JPH04142372A - Coating solution for forming metal oxide film - Google Patents
Coating solution for forming metal oxide filmInfo
- Publication number
- JPH04142372A JPH04142372A JP26524490A JP26524490A JPH04142372A JP H04142372 A JPH04142372 A JP H04142372A JP 26524490 A JP26524490 A JP 26524490A JP 26524490 A JP26524490 A JP 26524490A JP H04142372 A JPH04142372 A JP H04142372A
- Authority
- JP
- Japan
- Prior art keywords
- film
- metal
- coating
- oxide film
- alkoxide
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 9
- 150000004706 metal oxides Chemical class 0.000 title claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000001476 alcoholic effect Effects 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 3
- 239000010408 film Substances 0.000 description 59
- 239000010936 titanium Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 14
- 150000001298 alcohols Chemical class 0.000 description 12
- 239000010955 niobium Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- MKUWVMRNQOOSAT-UHFFFAOYSA-N methylvinylmethanol Natural products CC(O)C=C MKUWVMRNQOOSAT-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
- -1 transition metal alkoxides Chemical class 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- BVOSSZSHBZQJOI-UHFFFAOYSA-N 1-Hexen-3-ol Chemical compound CCCC(O)C=C BVOSSZSHBZQJOI-UHFFFAOYSA-N 0.000 description 2
- VHVMXWZXFBOANQ-UHFFFAOYSA-N 1-Penten-3-ol Chemical compound CCC(O)C=C VHVMXWZXFBOANQ-UHFFFAOYSA-N 0.000 description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- DINQVNXOZUORJS-UHFFFAOYSA-N butan-1-olate;niobium(5+) Chemical compound [Nb+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] DINQVNXOZUORJS-UHFFFAOYSA-N 0.000 description 2
- LTFTWJYRQNTCHI-UHFFFAOYSA-N hex-1-yn-3-ol Chemical compound CCCC(O)C#C LTFTWJYRQNTCHI-UHFFFAOYSA-N 0.000 description 2
- ODEHKVYXWLXRRR-UHFFFAOYSA-N hex-3-yn-1-ol Chemical compound CCC#CCCO ODEHKVYXWLXRRR-UHFFFAOYSA-N 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
- GOQJMMHTSOQIEI-UHFFFAOYSA-N hex-5-yn-1-ol Chemical compound OCCCCC#C GOQJMMHTSOQIEI-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- JEYLKNVLTAPJAF-UHFFFAOYSA-N xi-3-Methyl-3-buten-2-ol Chemical compound CC(O)C(C)=C JEYLKNVLTAPJAF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- OWFJMIVZYSDULZ-PXOLEDIWSA-N (4s,4ar,5s,5ar,6s,12ar)-4-(dimethylamino)-1,5,6,10,11,12a-hexahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O OWFJMIVZYSDULZ-PXOLEDIWSA-N 0.000 description 1
- BTSIZIIPFNVMHF-ONEGZZNKSA-N (E)-2-penten-1-ol Chemical compound CC\C=C\CO BTSIZIIPFNVMHF-ONEGZZNKSA-N 0.000 description 1
- 239000001586 (Z)-pent-2-en-1-ol Substances 0.000 description 1
- FSUXYWPILZJGCC-NSCUHMNNSA-N (e)-pent-3-en-1-ol Chemical compound C\C=C\CCO FSUXYWPILZJGCC-NSCUHMNNSA-N 0.000 description 1
- GJYMQFMQRRNLCY-ONEGZZNKSA-N (e)-pent-3-en-2-ol Chemical compound C\C=C\C(C)O GJYMQFMQRRNLCY-ONEGZZNKSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 description 1
- DZNLEQBXXLGELU-UHFFFAOYSA-N 3,4-dimethylpent-1-yn-3-ol Chemical compound CC(C)C(C)(O)C#C DZNLEQBXXLGELU-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- NSPPRYXGGYQMPY-UHFFFAOYSA-N 3-Methylbuten-2-ol-1 Natural products CC(C)C(O)=C NSPPRYXGGYQMPY-UHFFFAOYSA-N 0.000 description 1
- PUNRPAWKFTXZIW-UHFFFAOYSA-N 3-ethylpent-1-yn-3-ol Chemical compound CCC(O)(CC)C#C PUNRPAWKFTXZIW-UHFFFAOYSA-N 0.000 description 1
- DBAMUTGXJAWDEA-UHFFFAOYSA-N Butynol Chemical compound CCC#CO DBAMUTGXJAWDEA-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- NEEDEQSZOUAJMU-UHFFFAOYSA-N but-2-yn-1-ol Chemical compound CC#CCO NEEDEQSZOUAJMU-UHFFFAOYSA-N 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- OTJZCIYGRUNXTP-UHFFFAOYSA-N but-3-yn-1-ol Chemical compound OCCC#C OTJZCIYGRUNXTP-UHFFFAOYSA-N 0.000 description 1
- QORWLRPWMJEJKP-UHFFFAOYSA-N butan-1-olate;tantalum(5+) Chemical compound [Ta+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] QORWLRPWMJEJKP-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohex-2-en-1-ol Chemical compound OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- SHSFXAVQBIEYMK-UHFFFAOYSA-N hept-1-yn-3-ol Chemical compound CCCCC(O)C#C SHSFXAVQBIEYMK-UHFFFAOYSA-N 0.000 description 1
- OGDYROFIIXDTQK-UHFFFAOYSA-N hept-2-yn-1-ol Chemical compound CCCCC#CCO OGDYROFIIXDTQK-UHFFFAOYSA-N 0.000 description 1
- PSWHODJVUOXHKA-UHFFFAOYSA-N hept-3-yn-1-ol Chemical compound CCCC#CCCO PSWHODJVUOXHKA-UHFFFAOYSA-N 0.000 description 1
- XLTJVODPJJDQNG-UHFFFAOYSA-N hept-4-yn-1-ol Chemical compound CCC#CCCCO XLTJVODPJJDQNG-UHFFFAOYSA-N 0.000 description 1
- VOHBMHAELZLACG-UHFFFAOYSA-N hept-5-yn-3-ol Chemical compound CCC(O)CC#CC VOHBMHAELZLACG-UHFFFAOYSA-N 0.000 description 1
- MLRKYSNODSLPAB-UHFFFAOYSA-N hex-1-yn-1-ol Chemical compound CCCCC#CO MLRKYSNODSLPAB-UHFFFAOYSA-N 0.000 description 1
- IKROQHVDACEGBA-UHFFFAOYSA-N hex-4-yn-2-ol Chemical compound CC#CCC(C)O IKROQHVDACEGBA-UHFFFAOYSA-N 0.000 description 1
- AJYGRAORQSCNED-UHFFFAOYSA-N hex-5-yn-3-ol Chemical compound CCC(O)CC#C AJYGRAORQSCNED-UHFFFAOYSA-N 0.000 description 1
- SZYLTIUVWARXOO-UHFFFAOYSA-N hexa-1,5-dien-3-ol Chemical compound C=CC(O)CC=C SZYLTIUVWARXOO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- BTSIZIIPFNVMHF-UHFFFAOYSA-N nor-leaf alcohol Natural products CCC=CCO BTSIZIIPFNVMHF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- LBSKEFWQPNVWTP-UHFFFAOYSA-N pent-1-yn-3-ol Chemical compound CCC(O)C#C LBSKEFWQPNVWTP-UHFFFAOYSA-N 0.000 description 1
- WLPYSOCRPHTIDZ-UHFFFAOYSA-N pent-2-yn-1-ol Chemical compound CCC#CCO WLPYSOCRPHTIDZ-UHFFFAOYSA-N 0.000 description 1
- IDYNOORNKYEHHO-UHFFFAOYSA-N pent-3-yn-1-ol Chemical compound CC#CCCO IDYNOORNKYEHHO-UHFFFAOYSA-N 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- FSUXYWPILZJGCC-UHFFFAOYSA-N pent-4-en-1-ol Natural products CC=CCCO FSUXYWPILZJGCC-UHFFFAOYSA-N 0.000 description 1
- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 1
- CRWVOXFUXPYTRK-UHFFFAOYSA-N pent-4-yn-1-ol Chemical compound OCCCC#C CRWVOXFUXPYTRK-UHFFFAOYSA-N 0.000 description 1
- JTHLRRZARWSHBE-UHFFFAOYSA-N pent-4-yn-2-ol Chemical compound CC(O)CC#C JTHLRRZARWSHBE-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
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Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、Ｔｉ、 Ｚｒ、 Ｎｂ及びＴａの単一又は
複合の金属酸化物皮膜を、良質にかつ安定して形成させ
るコーティング液に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a coating liquid that can stably form a single or composite metal oxide film of Ti, Zr, Nb and Ta with good quality.
酸化チタン、酸化ジルコニウム、酸化ニオブ並びに酸化
タンタルの単一又は複合のコーティング皮膜は、誘電体
膜あるいは光電解膜として有用であり、またガラスの表
面反射の防止、表面硬度の向上や鉄鋼材料の耐食性、耐
熱性向上などに効果のあることが知られている。Single or composite coatings of titanium oxide, zirconium oxide, niobium oxide, and tantalum oxide are useful as dielectric films or photoelectrolytic films, and are also useful for preventing surface reflection of glass, improving surface hardness, and corrosion resistance of steel materials. It is known to be effective in improving heat resistance.
（従来の技術）
Ｔｉ、 Ｚｒ、 Ｎｂ及びＴａの金属酸化物皮膜のコー
ティングによる形成方法としては、かかる金属のアルコ
キシドを原料に用いた、いわゆるゾル・ゲル法が代表的
なものとして挙げられる。(Prior Art) A typical method for forming metal oxide films of Ti, Zr, Nb, and Ta by coating is the so-called sol-gel method using alkoxides of such metals as raw materials.
ゾル・ゲル法とは金属アルコキシドを、水溶液中又は有
機溶媒と水との混合溶液中で徐々に加水分解させて、酸
化物又は水酸化物がコロイド状で分散した溶液（ゾル）
を作り、これを基板上に塗布した後、水を蒸発させてゾ
ルを乾燥固化させてゲルとし、更に熱分解させて酸化物
皮膜とする方法である。What is the sol-gel method? A metal alkoxide is gradually hydrolyzed in an aqueous solution or a mixed solution of an organic solvent and water to create a solution (sol) in which the oxide or hydroxide is colloidally dispersed.
This method involves making a sol, applying it onto a substrate, evaporating the water, drying and solidifying the sol to form a gel, and then thermally decomposing it to form an oxide film.
しかしこのゾル・ゲル法は、加水分解時のｐＨ１金属ア
ルコキシドの濃度及び水との比率、コーティング液の温
度等、種々のパラメータを精密に制御しなければ成膜さ
せることができず、けい素のアルコキシド等の如き加水
分解の遅い一部の金属アルコキシドを除いて実際の成膜
工程に適用するのは難しかった。またゾル・ゲル法にて
２種以上の金属元素を成分として含有する複合酸化物皮
膜の形成を行うことは、原理的には可能であるが個々の
アルコキシドの加水分解速度が異なるためにｐＨや濃度
等のパラメータを最適化するためには多くの困難が伴う
。However, this sol-gel method cannot form a film unless various parameters such as the concentration of pH 1 metal alkoxide during hydrolysis, the ratio with water, and the temperature of the coating solution are precisely controlled. With the exception of some metal alkoxides that are slow to hydrolyze, such as alkoxides, it has been difficult to apply them to actual film forming processes. Although it is theoretically possible to form a composite oxide film containing two or more metal elements using the sol-gel method, the hydrolysis rate of each alkoxide is different, so the pH and Many difficulties arise in optimizing parameters such as concentration.
そこでかかるゾル・ゲル法のより実用的な方法として、
金属アルコキシドの、水を含まない有機溶媒溶液を直接
基板に塗布し、雰囲気中の水分により加水分解・重合ゲ
ル化させて硬化させる方法が知られている。この方法は
操作が単純で制御要因が少な（、量産向きであり、実際
にガラスやプラスチックス、高分子フィルム上へ光線反
射防止や表面硬化のためのコーティングに実用化されて
いる。（特開昭５７−３７３５号公報、特開昭６０−４
０１７１号公報、Ｆ、Ｇｅｏｔｔｉ−Ｂｉａｎｃｈｉｎ
ｉ他、Ｊ、Ｎｏｎ−Ｃｒｙｓｔａｌ。Therefore, as a more practical method of the sol-gel method,
A known method is to apply a water-free organic solvent solution of a metal alkoxide directly to a substrate, and then harden the solution by hydrolyzing and polymerizing into a gel due to moisture in the atmosphere. This method is simple to operate and requires few control factors, and is suitable for mass production, and has actually been put into practical use as a coating for glass, plastics, and polymer films to prevent light reflection and harden the surface. Publication No. 57-3735, Japanese Unexamined Patent Publication No. 60-4
Publication No. 0171, F. Geotti-Bianchin
i et al., J. Non-Crystal.
５ｏｌｉｄｓ、６３ ｐｐ２５１ （１９８４）等参照
）。5olids, 63 pp251 (1984), etc.).
しかし上記の方法でＴｔ＋ Ｚｒ、 Ｎｂ＋ Ｔａ等の
遷移金属の酸化物皮膜を成膜させようとすると、これら
遷移金属アルコキシドの加水分解速度は一般に極めて大
きいので、たいていの場合は重合・ゲル化せず、その結
果密着力のない細かい粉末になってしまうか、仮に皮膜
が得られたとしても非常に薄い膜になってしまう。した
がってこれらの遷移金属の酸化物を得るためにアルコキ
シドの有機溶媒溶液をコーティングしても良質の膜を形
成させることはできなかった。However, when attempting to form an oxide film of a transition metal such as Tt+Zr or Nb+Ta using the above method, the hydrolysis rate of these transition metal alkoxides is generally extremely high, so in most cases polymerization and gelation do not occur. As a result, it becomes a fine powder with no adhesion, or even if a film is obtained, it becomes a very thin film. Therefore, even if a solution of an alkoxide in an organic solvent was coated to obtain oxides of these transition metals, a film of good quality could not be formed.
このように成膜せず、粉末化してしまう原因は、金属ア
ルコキシドの加水分解が速すぎて、十分に重合・ゲル化
する時間がないためと考えられる。The reason why the metal alkoxide is not formed into a film but becomes powder is considered to be that the metal alkoxide is hydrolyzed too quickly and there is not enough time for it to polymerize and gel.
したがって上記のような金属酸化物皮膜を安定に形成さ
せるためには、アルコキシドの加水分解速度を粉末化し
ない程度まで遅くさせなければならない。Therefore, in order to stably form the metal oxide film as described above, the rate of hydrolysis of the alkoxide must be slowed down to such an extent that it does not turn into powder.
加水分解速度を遅くさせる手段としては、金属アルコキ
シドのアルコキシル基の一部又は全部を、アセチルアセ
トン等の錯体やステアリン酸等の高級脂肪酸基に置換す
る方法（Ｗ、 Ｃ，ＬａＣｏｕｒｓｅ他、Ｃｅｒａｍ、
Ｅｎｇ、 Ｓｃｉ、 Ｐｒｏｃ ８ （９−１０）
ｐｐＨ２８−１１３４（１９８７）等）が公知ではある
が、逆に安定化しすぎて加水分解が困難になり、その結
果炭素が残留したり、錯体や塩が結晶化・析出して膜に
ならなかったりする場合もあるので、前記遷移金属の酸
化物皮膜のコーティングに対しては必ずしも適当な手段
であるとは言い難かった。As a means of slowing down the hydrolysis rate, a method of substituting a part or all of the alkoxyl group of the metal alkoxide with a complex such as acetylacetone or a higher fatty acid group such as stearic acid (W, C, LaCourse et al., Ceram,
Eng, Sci, Proc 8 (9-10)
ppH 28-1134 (1987), etc.), but on the other hand, it becomes too stable and difficult to hydrolyze, resulting in carbon remaining or complexes and salts crystallizing/precipitating and failing to form a film. Therefore, it could not be said that this method is necessarily suitable for coating the transition metal oxide film.
（発明が解決しようとする課Ｂ）
この発明は、上記の問題を有利に解決するもので、金属
アルコキシド直接塗布法にてＴｉ、 Ｎｂ、 Ｚｒ。(Problem B to be Solved by the Invention) This invention advantageously solves the above-mentioned problems and coats Ti, Nb, and Zr using a metal alkoxide direct coating method.
Ｔａの良質な酸化物皮膜を形成させ得るコーティング液
を提案することを目的とする。The purpose of the present invention is to propose a coating liquid that can form a high-quality Ta oxide film.
（課題を解決するための手段）
発明者らは、金属アルコキシド類の水和速度と成膜性と
の間に密接な関係があることを発見し、水和速度を制御
する方法について鋭意探索した結果、不飽和アルコール
類が、加水分解速度の抑制に有効であり、かかる不飽和
アルコール類をコーティング液の溶媒に用いることによ
って成膜性を格段に向上させ得ることの知見を得た。(Means for Solving the Problems) The inventors discovered that there is a close relationship between the hydration rate of metal alkoxides and film forming properties, and conducted an intensive search for a method to control the hydration rate. As a result, it was found that unsaturated alcohols are effective in suppressing the rate of hydrolysis, and that film-forming properties can be significantly improved by using such unsaturated alcohols as a solvent in a coating liquid.
この発明は、上記の知見に立脚するものである。This invention is based on the above knowledge.
すなわちこの発明は、−重代：Ｍ（ＯＲ）、 （Ｍは
Ｔｉ、 Ｚｒ、 Ｎｂ及びＴａのうちの１種又は２種以
上、Ｒは飽和又は不飽和の炭化水素基、ｎは上記金属元
素の価数によって定まる整数を示す）で表される１種又
は２種以上の金属アルコキシド類を、不飽和アルコール
類からなる溶媒に溶解させてなる金属酸化物皮膜形成用
コーティング液である。That is, this invention provides the following features: - heavy group: M (OR), (M is one or more of Ti, Zr, Nb, and Ta, R is a saturated or unsaturated hydrocarbon group, and n is the above metal element This is a coating liquid for forming a metal oxide film, which is prepared by dissolving one or more metal alkoxides represented by (indicates an integer determined by the valence of ) in a solvent consisting of an unsaturated alcohol.
この発明の金属酸化物皮膜は、一部に水酸基又はアルコ
キシル基を含んだ重合体皮膜をも含む。The metal oxide film of the present invention also includes a polymer film partially containing hydroxyl groups or alkoxyl groups.
金属酸化物皮膜の原料となるアルコキシド類は、−重代
： Ｍ （ＯＲ）、で表される任意の組成のものが使
用できる。ここでＭは、Ｔｉ、 Ｎｂ、 Ｚｒ及びＴａ
のうちの１種又は２種以上を表す。ｎは金属の価数によ
って定まる整数で、−船釣には、Ｔｉ、 Ｚｒの場合は
４、Ｎｂ、 Ｔａの場合は５である。As the alkoxides serving as raw materials for the metal oxide film, those having an arbitrary composition represented by M (OR) can be used. Here, M is Ti, Nb, Zr and Ta
Represents one or more of the following. n is an integer determined by the valence of the metal; for boat fishing, it is 4 for Ti and Zr, and 5 for Nb and Ta.
Ｒは飽和又は不飽和炭化水素基であり、一般弐ＣｎＨ２
ｎ＋＋ の飽和アルキル基の他にも、環状アルキル基、
不飽和アルキル基、芳香族基（アリール基）又はこれら
の混合基を示す。R is a saturated or unsaturated hydrocarbon group, generally 2CnH2
In addition to n++ saturated alkyl groups, cyclic alkyl groups,
Indicates an unsaturated alkyl group, an aromatic group (aryl group), or a mixed group thereof.
ＭとしてＴｉを例にとると、金属アルコキシドとしては
、Ｔｉ （ＯＣＨ：Ｉ） ４（チタンテトラメトキシド
）Ｔｉ（ＯＣＪｓ）ａ （チタンテトラエトキシド）、
Ｔｉ （ＯＣ３＋（７） ａ （チタンテトラｎプロポ
キシド）、Ｔｉ （ＯＣＲ（ＣＨ３）ｚ ） ａ＜チタ
ンテトライソプロポキシド） 、ＴＩ（ＯＣ４）＋９）
４ （チタンテトラｎブトキシド）、Ｔｉ （ＯＣＨｚ
ＣＨ（ＣＨい２）４（チタンテトライソブトキシド）
、Ｔｉ（ＯＣ，Ｈ５）、 （チタンテトラフェノキシド
）、Ｔｉ（ＯＣｚ）Ｉｓ）ｚ（ＯＣＪｔ）ｚ （チタン
ジエトキシジｎプロポキシド） 、Ｔｉ （ＯＣ３Ｈ７
） ｚ （ＯＣ６Ｈ５） ２ （チタンジｎプロポキシ
ジフェノキシド）などが使用可能である。Taking Ti as an example, the metal alkoxides include Ti (OCH:I) 4 (titanium tetramethoxide) Ti (OCJs) a (titanium tetraethoxide),
Ti (OC3+(7) a (titanium tetran propoxide), Ti (OCR(CH3)z) a<titanium tetraisopropoxide), TI(OC4)+9)
4 (Titanium tetra n-butoxide), Ti (OCHz
CH(CH2)4(Titanium tetraisobutoxide)
, Ti(OC,H5), (Titanium tetraphenoxide), Ti(OCz)Is)z(OCJt)z (Titanium diethoxydin propoxide), Ti(OC3H7
) z (OC6H5) 2 (titanium di-propoxy diphenoxide) and the like can be used.
アルコキシル基としてどのようなものを持ったアルコキ
シドを使うかは、入手のしやすさ、取り扱いやすさ、有
機溶媒への溶解度等を考慮して適宜選択する。The type of alkoxide having an alkoxyl group to be used is appropriately selected in consideration of availability, ease of handling, solubility in organic solvents, and the like.
金属アルコキシド類は、Ｔｉ、 Ｎｂ、 Ｚｒ、、Ｔａ
の群から選ばれた単一のものの他、複数元素のアルコキ
シドを混合したものであってもよい。この場合、各金属
アルコキシドのアルコキシル基は互いに異なっていても
よい。また、アルコキシド１分子内に２種以上の金属元
素を含む、複合アルコキシドであってもよい。Metal alkoxides include Ti, Nb, Zr, Ta
In addition to a single alkoxide selected from the group, a mixture of alkoxides of multiple elements may be used. In this case, the alkoxyl groups of each metal alkoxide may be different from each other. Further, it may be a composite alkoxide containing two or more types of metal elements in one alkoxide molecule.
複数の金属アルコキシド類を混合することにより、また
複合アルコキシドを使うことにより、複合酸化物又は固
溶体酸化物の皮膜を容易に形成させることができる。形
成される固溶体皮膜中の金属成分の割合は、原料の混合
比を変えるだけで、正確かつ自由に制御できる。By mixing a plurality of metal alkoxides or by using a composite alkoxide, a composite oxide or solid solution oxide film can be easily formed. The proportion of metal components in the formed solid solution film can be accurately and freely controlled simply by changing the mixing ratio of raw materials.
金属アルコキシド類の溶媒には、室温で液体の不飽和ア
ルコール類を用いる。不飽和アルコール類の要件として
は、アルコール性水酸基を分子内に１つ以上有し、かつ
：
ａ）１つ以上の二重結合を分子内に有するｂＨつ以上の
三重結合を分子内に有するｃ） １つ以上の二重結合と
１つ以上の三重結合を分子内に同時に有する
のうちのいずれか１条件を満たすことである。Unsaturated alcohols that are liquid at room temperature are used as solvents for metal alkoxides. The unsaturated alcohols must have one or more alcoholic hydroxyl groups in the molecule, and: a) have one or more double bonds in the molecule; b) have at least one triple bond in the molecule; c) have one or more double bonds in the molecule; ) One of the conditions of simultaneously having one or more double bonds and one or more triple bonds in the molecule is satisfied.
上記要件を満たす不飽和アルコールとして当てはまるも
のは例えば、
（１）２−プロペン−１−オール（アリルアルコール）
、３−ブテン−１−オール、２−ブテン−１−オール（
クロチルアルコール）、２−メチル−２−フロペン−１
−オール（βメタリルアルコール）、３−ブテン２−オ
ール、４−ペンテン−１−オール、３〜ペンテン−１−
オール、２−ペンテン−１−オール、４−ペンテン−２
−オール、３−ペンテン−２−オール、１−ペンテン−
３−オール、３−メチル−３−ブテン−１〜オール、３
−メチル−２−ブテン−１−オール、３−メチル３−ブ
テン−２〜オール、２−メチル−３〜ブテン−２−オー
ル、２，２−ジメチル−２−プロペン−１−オール、１
−ヘキセン−３−オール、５−ヘキセン−１−オール、
２−シクロヘキセン−１−オール、１．５−へキサジエ
ン−３−オール、２，４−へキサジエン−１−オール、
２−ブテン−１，４−ジオール等のアルコ−ル性、
（２）２−プロピン−１−オール、１−ブチン−１−オ
ール、２−ブチン−１−オール、３〜ブチン−１−オー
ル、３゜メチル−１〜ブチン−３−オール、１−ペンチ
ン−３−オール、２−ペンチン−１−オール、３−ペン
チン−１−オール、４−ペンチン−１−オール、４−ペ
ンチン−２−オール、１−ヘキシン−３−オール、２−
ヘキシン−１〜オール、３−ヘキシン−１−オール、４
−ヘキシン−２−オール、５−ヘキシン−１−オール、
５−ヘキシン−３−オール、３−メチル−１−ペンチン
−３−オール、３，４−ジメチルペンチン−３−オール
、３エチル−１−ペンチン−３−オール、１−ヘプチン
−３−オール、２−ヘプチン−１−オール、３−ヘプチ
ン１−オール、４−ヘプチン−１−オール、５−ヘプチ
ン−３−オール、５−メチルｌ−ヘキシン−３−オール
、２−ブチン−１，４−ジオール、−３−ヘキシン−２
５−ジオール等のアルキノール（アセチレンアルコール
）類、
等が挙げられる。Examples of unsaturated alcohols that meet the above requirements are: (1) 2-propen-1-ol (allyl alcohol)
, 3-buten-1-ol, 2-buten-1-ol (
crotyl alcohol), 2-methyl-2-flopen-1
-ol (βmethallyl alcohol), 3-buten-2-ol, 4-penten-1-ol, 3-penten-1-ol
ol, 2-penten-1-ol, 4-penten-2
-ol, 3-penten-2-ol, 1-penten-
3-ol, 3-methyl-3-buten-1-ol, 3
-Methyl-2-buten-1-ol, 3-methyl-3-buten-2-ol, 2-methyl-3-buten-2-ol, 2,2-dimethyl-2-propen-1-ol, 1
-hexen-3-ol, 5-hexen-1-ol,
2-cyclohexen-1-ol, 1,5-hexadien-3-ol, 2,4-hexadien-1-ol,
Alcohols such as 2-butene-1,4-diol, (2) 2-propyn-1-ol, 1-butyn-1-ol, 2-butyn-1-ol, 3-butyn-1-ol , 3゜methyl-1-butyn-3-ol, 1-pentyn-3-ol, 2-pentyn-1-ol, 3-pentyn-1-ol, 4-pentyn-1-ol, 4-pentyn-2 -ol, 1-hexyn-3-ol, 2-ol
hexyn-1-ol, 3-hexyn-1-ol, 4
-hexyn-2-ol, 5-hexyn-1-ol,
5-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,4-dimethylpentyn-3-ol, 3ethyl-1-pentyn-3-ol, 1-heptyn-3-ol , 2-heptyn-1-ol, 3-heptyn-1-ol, 4-heptyn-1-ol, 5-heptyn-3-ol, 5-methyl l-hexyn-3-ol, 2-butyn-1,4 -diol, -3-hexyne-2
Examples include alkynols (acetylene alcohols) such as 5-diol, and the like.
かかる不飽和アルコール類中の、金属アルコキシド類の
濃度は、完全に相溶する範囲内であれば特に制限はない
。−船釣な傾向として、濃度が高い方が一回のコーティ
ング操作で得られる膜厚が厚くなるが、多孔質になり、
濃度の低い方が膜厚は薄くなるが膜の緻密度は上がる。The concentration of metal alkoxides in such unsaturated alcohols is not particularly limited as long as they are completely compatible. - As a general rule, the higher the concentration, the thicker the film obtained in one coating operation, but the more porous it becomes.
The lower the concentration, the thinner the film thickness, but the higher the density of the film.
したがってコーティングする目的、またコーティングさ
れる基材の種類によって、濃度は適宜選択する。Therefore, the concentration is appropriately selected depending on the purpose of coating and the type of substrate to be coated.
コーティングを実際に行う方法には、スプレー法、ロー
ルコート法、デイツプコート法、スピンコード法等が代
表的な方法として挙げられる。前２者は操作が簡単なた
めに大面積の基材に塗布するのに適していて、後２者は
低粘度の液を使って、非常に薄い膜を高均質に塗布する
のに適している。Typical methods for actually performing the coating include a spray method, a roll coating method, a dip coating method, a spin coating method, and the like. The first two are easy to operate and are suitable for coating large areas of substrates, while the latter two are suitable for coating very thin films with high uniformity using low viscosity liquids. There is.
この発明のコーティング液は、上記したいずれの塗布方
法にも適用可能であり、溶媒の不飽和アルコール類、オ
キシアルコール類として高粘度のものから低粘度のもの
まで種々選択できるので、目的にあったコーティング液
を調製することができる。The coating liquid of the present invention can be applied to any of the above-mentioned coating methods, and various unsaturated alcohols and oxyalcohols can be selected as solvents, from high to low viscosity, so that it can be applied to suit the purpose. A coating liquid can be prepared.
この発明のコーティング液に、増粘剤、表面張力調整剤
、有機樹脂のような、第３の添加剤を加えて更に、コー
ティングに適するようにすることができるのはもちろん
であるが、必須というわけではない。It is of course possible to add third additives to the coating solution of this invention to make it further suitable for coating, such as thickeners, surface tension modifiers, and organic resins, but there are some essential Do not mean.
コーティングを終えた基材を、通常の大気雰囲気中、又
は温度・湿度を制御した雰囲気中に放置し、溶媒を揮発
させて除去すると同時に雰囲気中の水により加水分解さ
せて皮膜を硬化させる。このときの溶媒の揮発速度と金
属アルコキシド類の加水分解速度との制御は重要な因子
であり、揮発速度が相対的に高いと、硬化が遅れ、ひび
割れやピンホール、ブラッシングの原因となる。逆に揮
発速度が低いと、いつまでも塗布面が湿潤状態となって
皮膜ができなかったり、溶媒を含んだまま硬化してしま
い、これもまた熱分解時に割れたり膨れたりする原因と
なり得る。したがって溶媒の選択、雰囲気の温度や湿度
の管理によって溶媒の揮発速度、金属アルコキシド類の
加水分解速度の両速度を制御する必要がある。The coated substrate is left in a normal atmospheric environment or in an atmosphere with controlled temperature and humidity to volatilize and remove the solvent and at the same time cause hydrolysis with water in the atmosphere to harden the film. Controlling the volatilization rate of the solvent and the hydrolysis rate of the metal alkoxides at this time is an important factor; if the volatilization rate is relatively high, curing will be delayed, causing cracks, pinholes, and brushing. On the other hand, if the volatilization rate is low, the coated surface will remain wet forever and no film will be formed, or it will harden while containing the solvent, which can also cause cracking or swelling during thermal decomposition. Therefore, it is necessary to control both the rate of volatilization of the solvent and the rate of hydrolysis of metal alkoxides by selecting the solvent and controlling the temperature and humidity of the atmosphere.
硬化させた皮膜の組成は、通常は一部に水酸基又はアル
コキシル基を含んだ重合体であり、用途によってはその
ままで使用できるが、酸化物としての機能を求める場合
は、硬化後に熱分解処理を行って酸化物とする。熱分解
の際の雰囲気はどのようなものであっても構わないが、
還元性雰囲気では有機成分の不完全分解によって炭素が
残りやすく、あまり好ましくないので、−船釣には大気
中で行う。また熱処理温度は、常温で硬化させた皮膜を
単に熱分解させて酸化物皮膜とするだけで良い場合は３
００〜６００°Ｃ程度の低温で行うことができる。ただ
し固相反応を行わせて複合酸化物組成の皮膜を形成させ
る場合や結晶性の良い皮膜を得ようとする場合には、さ
らに高温の熱処理が必要なことがある。The composition of the cured film is usually a polymer containing a portion of hydroxyl or alkoxyl groups, and depending on the application it can be used as is, but if it is required to function as an oxide, it may be thermally decomposed after curing. to form an oxide. The atmosphere during pyrolysis may be of any kind, but
In a reducing atmosphere, carbon tends to remain due to incomplete decomposition of organic components, which is not very desirable, so boat fishing is carried out in the atmosphere. In addition, the heat treatment temperature should be set to 3 if the film cured at room temperature is simply thermally decomposed to form an oxide film.
It can be carried out at a low temperature of about 00 to 600°C. However, when forming a film having a composite oxide composition by performing a solid phase reaction, or when attempting to obtain a film with good crystallinity, a higher temperature heat treatment may be necessary.
熱分解処理を行う装置、加熱方法や温度パターンは、特
に限定されない。目的とする皮膜及び基材の材質、形状
によって適宜選択する。The apparatus, heating method, and temperature pattern for performing the thermal decomposition treatment are not particularly limited. It is selected as appropriate depending on the material and shape of the desired film and base material.
（作 用）
不飽和アルコール類の、金属アルコキシド類に対する加
水分解安定化の機構は明らかでないが、以下のように推
察される。(Effect) The mechanism by which unsaturated alcohols hydrolytically stabilize metal alkoxides is not clear, but it is inferred as follows.
金属アルコキシドに結合しているアルコキシル基が、よ
り酸性の強い不飽和アルコールのアルコキシル基に置換
されることによって、金属原子の塩基性が減少して水分
子の攻撃を受けにくくなるために、加水分解に対して安
定化されると考えられる。金属原子の塩基性の減少によ
る加水分解安定化機構は、金属キレート化合物に見られ
るのと同様の理由と推察される。Hydrolysis occurs because the alkoxyl group bonded to the metal alkoxide is replaced with the alkoxyl group of a more acidic unsaturated alcohol, reducing the basicity of the metal atom and making it less susceptible to attack by water molecules. It is thought that it is stabilized against. The hydrolytic stabilization mechanism due to a decrease in the basicity of the metal atom is presumed to be the same reason as that seen in metal chelate compounds.
不飽和アルコールの金属アルコキシドへの２１０反応は
、過剰の不飽和アルコール類が共存すれば常温でも速や
かに進行すると考えられる。このため実際のコーティン
グの際には、溶媒としての不飽和アルコール類が大量に
存在するので、生成物を特に単離しなくても金属アルコ
キシドの安定化の目的は十分であると考えられる。言い
かえれば金属アルコキシド類を不飽和アルコール類に溶
解させるだけで安定なコーティング液が得られるわけで
ある。It is thought that the 210 reaction of unsaturated alcohols to metal alkoxides proceeds rapidly even at room temperature if an excess of unsaturated alcohols coexists. For this reason, during actual coating, a large amount of unsaturated alcohol is present as a solvent, so it is considered that the purpose of stabilizing the metal alkoxide is sufficient even without isolation of the product. In other words, a stable coating solution can be obtained simply by dissolving metal alkoxides in unsaturated alcohols.
（実施例）
裏旌班上
ジルコニウムテトラブトキシド（Ｚｒ（ＯＣ４Ｈ７）４
）１５ｇを３−ブテン−２−オール（ＣＨ２・ＣＨＣ）
Ｉ（ＯＨ）ＣＨ３） ８５ｇ中に溶解させたところ、淡
黄色の溶液を得た。(Example) Zirconium tetrabutoxide (Zr(OC4H7)4
) 15g of 3-buten-2-ol (CH2・CHC)
When dissolved in 85 g of I(OH)CH3), a pale yellow solution was obtained.
この溶液を、ポリエチレンフィルムの耐摩耗性と撥水性
を向上させる目的で、フィルム表面にローラーで塗布し
、大気中常温で乾燥させたところ、フィルム表面に透明
な薄い酸化ジルコニウムの皮膜が形成され、目的を達成
することができた。In order to improve the abrasion resistance and water repellency of polyethylene film, this solution was applied to the film surface with a roller and dried in the air at room temperature, resulting in the formation of a thin transparent zirconium oxide film on the film surface. I was able to achieve my goal.
実隻拠叉
チタンテトライソプロポキシド（Ｔｉ （ＯＣ３）１７
） ａ ）２０ｇを３−メチル−１−ブチン−３−オー
ル（ＣＨＥＣＣ（ＯＨ）（Ｃ）ｌ：１）２） ８０ｇに
混合させたところ、黄赤色の溶液が得られた。この溶液
に鏡面研摩した石英ガラスを浸漬し、１０ｍｍ／ｍｉｎ
で引き上げたところ、石英ガラス両面に薄い液膜が形成
された。Real ship-based titanium tetraisopropoxide (Ti (OC3)17
) a) 20 g were mixed with 80 g of 3-methyl-1-butyn-3-ol (CHECC(OH)(C)l:1)2), resulting in a yellow-red solution. A mirror-polished quartz glass was immersed in this solution, and the water was heated at 10 mm/min.
When the glass was pulled up, a thin liquid film was formed on both sides of the quartz glass.
この石英ガラスを温度２０°Ｃ１相対温度３０％の大気
中に放置したところ、約１ ｍｉｎで乾燥した。次いで
４００°Ｃに保持した電気炉に挿入し、そのまま３０分
間保持後取り出したところ、石英ガラス表面に厚さ約０
．５μｍの透明で強固な皮膜が形成された。この皮膜を
Ｘ線回折で分析したところ、二酸化チタンの膜であるこ
とがわかった。When this quartz glass was left in the atmosphere at a temperature of 20°C and a relative temperature of 30%, it dried in about 1 minute. Next, it was inserted into an electric furnace maintained at 400°C, kept as it was for 30 minutes, and then taken out.
．． A transparent and strong film of 5 μm was formed. When this film was analyzed by X-ray diffraction, it was found to be a titanium dioxide film.
災施拠主
ニオブペンタブトキシドＮｂ（ＯＣ４Ｈ７）ｓ ３０
ｇを３メチル−１−ブチン−３−オール（ＣＨＥＣＣ（
ＯＨ） （ＣＨ３）２７０ｇに混合したところ、黄色の
溶液が得られた。Disaster relief owner Niobium pentabutoxide Nb (OC4H7) s 30
g to 3methyl-1-butyn-3-ol (CHECC(
When mixed with 270 g of OH) (CH3), a yellow solution was obtained.
この溶液に電解研磨した厚さ０．３ ｍｍのＳＵＳ ３
０４ステンレス鋼板を浸漬し、３０ｍｍ／ｍｉｎで引き
上げたところ、鋼板上に薄い液膜が形成された。これを
温度２０゛Ｃ１相対湿度３５％の大気中に放置したとこ
ろ、約１ ｍｉｎで乾燥した。これを４００°Ｃに保持
した電気炉に挿入し、そのまま３０分保持後取り出した
ところ、表面に厚さ約０．５μｍの酸化ニオブの透明な
強固な皮膜が形成された。SUS 3 with a thickness of 0.3 mm was electrolytically polished in this solution.
When a 04 stainless steel plate was immersed and pulled up at a rate of 30 mm/min, a thin liquid film was formed on the steel plate. When this was left in the atmosphere at a temperature of 20°C and a relative humidity of 35%, it dried in about 1 minute. When this was inserted into an electric furnace maintained at 400° C., held for 30 minutes, and then taken out, a strong transparent film of niobium oxide with a thickness of about 0.5 μm was formed on the surface.
夫旌±土
原料のニオブペンタブトキシドをタンタルペンタブトキ
シドＴａ （ＯＣ４Ｆ１９） ｓに変えたほかは実施例
３と同一の方法で５ｔｌＳ ３０４ステンレス鋼板に成
膜したところ、同様の酸化タンタルの強固な皮膜が形成
された。When a film was formed on a 5TLS 304 stainless steel plate in the same manner as in Example 3, except that the raw material niobium pentatoxide was replaced with tantalum pentatoxide Ta (OC4F19)s, a similar strong film of tantalum oxide was obtained. Been formed.
裏施炭ｌ
ジルコニウムテトラブトキシド（Ｚｒ（ＯＣＪ、）ａ）
１０ｇとチタンテトラブトキシド（Ｔｉ （ＯＣ４Ｈ９
） ａ ） ５ｇとを３−ブテン−２−オール（Ｃｕｔ
・Ｃ［（ＣＨ（ＯＨ）ＣＩ（ｓ） ８５ｇ中に溶解した
ところ、淡黄色の溶液を得た。これをポリエチレンフィ
ルムの耐摩耗性と撥水性を向上させる目的でフィルムに
ローラーで塗布し、大気中で乾燥させたところ、フィル
ム表面に透明なＴｉＯ□とＺｒＯ□とを成分とする薄い
皮膜が形成され、目的を達成することができた。Back coating l Zirconium tetrabutoxide (Zr(OCJ,)a)
10g and titanium tetrabutoxide (Ti (OC4H9
) a) 5g and 3-buten-2-ol (Cut
- When dissolved in 85 g of C[(CH(OH)CI(s)), a pale yellow solution was obtained.This was applied to the polyethylene film with a roller for the purpose of improving its abrasion resistance and water repellency. When the film was dried in the air, a transparent thin film containing TiO□ and ZrO□ was formed on the film surface, and the objective could be achieved.
去隻±旦
チタンテトラブトキシド（Ｔｉ（ＯＣａＬ） ａ ）
１０ ｇ及びタンタルペンタブトキシドＴａ （ＯＣ４
Ｈ９） ｓｌｏ ｇを３メチル−１−ブチン−３−オー
ル（ＣＨＥＣＣ（ＯＨ）（ＣＨ３）２ ）８０ｇに混合
したところ、微黄色の溶液が得られた。Titanium tetrabutoxide (Ti(OCaL) a)
10 g and tantalum pentabutoxide Ta (OC4
When H9) slog was mixed with 80 g of 3methyl-1-butyn-3-ol (CHECC(OH)(CH3)2), a slightly yellow solution was obtained.
ガラスに反射防止コーティングを施す目的で、研摩した
はうけい酸ガラスをこの溶液中に浸漬し、３０ｍｍ／ｍ
ｉｎで引き上げたところ、ガラス両面に薄い液膜が形成
された。このガラスを温度２０°Ｃ１相対温度４０％の
大気中に放置したところ、約１ｍ１ｎで乾燥した。次い
で４００°Ｃに保持した電気炉に挿入し、そのまま３０
分間保持後取り出したところ、表面に厚さ約０．５μＩ
のＴｉ０ｚ及びＴａ、０．からなる透明皮膜が形成され
た。このガラスの光線反射特性を調べたところ、未処理
のガラスに比べ、高い反射特性を有することがわかった
。For the purpose of applying an anti-reflection coating to glass, polished silicate glass was immersed in this solution at a rate of 30 mm/m.
When the glass was pulled up, a thin liquid film was formed on both sides of the glass. When this glass was left in the air at a temperature of 20° C. and a relative temperature of 40%, it dried in about 1 ml. Then, it was inserted into an electric furnace maintained at 400°C and heated for 30 minutes.
When I took it out after holding it for a minute, there was a thickness of about 0.5μI on the surface.
TiOz and Ta, 0. A transparent film was formed. When the light reflection characteristics of this glass were investigated, it was found that it had higher reflection characteristics than untreated glass.
此ｍ
ジルコニウムテトラブトキシド（Ｚｒ （ＯＣａＨｌ）
ａ ）１５ｇをトルエン（Ｃ，Ｉ（、Ｃ）＋３）８５
ｇ中に溶解させたところほとんど無色の溶液を得た。こ
の溶液をポリエチレンフィルムの耐摩耗性と撥水性とを
向上させる目的で、ポリエチレンフィルムにローラーで
塗布し、大気中で乾燥させたところ、フィルム表面に白
色の細かい粉末が一面に生成し、これは簡単にフィルム
から落ちてしまい、目的を達成することはできなかった
。This m Zirconium tetrabutoxide (Zr (OCaHl)
a) 15 g toluene (C, I (, C) + 3) 85
When dissolved in g, an almost colorless solution was obtained. In order to improve the abrasion resistance and water repellency of polyethylene film, this solution was applied with a roller to polyethylene film and dried in the air, and a fine white powder was formed all over the film surface. It easily fell off the film and failed to achieve its purpose.
１較■）
チタンテトライソプロポキシド（Ｔｉ（ＯＣＪ、）ｍ）
２０ｇをイソプロピルアルコールｃ、Ｈｔｏ８８０ ｇ
に混合させたところ、はとんど無色の溶液が得られた。1 comparison■) Titanium tetraisopropoxide (Ti(OCJ, )m)
20g isopropyl alcohol c, Hto880g
When mixed, a mostly colorless solution was obtained.
この溶液に鏡面研摩した石英ガラスを浸漬し、３０ｍｍ
／ｗｉｎで引き上げたところ、ガラス両面に薄い液膜が
形成された。このガラスを温度２０°Ｃ１相対湿度４０
％の大気中に放置したところ、約１ａｉｎで乾燥したが
、表面はすりガラスのように白色化した。次いで４００
°Ｃに保持した電気炉に挿入し、そのまま３０分間保持
後取り出したところ、表面は粉をふいたようになり、簡
単に手でかき落とすことができた。この粉を集めてＸ線
回折で分析したところ、二酸化チタンの粉末であること
がわかった。A mirror-polished quartz glass was immersed in this solution, and a 30 mm
/win, a thin liquid film was formed on both sides of the glass. This glass is heated at a temperature of 20°C and a relative humidity of 40°C.
% of air, it dried in about 1 ain, but the surface turned white like frosted glass. then 400
When it was inserted into an electric furnace kept at °C and held there for 30 minutes, the surface looked like powder and could be easily scraped off by hand. When this powder was collected and analyzed by X-ray diffraction, it was found to be titanium dioxide powder.
止較Ｍ主
ニオブペンタブトキシドＮｂ（ＯＣＪ、）ｓ３０ｇをｎ
ブタノールＣ４Ｂ９０Ｂ ７０ｇに混合したところ、は
とんど無色の溶液が得られた。この溶液に電解研磨した
厚さ０．３ ｌ１ｔａのＳＯ３３０４ステンレス鋼板を
浸漬し、３０ｍ５／ｗｉｎで引き上げたところ、鋼板上
に薄い液膜が形成された。これを温度２０℃、相対湿度
３５％の大気中に放置したところ、約Ｉ ｌｌｌ１ｎで
乾燥したが、表面には無色鱗片状の細かい箔となって剥
がれ落ち、コーティングすることはできなかった。Stop comparison M main niobium pentabutoxide Nb (OCJ,)s 30g n
When mixed with 70 g of butanol C4B90B, a mostly colorless solution was obtained. When an electrolytically polished SO3304 stainless steel plate with a thickness of 0.3 l1ta was immersed in this solution and pulled up at a rate of 30 m5/win, a thin liquid film was formed on the steel plate. When this was left in the air at a temperature of 20° C. and a relative humidity of 35%, it dried in about 100 ml, but a colorless scale-like fine foil peeled off on the surface and could not be coated.
止較孤土
原料のニオブペンタブトキシドをタンクルペンタブトキ
シドＴａ（ＯＣＪＪｓに変えたほかは比較例３と同一の
方法でＳＯＳ ３０４ステンレス鋼板にコーティングし
たが、鱗片状に剥がれ落ち、皮膜は得られなかった。An SOS 304 stainless steel plate was coated in the same manner as in Comparative Example 3, except that niobium pentatoxide, which was a raw material, was changed to tankle pentatoxide Ta (OCJJs), but it flaked off in the form of scales, and no film was obtained. Ta.
（発明の効果）
この発明の金属酸化物皮膜形成用コーティング液は、金
属アルコキシド類を、不飽和アルコール類溶媒に溶解さ
せてなることによって、アルコキシドの加水分解速度を
制御することができ、その結果遷移金属の酸化物皮膜を
良質にかつ安定して成膜させることができ、その効果は
甚だ大である。(Effects of the Invention) The coating liquid for forming a metal oxide film of the present invention is made by dissolving metal alkoxides in an unsaturated alcoholic solvent, so that the hydrolysis rate of the alkoxides can be controlled, and as a result, It is possible to form a transition metal oxide film of high quality and stably, and the effect is enormous.
Claims (1)
びＴａのうちの１種又は２種以上、Ｒは飽和又は不飽和
の炭化水素基、ｎは上記金属元素の価数によって定まる
整数を示す）で表される１種又は２種以上の金属アルコ
キシド類を、不飽和アルコール類からなる溶媒に溶解さ
せてなる金属酸化物皮膜形成用コーティング液。1. General formula: M(OR)_n (M is one or more of Ti, Zr, Nb and Ta, R is a saturated or unsaturated hydrocarbon group, n is depending on the valence of the above metal element) 1. A coating liquid for forming a metal oxide film, which is obtained by dissolving one or more metal alkoxides represented by (indicating a predetermined integer) in a solvent consisting of an unsaturated alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26524490A JPH04142372A (en) | 1990-10-04 | 1990-10-04 | Coating solution for forming metal oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26524490A JPH04142372A (en) | 1990-10-04 | 1990-10-04 | Coating solution for forming metal oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04142372A true JPH04142372A (en) | 1992-05-15 |
Family
ID=17414535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26524490A Pending JPH04142372A (en) | 1990-10-04 | 1990-10-04 | Coating solution for forming metal oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04142372A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5759251A (en) * | 1996-05-24 | 1998-06-02 | Nihon Parkerizing Co., Ltd. | Titanium dioxide ceramic paint and methods of producing same |
| JP2008231418A (en) * | 2007-02-22 | 2008-10-02 | Kansai Paint Co Ltd | Coating material for forming titanium-zirconium film, method for forming titanium-zirconium film, metal substrate coated with titanium-zirconium film |
-
1990
- 1990-10-04 JP JP26524490A patent/JPH04142372A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5759251A (en) * | 1996-05-24 | 1998-06-02 | Nihon Parkerizing Co., Ltd. | Titanium dioxide ceramic paint and methods of producing same |
| CN1103802C (en) * | 1996-05-24 | 2003-03-26 | 日本帕卡濑精株式会社 | Titanium dioxide ceramic paint and method of producing same |
| JP2008231418A (en) * | 2007-02-22 | 2008-10-02 | Kansai Paint Co Ltd | Coating material for forming titanium-zirconium film, method for forming titanium-zirconium film, metal substrate coated with titanium-zirconium film |
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