluminum oxide@ff thin film using one or more alkoxides selected from zirconium, phosphorus, and boron alkoxides and aluminum alkoxide, a compound containing a 1,3- or β-diketone group is added to the alkoxide solution. It is characterized in that it is added in an amount of 0.1 to 10.0 times the mole of the mixed alkoxide, and water is further added as necessary.
本発明のアルミニウムアルコキシド化合物とは、例えば
、ＡＬ（ＯＲ）３においてＲが炭素＠２〜５程度のアル
キル基であり、またはＲの一部をアセトアセチル基等で
置換したものである。該アルミニウムアルコキシド化合
物を有機溶剤、例えば、イソフロハノール、ｎ−フタノ
ールなどのアルコール類、ｎ−へキサン、ｎ−ヘプタン
などの炭化水素類、トルエン、キシレンなどのアルキル
ベンゼン類、酢酸エチルなどのエステル類、アセトン、
メチルエチルケトンなどのケトン類から選ばれた溶解可
能な溶媒に溶解後、１，３−あるいはβ−ジケトン基を
含有する化合物、すなわちアセチルアセトンなどのジケ
トン類、マロン酸及びマロン酸ジエチルなどのマロン酸
誘導体、アセト酢酸及びアセト酢酸エチルなどのアセト
酢酸エチルをアルミニウムアルコキシド化合物に対して
０．１〜１０．０倍モル、好ましくは０．３〜３．０倍
モル添加することにある、 添加量が少なければ金属ア
ルコキシドの水に対する安定性が低下し、多すぎれば加
熱分解後にカーボンが残留し易くなる。The aluminum alkoxide compound of the present invention is, for example, AL(OR)3 in which R is an alkyl group having about 2 to 5 carbon atoms, or a part of R is substituted with an acetoacetyl group or the like. The aluminum alkoxide compound is treated with an organic solvent such as alcohols such as isofurohanol and n-phthanol, hydrocarbons such as n-hexane and n-heptane, alkylbenzenes such as toluene and xylene, esters such as ethyl acetate, and acetone. ,
After dissolving in a soluble solvent selected from ketones such as methyl ethyl ketone, compounds containing 1,3- or β-diketone groups, i.e. diketones such as acetylacetone, malonic acid and malonic acid derivatives such as diethyl malonate, Ethyl acetoacetate such as acetoacetic acid and ethyl acetoacetate is added by 0.1 to 10.0 times the mole, preferably 0.3 to 3.0 times the mole of the aluminum alkoxide compound. The stability of the metal alkoxide against water decreases, and if the amount is too large, carbon tends to remain after thermal decomposition.
更に、該溶液への適当量の水の添加は加熱処理に際し、
金属アルコキシドの昇華分解を防ぎ、又カーボンの残留
を防ぐ為であるが、多量に水を添加するとアルミニウム
の加水分解の沈澱が生成し、均一性が劣ることになり好
ましくない、すなわち、アルミニウムアルコキシド、ジ
ケトン化合物及び水の反応性により沈澱生成の起こる水
添加量の範囲は異なるので特定することはできないが、
例えば、アルミニウムアルコキシド化合物に対して等モ
ルのアセト酢酸エチルを添加した場合３．０モルまでの
水添加でも沈澱は生成しないし、マロン酸ジエチルでは
１．０モルまでの水添加でも沈澱は生成しない。Furthermore, adding an appropriate amount of water to the solution during heat treatment,
This is to prevent sublimation and decomposition of metal alkoxides and to prevent carbon from remaining. However, if a large amount of water is added, a precipitate of aluminum hydrolysis will be formed, resulting in poor uniformity, which is undesirable. In other words, aluminum alkoxide, The range of water addition at which precipitation occurs varies depending on the reactivity of the diketone compound and water, so it cannot be specified.
For example, when an equimolar amount of ethyl acetoacetate is added to an aluminum alkoxide compound, no precipitate is formed even when up to 3.0 mol of water is added, and with diethyl malonate, no precipitate is formed even when up to 1.0 mol of water is added. .
かくして調整したコーティング溶液を特に温度、湿度を
制御することな（大気中で石英ガラス等の基板にデイツ
プコーティングあるいはスピンコーティングし、電気炉
で４００〜７００ ’Ｃ１好ましくは４５０〜６００°
Ｃまで熱処理することにより透明性の高いアルミニウム
の酸化物薄膜を製造することができる。The thus prepared coating solution is dip coated or spin coated on a substrate such as quartz glass in the atmosphere without particularly controlling the temperature and humidity, and heated in an electric furnace at 400 to 700°C, preferably 450 to 600°C.
A highly transparent aluminum oxide thin film can be produced by heat treatment to C.
更に、本発明の効果は、無機顔料の表面改質において羅
著である。すなわち、定法によれば無機顔料あるいはそ
の原料粉末は水を媒体とする所謂湿式法で合成され、水
洗、乾燥され必要に応じて焼成されるが、顔料は大気中
の水分を多く吸着している場合が常である。従って、金
属アルコキシド溶液に顔料を投入すると吸着水分により
加水分解が起こり、該スラリーは均一性が低下すること
になるが、ジケトン基含有化合物を予め金属アルコキシ
ド溶液に添加しておくことによりその均一性が向上でき
る。Furthermore, the effects of the present invention are remarkable in surface modification of inorganic pigments. In other words, according to the standard method, inorganic pigments or their raw material powders are synthesized by a so-called wet method using water as a medium, washed with water, dried, and fired as necessary, but pigments absorb a lot of moisture in the atmosphere. This is always the case. Therefore, when a pigment is added to a metal alkoxide solution, hydrolysis occurs due to adsorbed water, and the uniformity of the slurry decreases. However, by adding a diketone group-containing compound to the metal alkoxide solution in advance, the uniformity of the slurry can be improved. can be improved.
以下、実施例及び比較例により本発明の方法及びその効
果を詳細に説明する。Hereinafter, the method of the present invention and its effects will be explained in detail using Examples and Comparative Examples.
実施例−１
室温において、アルミニウムアルコキシドとしてＡＬ（
０−ｓｅｅ−Ｂｕ） ｓを用い、これの１モルに対して
１０倍モルのイソプロパツールに希釈し、マロン酸ジエ
チルを１倍モル添加し、１時間攪拌した。更に攪拌しな
がら水１倍モルを２時間かけ添加して加水分解させ、透
明なコーティング溶液を得た。Example-1 At room temperature, AL(
0-see-Bu) s was diluted with isopropanol in an amount of 10 times the mole per mole thereof, diethyl malonate was added in a mole of 1 times, and the mixture was stirred for 1 hour. Further, while stirring, 1 mole of water was added over 2 hours to cause hydrolysis, and a transparent coating solution was obtained.
大気中で石英製スライドガラス基板にデイツプコーティ
ングし乾燥後電気炉で５００°Ｃまで加熱処理を行った
。得られたアルミナコーティングガラス基板は透明であ
った。A quartz slide glass substrate was dip-coated in the atmosphere, dried, and then heated to 500°C in an electric furnace. The obtained alumina coated glass substrate was transparent.
比較例−１
室温において、アルミニウムアルコキシドとしてＡＬ（
０−ｓｅｃ−Ｂｕ）ｚを用い、これの１モルに対して３
倍モルのイソプロパツールに希釈し、マロン酸ジエチル
を１倍モル添加し、１時間攪拌した。更に攪拌しながら
水３倍モルを６時間かけ添加して加水分解させたが溶液
はやや濁っていた。大気中で石英製スライドガラス基板
にデイツプコーティングし乾燥後電気炉で５００℃まで
加熱処理を行った。得られたアルミナコーティングガラ
ス基板は白濁していた。Comparative Example-1 At room temperature, AL(
0-sec-Bu)z, and 3 for 1 mole of this.
The mixture was diluted with twice the molar amount of isopropanol, 1 times the molar amount of diethyl malonate was added, and the mixture was stirred for 1 hour. Further, while stirring, 3 times the mole of water was added over 6 hours to cause hydrolysis, but the solution was slightly cloudy. A quartz slide glass substrate was dip-coated in the atmosphere, dried, and then heated to 500° C. in an electric furnace. The obtained alumina-coated glass substrate was cloudy.
実施例−２
室温において、アルミニウムアルコキシドとしてＡＬ（
０−ｉｓｏ−Ｐｒ）ｓを用い、これの１モルに対して１
００倍モルのイソプロパツールに攪拌しながら２時間加
熱溶解し室温まで放冷した後アセト酢酸エチルを１．０
倍モル添加した。更に水を３倍モル添加して加水分解さ
せ、透明なコーティング溶液を得た。大気中で石英製ス
ライドガラス基板にデイツプコーティングし乾燥後電気
炉で５００℃まで加熱処理を行った。得られたアルミナ
コーティングガラス基板は透明であった。Example-2 At room temperature, AL(
0-iso-Pr)s, and 1 mole thereof
After heating and dissolving in 00 times the molar amount of isopropanol with stirring for 2 hours and cooling to room temperature, 1.0 times the amount of ethyl acetoacetate was added.
Double the mole amount was added. Furthermore, 3 times the mole of water was added to cause hydrolysis, and a transparent coating solution was obtained. A quartz slide glass substrate was dip-coated in the atmosphere, dried, and then heated to 500° C. in an electric furnace. The obtained alumina coated glass substrate was transparent.
実施例−３
室温において、アルミニウムアルコキシドとして＾Ｌ（
０−ｓｅｃ−Ｂｕ） ｓを用い、これの１モルに対して
１０倍モルのイソプロパツールに希釈し、アセト酢酸エ
チルを０．５倍モル添加した。更に水を１倍モル添加し
て加水分解させ、透明なコーティング溶液を得た。大気
中で石英製スライドガラス基板にデイツプコーティング
し乾燥後電気炉で５００°Ｃまで加熱処理を行った。得
られたアルミナコーティングガラス基板は透明であった
。Example-3 At room temperature, aluminum alkoxide ^L(
0-sec-Bu)s was diluted with 10 times the mole of isopropanol per 1 mole of this, and 0.5 times the mole of ethyl acetoacetate was added. Further, 1 mole of water was added to cause hydrolysis, and a transparent coating solution was obtained. A quartz slide glass substrate was dip-coated in the atmosphere, dried, and then heated to 500°C in an electric furnace. The obtained alumina coated glass substrate was transparent.
比較例−２
十分に乾燥した窒素ボックス中でアルミニウムアルコキ
シドとしてＡＬ（０−ｉｓｏ−Ｐｒ） ｓを用い、これ
の１モルに対して１００倍モルのイソプロパツールに攪
拌しながら２時間加熱溶解し放冷後、透明なコーティン
グ溶液を得た。乾燥した窒素ボックス中で石英製スライ
ドガラス基板にデイツプコーティングし乾燥した。得ら
れたアルミナコーティングガラス基板は白く濁っていた
。Comparative Example 2 In a sufficiently dry nitrogen box, AL(0-iso-Pr)s was used as aluminum alkoxide, and 1 mole of AL(0-iso-Pr)s was dissolved by heating with stirring in 100 times the mole of isopropanol for 2 hours. After cooling, a transparent coating solution was obtained. A quartz slide glass substrate was dip coated and dried in a dry nitrogen box. The obtained alumina-coated glass substrate was white and cloudy.
実施例−４
室温において、アルミニウムアルコキシドとして＾Ｌ
（０−ｓｅｃ−Ｂｕ） ３を用い、これの１モルに対し
て１０倍モルのイソプロパツールに希釈し、アセチルア
セトンを１．０倍モル添加し、透明なコーティング溶液
を得た。大気中で石英製スライドガラス基板にデイツプ
コーティングし乾燥後電気炉で５００℃まで加熱処理を
行った。得られたアルミナコーティングガラス基板は透
明であった。Example-4 At room temperature, as aluminum alkoxide ^L
(0-sec-Bu) 3 was diluted with 10 times the mole of isopropanol per 1 mole of this, and 1.0 times the mole of acetylacetone was added to obtain a transparent coating solution. A quartz slide glass substrate was dip-coated in the atmosphere, dried, and then heated to 500° C. in an electric furnace. The obtained alumina coated glass substrate was transparent.
実施例−５ 本実施例は顔料の表面改質に関する効果の一例である。Example-5 This example is an example of effects related to surface modification of pigments.
すなわち、硫酸第一鉄溶液を水酸化ナトリウム溶液で加
水分解した後、空気を流通することにより黄色顔料であ
るオキシ水酸化鉄を合成した。濾過、水洗し乾燥後、大
気中で粉砕した。比表面積（ＳＡ）は６１．１ボ／ｇ、
透過型電子顕微鏡観察による長袖及び短軸の比（Ｌ／Ｄ
）は１２であった。 室温において、アルミニウムアル
コキシドとしてＡＬ（０−ｓｅｅ−Ｂｕ） ｓを用い、
これの０．０５モルに対して３００倍モルのイソプロパ
ツールに希釈し、マロン酸ジエチルを０．０５倍モル添
加し、透明なコーティング溶液を得た。該オキシ水酸化
鉄４０ｇｒを加え大気中で４８時間攪拌した後、濾過、
乾燥、粉砕し原料粉とした。That is, iron oxyhydroxide, which is a yellow pigment, was synthesized by hydrolyzing a ferrous sulfate solution with a sodium hydroxide solution and then passing air through the solution. After filtering, washing with water, drying, and pulverizing in the air. Specific surface area (SA) is 61.1 bo/g,
Long sleeve and short axis ratio (L/D) observed by transmission electron microscopy
) was 12. At room temperature, using AL(0-see-Bu)s as aluminum alkoxide,
0.05 mole of this was diluted with 300 times the mole of isopropanol, and 0.05 times mole of diethyl malonate was added to obtain a transparent coating solution. After adding 40g of the iron oxyhydroxide and stirring in the atmosphere for 48 hours, filtration,
It was dried and ground into raw material powder.
該表面積改質オキシ水酸化鉄１０ｇｒを固定床方式の還
元炉に充填し、窒素ガスをガス空間速度＝２ＯＮｒｒｆ
−Ｎｚ／ｋｇｒ−Ｆｅ−Ｈｒで流通し、温度５００°Ｃ
，４時間仮焼後、水素ガスによる気相接触還元反応（温
度＝３５０°Ｃ１１０時間、ガス空間速度−２ＯＮｒｒ
ｆ−Ｈｚ／ｋｇｒ−Ｆｅ−Ｈｒ）により還元鉄粉とした
０次いで該微粒子を充分トルエンに浸漬して後、該微粒
子スラリーをホーロー製バット上に２＋ａｍ程の厚みに
なる様に移し、大気中でトルエンの飛散処理を加えた。10g of the surface-modified iron oxyhydroxide was charged into a fixed-bed reduction furnace, and nitrogen gas was added at a gas hourly velocity of 2ONrrf.
-Nz/kgr-Fe-Hr, temperature 500°C
, After calcination for 4 hours, gas phase catalytic reduction reaction with hydrogen gas (temperature = 350°C 110 hours, gas space velocity -2ONrr
f-Hz/kgr-Fe-Hr) to form reduced iron powder.Then, the fine particles were sufficiently immersed in toluene, and the fine particle slurry was transferred onto an enamel vat to a thickness of about 2+ am, and then soaked in the air. Added toluene scattering treatment.
溶剤が無くなった段階で磁性粉を回収し、風乾金属鉄粉
とした。該風乾金属鉄粉の形状を透過かた電子顕微鏡で
観察すると、イメージ上は一次原料のオキシ水酸化鉄の
形状を良く継承し、破損、破壊、更に粒子間焼結の類は
殆ど見られなかった。該風乾金属鉄粉の磁気特性を東英
工業社製試料振動型磁力計（ＶＳＭ−１１１）により測
定し、又、比表面積を測定したところ、Ｈｃ−１５００
０ｅ、 σ５＝１３５ ｅｍｕ／ｇ＋Ｒ・０．５２．
ＳＡ・５３．２ボ／ｇであり、優れた磁気特性であるこ
とがわかった。When the solvent ran out, the magnetic powder was collected and made into air-dried metal iron powder. When the shape of the air-dried metallic iron powder was observed using a transmission electron microscope, it appeared to closely follow the shape of the primary raw material, iron oxyhydroxide, with almost no breakage, destruction, or interparticle sintering observed. Ta. The magnetic properties of the air-dried metallic iron powder were measured using a vibrating sample magnetometer (VSM-111) manufactured by Toei Kogyo Co., Ltd., and the specific surface area was measured.
0e, σ5=135 emu/g+R・0.52.
It was found that the magnetic properties were excellent, with an SA of 53.2 bo/g.
比較例−３
室温において、アルミニウムアルコキシドとしてＡＬ（
０−ｓｅｅ−Ｂｕ）ｓを用い、これの０．０５モルに対
して３００モルのイソプロパツールに希釈し、透明なコ
ーティング溶液を得た。実施例−５と同様のオキシ水酸
化鉄４０ｇｒを加え大気中で攪拌しながらアルコキシド
に対して３倍モルの水を添加後、濾過、乾燥、粉砕し原
料粉とした。実施例−５と同様の仮焼、還元、風乾を行
い金属鉄粉とした。該風乾金属鉄粉の形状を透過型電子
顕微鏡で観察すると、イメージ上は一次原料のオキシ水
酸化鉄の形骸粒子は焼結しており、形骸粒子のほかに繊
維状の異物が見られた。該風乾金属鉄粉の磁気特性及び
比表面積を測定したところ、Ｈｃ＝１４２００ｅ、
σｓ＝１３０ｅｍｕ／ｇ、Ｒ＝０．４８．３Ａ−６２，
８１Ｔｆ／ｇであった。Comparative Example-3 At room temperature, AL(
0-see-Bu)s was used and diluted to 300 moles of isopropanol to 0.05 moles of this to obtain a clear coating solution. 40 grams of iron oxyhydroxide as in Example 5 was added, and while stirring in the atmosphere, 3 times the mole of water relative to the alkoxide was added, followed by filtration, drying, and pulverization to obtain a raw material powder. The same calcining, reduction, and air drying as in Example 5 were performed to obtain metallic iron powder. When the shape of the air-dried metallic iron powder was observed using a transmission electron microscope, it appeared that the skeleton particles of the primary raw material iron oxyhydroxide were sintered, and fibrous foreign matter was observed in addition to the skeleton particles. When the magnetic properties and specific surface area of the air-dried metallic iron powder were measured, Hc = 14200e,
σs=130emu/g, R=0.48.3A-62,
It was 81Tf/g.
実施例−６
室温において、０．０４モルのＡＬ（０−ｓｅｅ−Ｂｕ
） ３及び。Example-6 At room temperature, 0.04 mol of AL (0-see-Bu
) 3 and.
０．０１モルの５ｉ（０−Ｅｔ）４を３００モルのイソ
プロパツールに希釈し、アセト酢酸エチルを０．０５モ
ル添加し、透明なコーティング溶液を得た。実施例−５
と同様のオキシ水酸化鉄４０ｇｒを加え大気中で４０°
Ｃ１４８時間攪拌した後濾過、乾燥、粉砕し原料粉とし
た。実施例−５と同様の仮焼、還元、風乾を行い金属鉄
粉とした。該風乾金属鉄粉の形状を透過型電子顕微鏡で
観察すると、イメージ上は一次原料のオキシ水酸化鉄の
形状を良（継承し、破損、破壊、更に粒子間焼結の類は
殆ど見られなかった。該風乾金属鉄粉の磁気特性及び比
表面積を測定したところ、Ｈｃ＊１５３００ｅ、 １
ＦＳ＝１３６ ｅｍｕ／ｇ、Ｒ−０，５１，５Ａ−５６
，２ｒｒｆ／ｇであり、優れた磁気特性であることがわ
かった。0.01 mol of 5i(0-Et)4 was diluted in 300 mol of isopropanol and 0.05 mol of ethyl acetoacetate was added to obtain a clear coating solution. Example-5
Add 40g of iron oxyhydroxide and heat at 40° in the atmosphere.
After stirring for 148 hours, the mixture was filtered, dried, and ground to obtain a raw material powder. The same calcining, reduction, and air drying as in Example 5 were performed to obtain metallic iron powder. When the shape of the air-dried metallic iron powder was observed using a transmission electron microscope, the shape of the iron oxyhydroxide, which was the primary raw material, was observed to be good (inherited), and there was hardly any breakage, destruction, or interparticle sintering. When the magnetic properties and specific surface area of the air-dried metallic iron powder were measured, it was found that Hc*15300e, 1
FS=136 emu/g, R-0,51,5A-56
, 2rrf/g, and was found to have excellent magnetic properties.
本発明においては、金属アルコキシド溶液のコーティン
グにより酸化物薄膜を製造するに際して、ジケトン基含
有化合物を添加することにより、極めて容易に均質性の
高い、透明性の優れた薄膜を提供することが出来、産業
上極めて有益である特許出願人 三井東圧化学株式会社
手続補正書印発）
平成１年］月３日
特許庁長官 吉 １）文 毅 殴
１、事件の表示
昭和６３年特許願第１０２７５９号
２、発明の名称
ゾル−ゲル法によるアルミナ含有薄膜
の製造方法
３、補正をする者
事件との関係 特許出願人
住所 東京都千代田区霞が関三丁目２番５号名称（３１
２） 三井東圧化学株式会社４、補正により増加する
請求項の数 零５、補正の対象
明細書の発明の詳細な説明の欄
６、補正の内容
ＲＭｌｉ」と訂正する。In the present invention, when producing an oxide thin film by coating with a metal alkoxide solution, by adding a diketone group-containing compound, a thin film with high homogeneity and excellent transparency can be provided very easily. Patent that is extremely useful for industry (Applicant: Mitsui Toatsu Chemical Co., Ltd. Procedural amendments issued) January 3, 1999 Director General of the Japan Patent Office Yoshi 1) Takeshi Moon 1, Indication of the case Patent Application No. 102759 of 1988 2. Name of the invention Method for manufacturing alumina-containing thin film by sol-gel method 3. Relationship with the case of the person making the amendment Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (31
2) Mitsui Toatsu Kagaku Co., Ltd. 4. Number of claims increased by the amendment: 0 5. Column 6: Detailed explanation of the invention in the specification subject to the amendment. Contents of the amendment: RMli."
（２）明細書第９頁第１行の記載「性が向上できる。ｊ
のあとに次の文言を加える。「叉、本発明の方法は、金
属顔料の表面改質にも適用出来る。アルミフレークやブ
ロンズパウダーなどの金属顔料は表面に強固な酸化被膜
を有しており、その酸化被膜上に透明性の高いアルミナ
含有コーティング薄膜を形成することによって金属顔料
固有の優れた色調を保持したままで耐薬品性や耐候性の
向上を図ることが出来る。」
（３）明細書第９頁第１９行〜２０行に記載の「マロン
酸ジエチルを１倍モル添加し、」の文言を削除する。(2) Statement on page 9, line 1 of the specification: ``Sexuality can be improved.
Add the following phrase after. "Also, the method of the present invention can also be applied to surface modification of metal pigments. Metal pigments such as aluminum flakes and bronze powder have a strong oxide film on the surface, and a transparent layer is formed on the oxide film. By forming a thin coating film containing high alumina, it is possible to improve chemical resistance and weather resistance while maintaining the excellent color tone inherent to metal pigments.'' (3) Specification, page 9, lines 19 to 20. Delete the words "Add 1 molar amount of diethyl malonate" in the line.
（４）明細書第１２頁第１７行にｒｏ、０５倍モル添加
しｊとあるのをｒｏ、ｏｓモル添加し」と訂正する。(4) On page 12, line 17 of the specification, the text ``ro, 05 times the molar addition and j'' is corrected to ``ro, os molar addition''.
（５）明細書第１３頁第１行に「該表面積改質」とある
のを「該表面改質」と訂正する。(5) In the first line of page 13 of the specification, "the surface area modification" is corrected to "the surface modification."
（６）明細書第１３頁第１１行に「透過がた」とあるの
を「透過型」と訂正する。(6) On page 13, line 11 of the specification, the phrase "transparent type" is corrected to "transparent type."
Claims (1)
化物薄膜を形成するに際し、前記アルコキシド溶液に１
，３−あるいはβ−ジケトン基を含有する化合物をアル
ミニウムアルコキシドに対して０．１〜１０．０倍モル
添加し、更に必要に応じて水を添加することを特徴とす
るゾルーゲル法によるアルミナ含有薄膜の製造方法。 ２、シリコン、チタン、ジルコニウム、リン、ホウ素の
アルコキシドから選ばれた一種以上のアルコキシドとア
ルミニウムアルコキシドを用いてアルミニウム含有酸化
物薄膜を形成するに際し、前記アルコキシド溶液に１，
３−あるいはβ−ジケトン基を含有する化合物を混合ア
ルコキシドに対して０．１〜１０．０倍モル添加し、更
に必要に応じて水を添加することを特徴とするゾルーゲ
ル法によるアルミナ含有薄膜の製造方法。[Claims] 1. When forming an aluminum oxide thin film using aluminum alkoxide, 1.
, 3- or β-diketone group is added in moles of 0.1 to 10.0 times the mole of aluminum alkoxide, and further water is added as necessary. manufacturing method. 2. When forming an aluminum-containing oxide thin film using one or more alkoxides selected from silicon, titanium, zirconium, phosphorus, and boron alkoxides and aluminum alkoxide, 1,
Preparation of an alumina-containing thin film by a sol-gel method, characterized in that a compound containing a 3- or β-diketone group is added in moles of 0.1 to 10.0 times the mole of the mixed alkoxide, and water is further added as necessary. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10275988A JPH01275763A (en) | 1988-04-27 | 1988-04-27 | Production of alumina-containing thin film by sol-gel process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10275988A JPH01275763A (en) | 1988-04-27 | 1988-04-27 | Production of alumina-containing thin film by sol-gel process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01275763A true JPH01275763A (en) | 1989-11-06 |
Family
ID=14336126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10275988A Pending JPH01275763A (en) | 1988-04-27 | 1988-04-27 | Production of alumina-containing thin film by sol-gel process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01275763A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004014986A1 (en) * | 2002-08-07 | 2004-02-19 | Showa Denko K. K. | Metal alkoxide hydrolytic polycondensation solution and transparent films manufactured therefrom |
| JP2011251890A (en) * | 2010-05-07 | 2011-12-15 | Canon Inc | Precursor sol of aluminum oxide, optical member, and method for the producing optical member |
-
1988
- 1988-04-27 JP JP10275988A patent/JPH01275763A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004014986A1 (en) * | 2002-08-07 | 2004-02-19 | Showa Denko K. K. | Metal alkoxide hydrolytic polycondensation solution and transparent films manufactured therefrom |
| JP2011251890A (en) * | 2010-05-07 | 2011-12-15 | Canon Inc | Precursor sol of aluminum oxide, optical member, and method for the producing optical member |
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